JP4248475B2 - Ionic liquid electrolyte gas sensor - Google Patents

Description

  The present invention relates to a material for a gas sensor using a liquid electrolyte.

As an electrochemical gas sensor, one using a solid electrolyte such as a proton conductor (Patent Document 1) or one using a liquid electrolyte such as sulfuric acid (Patent Document 2) is used. In the case of using a proton conductor, the proton conductor does not function as an electrolyte at low humidity, so it is necessary to replenish water vapor from a water reservoir. When the water in the water reservoir is exhausted, the gas sensor reaches the end of its life, so a large water reservoir is required. In order to reduce the water vapor lost from the water reservoir, there is a limit to the amount of gas that can be introduced into the working electrode on the proton conductor, making it difficult to detect low concentration gas. In addition, in a gas sensor using a liquid electrolyte, in order to supplement the loss of the electrolyte, a liquid reservoir for the electrolytic solution is necessary, and the gas sensor is also increased in size. Also, electrolytes such as sulfuric acid are dangerous if they leak out. Although sulfuric acid is a substance having a low melting point, it decomposes at, for example, 100 ° C. or higher, so a gas sensor cannot be used, and the operating temperature on the high temperature side is limited.
USP5650,054 USP 5126,035

  A basic object of the present invention is to provide a compact electrochemical gas sensor that does not require a liquid reservoir.

The ionic liquid electrolyte gas sensor according to the present invention does not include a liquid reservoir such as a water reservoir or a liquid electrolyte reservoir, supports the ionic liquid on a porous separator, and at least a pair of the separator having a working electrode and a counter electrode. By providing a metal plate on each side of the pair of electrodes opposite to the separator, and by providing means for pressing the metal plates toward the pair of electrodes, These electrodes are connected so as to obtain ionic conductivity.

An ionic liquid is an ionic substance that is in a liquid state at room temperature, and is an organic salt that melts at room temperature.For example, cations include butylpyridium ion, ethylmethylimidazolium ion, and hexyltrimethylammonium ion. These are +1 valent organic ions, and the anions include BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , and PF ₆ ⁻ . In addition, the combination of a cation and an anion can be changed suitably.

Preferably , as the metal plate, a plate-like portion at the bottom of the metal can and a plate-like portion at the bottom of the sealing body are used, and the separator, the working electrode, and the counter electrode are sandwiched between these, By caulking the can and the sealing body, the working electrode and the counter electrode are pressed from the sealing body and the metal can toward the separator.

  Preferably, a porous conductive film is provided between each electrode and the corresponding metal plate.

  Preferably, at least one of the pair of electrodes is brought into contact with the separator via a proton or hydroxide ion conductive solid electrolyte membrane.

  Ionic liquids are liquid over a wide temperature range and are flame retardant because they have no vapor pressure. Since the ionic liquid is not lost by evaporation, a liquid reservoir for replenishing the electrolyte is unnecessary, and since the conductivity does not depend on humidity or water vapor, a water reservoir for humidification is also unnecessary. Therefore, a compact gas sensor without a liquid reservoir can be obtained. In the case of a gas sensor having a water reservoir for humidification, if the water is lost from the water reservoir, the life of the sensor is exhausted, but the present invention has no such limitation. When a water reservoir is used, it is necessary to limit the supply of gas to the working electrode in order to limit the loss of water vapor. By the way, since the ionic liquid has a high conductivity of about 10 to 1000 S / cm and it is not necessary to consider the loss of water vapor, in the present invention, it is necessary to reduce the supply of gas to the working electrode and reduce the output. Absent.

  Since the ionic liquid is a liquid in a wide temperature range and exhibits high conductivity, the gas sensor can be used in a wide temperature range from a low temperature to a high temperature. For example, the gas sensor can be used in a temperature range of about −40 ° C. to 100 ° C. or more. Furthermore, since the decomposition voltage is high, it is possible to apply a large voltage between the working electrode and the counter electrode, and it is possible to detect a hardly decomposable gas such as methane.

Here, when a metal plate is provided on the side opposite to the separator of the working electrode and the counter electrode, and these metal plates are pressed toward the separator side, the connection between the metal plate and the working electrode or the counter electrode and the working electrode or the counter electrode and the separator is established. Can be easily obtained.
Furthermore, if the separator, working electrode and counter electrode are accommodated between the metal can and the sealing body, and the metal can and the sealing body are caulked, the output can be easily taken out with a simple structure. A gas sensor with reliable connection between members can be obtained.

When a porous conductive film is provided between one electrode and one metal plate or between the other electrode and the other metal plate, gas distribution to the working electrode and the counter electrode is facilitated. If the conductive film is made hydrophobic, water can be prevented from entering the electrode and the separator during dew condensation.
When a proton conductive or hydroxide ion conductive solid electrolyte membrane is sandwiched between at least one electrode and the separator, hydrogen ions and hydroxide ions necessary for the electrode reaction can be transported to the ionic liquid. For this reason, even if the ionic liquid is brought into direct contact with the electrode, the electrode reaction proceeds efficiently even if the ionic liquid does not serve as a conduction path for hydrogen ions or hydroxide ions related to the electrode reaction.

The inventor has also found that, when left at a high temperature such as 70 ° C. for a long time, the ionic liquid flows and corrodes the solid electrolyte membrane, and as a result, the activity of the counter electrode is lowered and the sensitivity may be lowered. I found it. Such a phenomenon is not usually a problem, but if the counter electrode is a metal oxide electrode such as MnO ₂ , ZnO, NiOOH, etc., the decrease in sensitivity due to experiencing high temperatures can be reduced.

  In the following, an optimum embodiment for carrying out the present invention will be shown.

  1 to 12 show an embodiment and its modifications. In addition, in each modification, it is the same as that of the Example of FIG. 1 except the point pointed out especially, and the same term and the same code | symbol represent the same thing. FIG. 1 shows a gas sensor 2 according to an embodiment, 4 is a sensor body, 5 and 6 are porous hydrophobic conductive films, 8 is a diffusion control plate, and the diffusion holes 10 through the hydrophobic conductive film 5. The gas is supplied to the working electrode side of the sensor body 4. A sealing body 12 supplies the gas introduced from the opening 14 to the diffusion control plate 8 side from the opening 16. A filter material 18 is accommodated in the sealing body 12 to remove toxic gases and the like, and activated carbon, zeolite, silica gel or the like is used. 20 is a metal housing and 22 is a gasket.

  For example, stainless steel or the like is used for the metal housing 20 and the sealing body 12, and the hydrophobic conductive film 6 is located between the sensor body 4 and the bottom surface of the metal housing 20 to electrically connect them. Oxygen or the like is supplied to the counter electrode side of the main body 4. The hydrophobic conductive film 5 electrically connects the sensor body 4 and the sealing body 12 and supplies gas from the diffusion hole 10 to the working electrode side of the sensor body 4. For the hydrophobic conductive films 5 and 6, for example, carbon paper or carbon sheet having a thickness of about 10 to 40 μm is treated with PTFE (polytetrafluoroethylene) to be hydrophobized. The hydrophobic conductive films 5 and 6 distribute gas to the working electrode and the counter electrode, and prevent condensation on the working electrode and the counter electrode in high humidity. Further, when detecting a reducing gas such as CO, hydrogen, or alcohol, the hydrophobic conductive film 6 on the counter electrode side serves as a buffer for supplying oxygen to the counter electrode. If condensation is not particularly problematic, a simple porous conductive film may be used instead of the hydrophobic conductive films 5 and 6. For example, a carbon sheet or carbon paper that has not been treated with PTFE can be used as a porous conductive film.

  As a result, the metal housing 20 becomes an external terminal on the counter electrode side, and the outer surface of the sealing body 12 becomes an external terminal on the working electrode side. The sealing body 12 and the metal housing 20 are insulated by the gasket 22, and the connection from the sealing body 12 to the metal housing 20 through the sensor body 4 is maintained by the pressing force of the gasket 22. Here, the diffusion control plate 8 is a thin plate of stainless steel or titanium, but may be a gas selective permeable membrane or the like. Further, the gas sensor of the present invention does not require a water reservoir or a liquid reservoir.

  In the embodiment of FIG. 1, the working electrode is disposed on the sealing body 12 side and the counter electrode is disposed on the metal housing 20 side. However, these arrangements may be reversed. In the gas sensor 32 of FIG. 2, a diffusion hole 34 is provided in the metal housing 21 to supply gas to the working electrode, and the sealing body 13 is airtight without an opening. And when it is necessary to provide a filter, it arrange | positions outside the diffusion hole 34, for example.

  FIG. 3 shows the sensor body 4 and the surrounding arrangement. Reference numeral 40 denotes a porous separator that uses a disk such as glass wool or silica gel, a porous PTFE sheet, etc., as long as it can hold an ionic liquid, and has a heat resistance so that the gas sensor can operate even at high temperatures. A high one is preferred. The separator 40 accommodates and holds the ionic liquid and has a thickness of 10 μm to 1 mm, for example. 42 is a working electrode, for example, a film-like electrode in which a mixed catalyst of Pt and Ru is supported on carbon, and a proton conductor such as Nafion (Nafion is a registered trademark of DuPont) and a binder such as PTFE are added. is there. The counter electrode 43 is an electrode similar to the working electrode 42 except that Pt-supported carbon is used as a catalyst, and the electrodes 42 and 43 may be thin film electrodes such as Pt. The working electrode 42 and the counter electrode 43 have a thickness of about 1 to 40 μm, for example, and are disposed on both front and back surfaces of the separator 40 via proton conductor films 44 and 44 having a thickness of about 1 to 40 μm. As the proton conductor film 44, a Nafion film or the like may be used, and a hydroxide ion conductor or the like may be used instead of the proton conductor.

  In the gas sensor 52 of FIG. 4, the airtight film 54 is used to prevent hydrogen from flowing from the hydrophobic conductive film 5 side to the counter electrode side of the sensor body 4. This increases the sensitivity to hydrogen, which has a low molecular weight and is likely to wrap around the counter electrode. As the airtight film 54, an adhesive sheet or the like in which a portion corresponding to the hydrophobic conductive film 5 is cut out is used.

  When the operation of the sensor body 4 is shown, a gas such as hydrogen or CO supplied from the hydrophobic conductive film 5 to the working electrode 42 is decomposed by the electrode catalyst and changed to hydrogen ions. The ions move from the proton conductor mixed in the working electrode 42 into the ionic liquid held in the separator 40 through the proton conductor film 44. On the counter electrode 43 side, hydrogen ions move from the ionic liquid of the separator 40 to the proton conductor of the counter electrode 43 through the proton conductor film 44, and are combined with oxygen by the electrode catalyst to change into water vapor or the like. To do. A current generated thereby is detected as a current from the sealing body 12 to the metal housing 20.

  It is unclear how protons move in the ionic liquid, but in the examples, outputs proportional to the CO concentration and hydrogen concentration were obtained in a wide temperature range of about -10 ° C to 60 ° C. Further, the characteristics of the gas sensor were stable, and no change was observed even after about 20 weeks from the production.

The characteristics of the gas sensor of FIG. 1 are shown in FIGS. A porous PTFE sheet (thickness 20 μm) was used as a separator, and an ionic liquid composed of ethylmethylimidazolium ions and (CF ₃ SO ₂ ) ₂ N ^- ions was used. An output obtained by amplifying the current flowing between the sealing body and the metal housing is shown as an output, and the output is adjusted so that the output is 1 V when the current between the two electrodes is zero.

  5 to 7 show the characteristics of a low concentration gas sensor, in which the sensor output is increased by increasing the diameter of the diffusion hole. The output is proportional to the gas concentration and can be detected even with about 1 ppm of CO or about 1 ppm of ethanol.

  8 to 10 show the 20-week aging characteristics with respect to 30 to 1000 ppm of CO. In this example, the diffusion hole is made small so that the output is not saturated even at about 1000 ppm. Further, the standing atmosphere is room temperature and the relative humidity is about 40%. As is apparent from FIGS. 8 to 10, the sensor characteristics do not change greatly even after being left for 20 weeks.

  FIG. 11 shows the sensor output for 400 ppm CO in the range of −10 ° C. to 60 ° C. The type of sensor is the same as in FIG. From -10 ° C to 60 ° C, the sensor output changes monotonously with temperature, and gas can be detected in a wide temperature range.

FIG. 12 shows a tripolar gas sensor 62 provided with a reference electrode. Reference numeral 63 denotes a working electrode, which is a (Pt + RuO ₂ ) / C + PTFE + proton conductor electrode laminated with a proton conductor film or the like. 40 is a separator containing an ionic liquid, 64 is a working electrode, and 65 is a reference electrode. The counter electrode 64 is obtained by forming an electrode film such as Pt / C + PTFE + proton conductor on a thin proton conductor film. Reference numeral 66 denotes an insulating terminal plate, which is provided with a conductive plate 68 corresponding to the counter electrode 64 and a conductive plate 70 corresponding to the reference electrode 65. Otherwise, the working electrode 63 and the counter electrode 64 may be provided on the same side of the separator 40, for example, concentrically.

  13 and 14 show a gas sensor of a fourth modification. The sensor body 4 and the hydrophobic conductive films 5 and 6 are the same as those in the embodiment. These are sandwiched between a pair of metal plates 72, 73, and synthetic resin films 76, 77 are arranged above and below them, and the synthetic resin films 76, 77 are thermocompression bonded. Then, the contraction force at the time of thermocompression bonding provides a connection from the metal plate 72 to the metal plate 73, and gas is supplied to the working electrode from the opening 78 provided in the synthetic resin film 76 through the diffusion hole 10. Furthermore, when the leads 74 and 75 protruding from the synthetic resin films 76 and 77 are provided on the metal plates 72 and 73, the output can be easily taken out. The synthetic resin films 76 and 77 are made of, for example, a thermoplastic synthetic resin film and are airtight, for example. Furthermore, the diameters of the sensor body 4, the hydrophobic conductive films 5, 6 and the metal plates 72, 73 are, for example, about 5 to 20 mm.

  FIG. 15 shows a fifth modification. In this modification, the sensor body 4 and the hydrophobic conductive films 5 and 6 are sandwiched between the metal plate 82 with the diffusion hole 10 and the metal plate 83. For example, a ring 84 of thermoplastic resin is provided so as to cover the sensor body 4 sandwiched with the side surfaces of the circular metal plates 82 and 83, the side surfaces of the hydrophobic conductive films 5 and 6, and the outer peripheral portions of the metal plates 82 and 83. Is provided. In manufacturing the gas sensor, the sensor body 4, the hydrophobic conductive film 5, 6, and the metal plates 82 and 83 are set in a ring made of thermoplastic resin, and the ring is heated. The thermoplastic resin 84 contracts by heating, and the pressure which presses the metal plate 82 to the hydrophobic conductive film 5 side and the metal plate 83 to the hydrophobic conductive film 6 side is obtained, and the connection between these is ensured. In addition, the metal plates 82 and 83 become external terminals.

FIG. 16 shows an example in which a metal oxide electrode is used as a counter electrode. The metal oxide electrode 93 is brought into contact with the separator 40 supporting the ionic liquid, and the proton conductor film 44, the working electrode 42, and the hydrophobic conductive film 5 are laminated on, for example, the opposite surface of the metal oxide electrode 93 of the separator. . The material, arrangement, and operation of the separator 40, the ionic liquid, the proton conductor film 44, the working electrode 42, and the hydrophobic conductive film 5 are the same as those of the gas sensor of FIG. The proton conductor film 44 may not be provided, but in that case, the response speed to the gas is slightly reduced. The metal oxide electrode 93 is obtained by supporting a metal oxide such as MnO ₂ , ZnO, or NiOOH on a conductive and preferably porous support such as a hydrophobic conductive film. It is good to knead the paste on the support. The metal oxide electrode 93 is preferably an electrode to which no solid electrolyte is added, and it is preferable that no solid electrolyte membrane is interposed between the metal oxide electrode 93 and the separator 40. The metal oxide electrode 93 generates a reactant such as water by reducing ionic species such as hydrogen ions transported from the ionic liquid. In the examples, a MnO ₂ electrode was used as the metal oxide electrode 93, and as a high concentration gas sensor having a large diffusion hole as in the case of FIG. 8, etc., aging was performed at 70 ° C. for 4 weeks to evaluate high temperature durability. .

FIGS. 17 and 18 show the characteristics (four each) of the sensor using metal oxide electrodes, FIG. 17 shows the initial characteristics, and FIG. 18 shows the characteristics after being left at 70 ° C. for 4 weeks. 19 and 20 show the characteristics of the gas sensor (for high concentration) having the structure of FIG. 3, FIG. 19 shows the initial characteristics, and FIG. 20 shows the characteristics after being left at 70 ° C. for 4 weeks. Even if the counter electrode was MnO ₂ and the proton conductor film 44 was not interposed between the counter electrode and the separator, the initial characteristics were the same. When the temperature of 70 ° C. was experienced for 4 weeks, the sensitivity of the gas sensor of FIG. 3 decreased as shown in FIGS. 19 to 20, but the sensitivity of the sensor using MnO ₂ as a counter electrode material was not changed. Further, in the gas sensor for low concentration with a small diffusion hole, the influence of 70 ° C. experience was smaller even in the gas sensor of FIG.

When the sensor that has experienced 70 ° C. for 4 weeks is disassembled, the proton conductor film 44 turns yellow, which means that the ionic liquid penetrates the proton conductor film 44 and causes the proton conductor to surround the sulfonic acid group. It suggests that it was disassembled at such a position. This corresponds to the fact that the sensitivity of the sensor of FIG. 16 in which no proton conductor is used for the counter electrode did not decrease. Further, the proton conductor on the working electrode side had little influence on the characteristics even when it was decomposed by the ionic liquid (FIGS. 17 and 18). Although the characteristics of the MnO ₂ counter electrode are shown here, the same applies to other metal oxide counter electrodes such as NiOOH and ZnO.

By using the liquid electrolyte as an ionic liquid, the following effects can be obtained.
(1) No water vapor is required to obtain conductivity, and there is no vapor pressure, so it is not lost. For this reason, a liquid reservoir is unnecessary and a gas sensor can be made compact.
(2) There is no limit of life due to the loss of water in the liquid reservoir, and the amount of gas introduced into the working electrode can be increased, so even low concentration gas can be detected.
(3) Since it does not solidify to about −40 ° C. and can be used as a conductor up to about 300 ° C., the operating temperature range is wide.
(4) Since it does not decompose even when a voltage up to about 4V is applied, it is possible to easily detect methane by applying a large bias voltage.
(5) The hydrophobic conductive films 5 and 6 can prevent dew condensation on the separator and the electrode when the sensor is left in a dewed atmosphere, and facilitate gas distribution to the electrode.
(6) Proton transfer is facilitated between the electrode and the ionic liquid by mixing a proton conductor into the electrode and providing a proton conductor film between the electrode and the separator. Instead of the proton conductor, a hydroxide ion conductor may be added to the electrode, or a hydroxide ion conductor film may be provided between the electrode and the separator.

Sectional view of the gas sensor of the embodiment Sectional view of the first modified gas sensor Sectional drawing from the separator in the examples to the upper and lower hydrophobic conductive films Sectional drawing of the gas sensor of the 2nd modification The characteristic diagram of the gas sensor of the example shows the output to CO 0.3 to 30 ppm The characteristic diagram of the gas sensor of the example shows the output to 0.3 to 30 ppm of H2. The characteristic diagram of the gas sensor of the example shows the output to ethanol H2 0.3 to 30 ppm Diagram showing initial characteristics of gas sensor for high concentration The figure which shows the characteristic after 5 weeks from the measurement of FIG. The figure which shows the characteristic after 20-week progress from the measurement of FIG. The figure which shows the temperature characteristic in -10 degreeC-60 degreeC of the gas sensor of an Example. The figure which decomposes | disassembles and shows the gas sensor of a 3rd modification. Sectional drawing of the gas sensor of a 4th modification The top view of the gas sensor of the 4th modification Sectional drawing of the gas sensor of a 5th modification Sectional drawing of the circumference | surroundings of the separator in the gas sensor of a 6th modification It is a characteristic view of the gas sensor of the 6th modification, and shows the output to CO 30-1000ppm before high temperature experience It is a characteristic view of the gas sensor for high concentration of an example, and shows an output to CO 30 to 1000 ppm after being left at 70 ° C. for 4 weeks. It is a characteristic view of the gas sensor for high concentration of the example, and shows an output to 30 to 1000 ppm of CO before high temperature experience. In the characteristic figure of the gas sensor of the 6th modification, it shows the output to CO 30-1000 ppm after leaving at 70 ° C for 4 weeks.

Explanation of symbols

2, 32, 52, 62 Gas sensor 4 Sensor body 5, 6 Hydrophobic conductive film 8 Diffusion control plates 10, 34 Diffusion holes 12, 13 Sealing bodies 14, 16 Opening 18 Filter material 20, 21 Metal housing 22 Gasket 40 Separator 42 Working electrode 43 Counter electrode 44 Proton conductor film 54 Airtight film
63 Working electrode 64 Counter electrode 65 Reference electrode 66 Terminal plate 68, 70 Conductive plate 72, 73 Metal plate 74, 75 Lead 76, 77 Synthetic resin film 78 Opening 82, 83 Metal plate 84 Thermoplastic resin ring 93 Metal oxide electrode

Claims (4)

The porous separator supports the ionic liquid, and at least a pair of electrodes composed of a working electrode and a counter electrode is connected to the separator, and a metal plate is provided on each side of the pair of electrodes opposite to the separator. By providing means for pressing these metal plates toward the pair of electrodes, the ion plate is connected so as to obtain ionic conductivity between the pair of electrodes, and further has no liquid reservoir. Liquid electrolyte gas sensor. As the metal plate, a plate-like portion at the bottom of the metal can and a plate-like portion at the bottom of the sealing body are used, and the separator, the working electrode, and the counter electrode are sandwiched between the metal can and the sealing hole. The ionic liquid electrolyte gas sensor according to claim 1 , wherein the working electrode and the counter electrode are pressed from the sealing body and the metal can toward the separator by caulking the body. The ionic liquid electrolyte gas sensor according to claim 1 or 2, wherein a porous conductive film is provided between each of the electrodes and the corresponding metal plate. The ionic liquid electrolyte gas sensor according to any one of claims 1 to 3 , wherein at least one of the pair of electrodes is brought into contact with the separator via a proton or hydroxide ion conductive solid electrolyte membrane. .

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