JP3013874B2 - Diaphragm-type gas sensor device and its operation method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a diaphragm type gas sensor used for measuring the concentration of a gas component. More specifically, the present invention relates to a diaphragm-type gas sensor device widely used for measuring the purity of various industrial gases, preventing explosion and fire, and preventing poisoning of toxic gas in ships, manholes, and tunnels.

[0002]

2. Description of the Related Art A diaphragm type gas sensor is a sensor that guides a gas component to be detected onto an electrode having a catalytic action through a diaphragm and reduces or oxidizes the gas to output a voltage or a current corresponding to the gas concentration. Since it is small, lightweight, operates at normal temperature and pressure, has high reliability and is relatively inexpensive, it is widely used for industrial and medical purposes.

[0003] A general configuration of a diaphragm type gas sensor which has been widely put into practical use conventionally is as shown in FIG. The operation principle of the diaphragm type gas sensor will be described with reference to FIG. The gas that has passed through the diaphragm (1) that selectively permeates the gas to be detected and limits the amount of permeation to an appropriate value is subjected to an electrochemical reduction or oxidation reaction of the gas via the electrolyte (3). A counter electrode (4) whose material is selected so as to favor the reaction between the working electrode (2) carrying an effective catalyst and the gas;
Causes an inherent electrochemical reaction of the gas. The potential of the working electrode is maintained at an appropriate potential for the reaction by an external circuit with respect to the reference electrode (5), if necessary. At this time, a current corresponding to the reaction amount flows between the working electrode (2) and the counter electrode (4).
By guiding the gas to the outside through (7), the gas concentration can be detected.

At this time, the counter electrode causing an oxidation-reduction reaction with the gas is consumed according to the reaction amount, that is, the gas concentration, the reaction time, the reaction temperature, and other conditions, and the life of the sensor is eventually exhausted. In addition, the product formed by the oxidation-reduction reaction between the gas and the counter electrode is removed outside the system by dissolving in the electrolytic solution, etc., and the reaction continues continuously. When the saturation is reached, the continuation of the reaction is hindered due to the deposition of the product on the electrode and the like, and the life of the sensor also ends.

In order to explain the operation more practically, an oxygen sensor which is a typical example of this type of sensor will be described. The principle of operation of the sensor is as follows.Oxygen that has passed through a diaphragm that selectively permeates oxygen and limits the amount of permeation to match the electrode reaction is electrochemically reduced at the working electrode made of a noble metal catalyst, The following electrochemical reaction occurs between the liquid and the counter electrode made of lead through the liquid.

[0006] 1. When the electrolytic solution is acidic Cathode reaction: O ₂ + 4H ⁺ + 4e ⁻ → 2H ₂ O Anode reaction: 2Pb + 2H ₂ O → 2PbO + 4H ⁺ +
4e ^— total reaction: 2Pb + O ₂ → 2PbO When the electrolytic solution is alkaline Cathode reaction: O ₂ + 2H ₂ O + 4e ⁻ → 4OH ⁻ Anode reaction: 2Pb + 4OH ⁻ → 2PbO + 2H ₂ O
+ 4e ^- total reaction: 2Pb + O ₂ → 2PbO In the case of an oxidizing gas such as oxygen, the reaction of oxygen itself causes a reduction reaction, so that the working electrode acts electrochemically as a cathode, and the reaction amount of oxygen, that is, the oxygen concentration is It is detected as the value of the cathode current. The charge carrier varies depending on whether the electrolytic solution is acidic or alkaline, but in any case, a cathode current corresponding to the oxygen concentration is generated.

FIG. 2 shows current and voltage characteristics of such a sensor. When the relationship between the cathode potential and the anode potential is in the oxygen reduction reaction region, oxygen is reduced at the working electrode, which is the cathode, and current flows.However, when the supply of oxygen to the working electrode is limited by the diaphragm, the diaphragm is The total amount of diffused and transmitted oxygen is reduced, the reduction current reaches saturation at a certain value, and the limiting current region shown in FIG. 2 appears.
In the limit current region, the current value is constant even if the potential difference between the cathode and the anode changes. On the other hand, the limit current value changes depending on the oxygen concentration, and becomes small when the oxygen concentration is low and becomes large when the oxygen concentration is high. The three graphs (A), (B), and (C) in FIG. 2 illustrate changes in the limiting current value when the oxygen concentration is a, b, and c%, respectively, where the oxygen concentration is a>b> c. It is. Since this limit current value is accurately proportional to the oxygen concentration, the oxygen concentration can be detected. In order to maintain the potential difference between the cathode and the anode in the limit current region, the potential of the working electrode is kept constant by an external electric circuit with reference to the reference electrode, or the natural electrode is formed by appropriately combining the anode and cathode electrode materials. An electric potential may be used. Generally, the former is called a constant potential electrolytic sensor, and the latter is called a galvanic cell sensor, which is widely used.

In the case of an oxygen sensor, lead as a counter electrode is converted into lead oxide by an oxidation reaction, but reacts with an electrolyte component and is dissolved in the electrolyte in the form of a salt or a hydroxide. Therefore, when the concentration of the salt or hydroxide in the electrolyte is saturated and the lead oxide no longer dissolves, the oxidation reaction of lead does not proceed and the life of the sensor is exhausted. Also, when lead is consumed and disappears, the reaction as the sensor does not occur, and the life of the sensor is exhausted.

The principle is the same for other gas components other than oxygen. In addition to oxygen, an oxidizing gas such as ozone is detected as a cathode reaction, and a reducing gas such as hydrogen, carbon monoxide, and hydrogen sulfide is detected. Detected as an anodic reaction. In order to more practically explain the operation of the sensor of the reducing gas component, an example of a hydrogen sensor will be described.

The principle of operation of the sensor is as follows. Hydrogen that has passed through a diaphragm that selectively permeates hydrogen and limits the amount of permeation to match the electrode reaction is electrochemically oxidized at a working electrode made of a noble metal catalyst. Then, the following electrochemical reaction occurs with the counter electrode made of lead dioxide through the electrolytic solution.

Anode reaction: H ₂ → 2H ⁺ + 2e ⁻ Cathode reaction: PbO ₂ + 2H ⁺ + 2e ⁻ → PbO + H
₂ O total reaction: H ₂ + PbO ₂ → PbO + H ₂ O In the case of a reducing gas such as hydrogen, the reaction of hydrogen itself causes an oxidation reaction, so that the working electrode electrochemically acts as an anode, and the reaction amount of hydrogen. That is, the hydrogen concentration is detected as the value of the anode current. As in the case of the oxygen sensor, when the potential between the anode and the cathode is kept at a constant value, the limiting current value and the hydrogen concentration value show a good correlation, and a hydrogen sensor is obtained.

In the case of such a hydrogen sensor, lead dioxide as a counter electrode is converted into lead oxide by a reduction reaction, but reacts with components of the electrolytic solution and is dissolved in the electrolytic solution in the form of a salt. Therefore, when lead dioxide on the counter electrode is consumed and all lead oxide is formed, no reaction occurs and the life of the sensor is exhausted. Further, when the salt in the electrolyte is saturated and the lead oxide is not dissolved, the reduction reaction of the lead dioxide does not proceed, and the life of the sensor also ends.

The sensor output thus obtained is usually amplified by an external circuit and processed into an appropriate signal form such as a concentration display or a meter indication.

[0014]

The diaphragm type gas sensor is excellent as a means for electrically measuring various gas concentrations, but its output is obtained by reacting a gas component with a sensor electrode material. In addition, there is a life due to consumption of the electrode material. Further, when a product generated by the reaction is dissolved in the electrolytic solution, there is an output fluctuation and a life due to a change in the composition of the electrolytic solution.

Therefore, when such a diaphragm type gas sensor is usually used, it is necessary to check and calibrate the sensor output before use, and even when the gas sensor is used continuously for a long period of time, the accuracy may be reduced. In order to maintain reliability and reliability, it is necessary to periodically interrupt the measurement and calibrate or replace the sensor.

Furthermore, when the sensor is not easily replaced because it is disposed inside a mechanical device or building equipment, or when used for equipment having a very long maintenance inspection interval, a very long sensor life is required.

In order to solve such a problem, the life of the diaphragm type gas sensor may be extended by increasing the amount of the electrode material and the amount of the electrolytic solution. However, the manufacturing cost of the sensor is increased and the shape of the sensor is increased. Therefore, the characteristics of this type of sensor, which is small, lightweight, and relatively inexpensive, are impaired. In addition, if the size is not changed, the life span that is extended becomes small.

[0018]

In order to solve the above-mentioned problems, a diaphragm type gas sensor device according to the present invention comprises a diaphragm type gas sensor, a switch section for turning on and off a sensor detection current circuit, and an on state of the switch section. The ratio TON / TOFF between the time TON and the time TOFF in the OFF state is 1/3 or more, 4 /
And a switch control unit for controlling the switch unit so as to be 1 or less.
By controlling the switch unit so as to fall within the above range, the diaphragm type gas sensor device is operated intermittently.

[0019]

The diaphragm type gas sensor uses a current caused by a reduction or oxidation reaction of gas components as a means for detecting a gas concentration. Conversely, an anode and a cathode, that is, an electrode between a working electrode and a counter electrode are electrically connected. Only when connected and a current flows, a reduction or oxidation reaction occurs and functions as a sensor.

Therefore, if the electrical connection between the working electrode and the counter electrode is cut off from the outside, no reduction or oxidation reaction of the gas components occurs, and no consumption of the electrodes and no dissolution of the product in the electrolyte occurs.

On the other hand, in normal gas concentration measurement, the output of the sensor is not always measured without a break, but the output of the sensor is taken into a measurement circuit at a certain sampling period, converted into a concentration and measured. I have.
This is to reduce the power consumption of the circuit and to reduce the effects of external noise.However, this type of sensor utilizes the diffusion of gas in the diaphragm and the electrolyte, so the response speed of the sensor is reduced. Is much slower than the operation speed of the circuit that processes the electric signal, so that even if the sensor output is taken in periodically, the measurement can be performed at a speed sufficiently matching the response speed of the sensor.

From these facts, it is not necessary for the diaphragm type gas sensor to always function as a sensor, and it affects the response speed of the sensor and the sampling period of the measurement circuit which are determined by the diffusion speed of gas in the diaphragm and the electrolyte. Even if the sensor is operated intermittently within the range, there is no inconvenience in measurement. In addition, when the electrical connection between the working electrode and the counter electrode of the sensor is cut off, the function of the sensor is stopped, and the electrode is not consumed and the reaction product is not dissolved in the electrolyte.

Therefore, by intermittently driving the sensor at an arbitrary cycle, the life can be greatly extended without impairing the excellent characteristics of the conventional diaphragm type gas sensor. In this case, in order to greatly extend the life while maintaining high detection accuracy, the ratio TON / TOFF of the time TON when the switch is on and the time TOFF when the switch is off is 1 by the switch control unit. It is necessary to control the switch unit so that it is not less than / 3 and not more than 4/1, and TON / TOFF is 1
If it is less than / 3, the detection accuracy is deteriorated, and if it exceeds 4/1, it is difficult to greatly extend the life.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a diaphragm type gas sensor device according to the present invention will be described in detail with reference to preferred drawings.

Embodiment 1 FIG. 3 is a schematic diagram of a diaphragm type gas sensor device according to the present invention. Here, the oxygen gas sensor will be described in detail as a diaphragm type gas sensor.

In FIG. 1, reference numeral 2 denotes a working electrode, which is a gold or silver catalyst material. 4 is a counter electrode made of lead. Reference numeral 1 denotes a membrane, which is a 25 μm-thick nonporous film made of a copolymer of tetrafluoroethylene and hexafluoropropylene. Reference numeral 3 denotes an electrolytic solution, which is an acidic aqueous solution having a composition of 6 mol / L acetic acid, 5 mol / L potassium acetate, and 0.1 mol / L lead acetate. Reference numerals 6 and 7 denote external lead wires, and 8 denotes a switch circuit as a switch unit.

10 is a pulse generator, 11 is a frequency divider, 12 is a monostable multivibrator circuit, and the pulse generator 10, the frequency divider 11, and the monostable multivibrator circuit 12 are switch control units. .

The response speed of this sensor to changes in gas concentration was about 30 seconds. Oxygen reaching the working electrode via the diaphragm 1 causes an electrochemical reaction with the counter electrode 4, and a current corresponding to the oxygen concentration flows between the working electrode 2 and the counter electrode 4. Insoluble lead oxide is produced as a reaction product at this time, but after the reaction, it reacts with an acetic acid component in the electrolytic solution to become water-soluble lead acetate and is dissolved in the electrolytic solution. Therefore, the point at which the concentration of lead acetate in the electrolyte reaches saturation is the sensor life. Also, the sensor life will be the same if the total amount of lead on the counter electrode has reacted.

The external lead wires 6 and 7 of this oxygen sensor
A switch circuit 8 composed of a semiconductor analog switch element having bidirectional characteristics was connected, and the element was turned on / off at appropriate intervals to conduct / cut off the output current of the sensor, that is, the current due to the reduction reaction of oxygen. The on / off control of the semiconductor analog switch element was performed as follows. A high-frequency pulse of about 4 MHz is oscillated by a pulse generator, which is adjusted to an appropriate value Tc as a cycle for turning on / off the sensor current using a frequency divider, and further turned on / off by a monostable multivibrator circuit A control signal in which the ON / OFF time ratio TON / TOFF was adjusted by the control circuit was obtained. This signal was input to a semiconductor analog switch element, and conduction / cutoff control of the sensor current was performed.

The sensor current is turned on / off at appropriate intervals.
The circuit for turning off is not limited to the method shown in FIG. 3, but may be another circuit using a microcomputer or a sequencer, for example. Further, the OFF resistance of the semiconductor analog switch element of the present embodiment is a resistance value of 7 Mohm or more, but in order to obtain the effect of the present invention, a value multiplied by the sensor output current, that is, between the cathode and the anode shown in FIG. It is sufficient that the potential difference is equal to or greater than a resistance value that exceeds the limit current region. In this embodiment, about 100 kOhm is enough to obtain the effect of the invention.

Further, here, a semiconductor analog switch element is used as the switch section, but the present invention is not limited to this.

In this case, a waveform as shown in FIG. 4 was obtained as a sensor output for a certain oxygen concentration. At the moment when the semiconductor analog switch was turned on and the lead wire working electrode and the counter electrode of the sensor were electrically connected, the output current of the sensor showed a steep rise and exhibited a characteristic that reached an equilibrium value with time. This equilibrium value ig is considered to be appropriate as the output value of the sensor at that gas concentration.

Next, in order to check the accuracy of the oxygen sensor which has performed such control, purity is 99.99 as zero gas.
% Or more of nitrogen gas, purity 99.99% as span gas
Dry air (oxygen 20.
9%) in sequence and the output of the oxygen sensor was measured. Further, the intermittent cycle (TC) of the oxygen sensor output, the sensor current conduction time (TON), and the cutoff time (TOFF) are changed.
We investigated how those values affect the measurement accuracy. The detection accuracy of the oxygen sensor is measured by measuring the equilibrium value of the sensor current at each gas concentration and comparing the value for the dry air calculated from the values for the zero gas and span gas with the actually measured value when the dry air is actually flowed. I asked.
Table 1 shows the obtained results. Further, the consumption rate of the counter electrode (Pb) and the production rate of the reaction product (PbO) when the sensor is driven under each condition, and the extension rate of the sensor life associated therewith are determined by continuously driving the sensor current without interrupting the sensor current. 1.00.

[0034]

[Table 1] Tests # 1 to # 5 in Table 1 indicate the intermittent cycle of the sensor current (TC
), That is, the result when the intermittent cycle is fixed to 0.01 second and the ratio TON / TOFF of the conduction time (TON) and the interruption time (TOFF) is changed. Usually, the detection accuracy of this type of gas concentration measuring instrument is said to be ± 2%, but from the results of Tests # 2 to # 5, this detection accuracy can be obtained.
It can be seen that F is 1/3 or more. TON / TOFF is 1
In test # 1 of / 4, the detection accuracy was deteriorated. This is TON
This is because the sensor output current did not reach the equilibrium value ig described earlier with reference to FIG. 4 because the time was too short. Tests # 6 to # 10 are the results of the same test with the intermittent cycle set to 0.02 seconds, but the value of TON / TOFF was 1/3 or more, and good detection accuracy was obtained. Although the intermittent cycle was gradually increased after test # 11, TON / T was used for # 36-40.
Even if OFF was 1/3 or more, the detection accuracy was not good. This is because the intermittent cycle is longer than the response speed of the sensor, which is about 30 seconds, so that the detection accuracy is deteriorated.

From the experimental results described above, the intermittent cycle Tc is less than 1/3 of the response time, and the ratio TON /
An oxygen sensor having better detection accuracy can be obtained with TOFF of 1/3 or more. In this case, the effect of the present invention is larger than that of the conventional method in which the sensor is continuously driven without interrupting the sensor current. The life of the sensor can be significantly extended. On the other hand, if the value of TON / TOFF is too large, the conduction time of the sensor current becomes longer, which departs from the gist of the present invention to extend the life of the sensor. Therefore, TON / TOFF is desirably 4/1 or less.

Example 2 A similar experiment was conducted for a sensor for detecting a representative hydrogen gas as a reducing gas. In this case, the basic configuration of the sensor is the same as that of FIG. 3 described above.

Reference numeral 2 denotes a working electrode, which is a catalyst material made of platinum or a platinum / ruthenium alloy or a platinum / iridium alloy. 4 is a counter electrode made of lead dioxide, 1 is a diaphragm,
It is a non-porous film of 25 μm thick tetrafluoroethylene-6-fluoropropylene copolymer. 3 is an electrolyte,
An acidic aqueous solution having a composition of 6 mol / L acetic acid, 5 mol / L potassium acetate, and 1 mol / L lead acetate is used as the electrolytic solution.

Reference numeral 10 denotes a pulse generator, 11 denotes a frequency divider, 12 denotes a monostable multivibrator circuit, and the pulse generator 10, the frequency divider 11, and the monostable multivibrator circuit 12 constitute a switch control unit. .

The response speed of this sensor to changes in gas concentration was about 20 seconds. Hydrogen reaching the working electrode via the diaphragm causes an electrochemical reaction with the counter electrode, and a current corresponding to the hydrogen concentration flows between the working electrode and the counter electrode. Insoluble lead oxide is produced as a reaction product at this time, but after the reaction, it reacts with an acetic acid component in the electrolytic solution to become water-soluble lead acetate and is dissolved in the electrolytic solution. Therefore, the point at which the concentration of lead acetate in the electrolyte reaches saturation is the sensor life. Also, the sensor life will be the same when the total amount of lead dioxide at the counter electrode has reacted.

The external lead wires 6 and 7 of this hydrogen sensor
A semiconductor analog switch element having bidirectional characteristics was connected, and the element was turned on / off at appropriate intervals to conduct / cut off the output current of the sensor, that is, the current due to the oxidation reaction of hydrogen. The on / off control of the semiconductor analog switch element was performed as follows. 4 by pulse generator
A high-frequency pulse of about MHz is oscillated, which is adjusted to an appropriate value Tc as a cycle for turning on / off the sensor current using a frequency divider, and further turned on by an on / off control circuit comprising a monostable multivibrator circuit. A control signal in which the ON / OFF time ratio TON / TOFF was adjusted was obtained. This signal was input to a semiconductor analog switch element, and conduction / cutoff control of the sensor current was performed. In this case, a waveform as shown in FIG. 4 was obtained as a sensor output for a certain hydrogen concentration, similarly to the oxygen sensor described above. At the moment when the semiconductor analog switch is turned on and the lead wire working electrode and the counter electrode of the sensor are electrically connected, the output current of the sensor has a steep rise and reaches the equilibrium value ig with time.

Although a semiconductor analog switch element is used as the switch section 8 here, the invention is not limited to this.

Next, in order to check the accuracy of the hydrogen sensor which has performed such control, purity is 99.99 as a zero gas.
% Or more of nitrogen gas, purity 99.99% as span gas
The mixture composition ratio of the hydrogen gas and the intermediate gas is 50 hydrogen.
The output of the hydrogen sensor was measured by sequentially flowing a standard gas of 50% nitrogen. In addition, the intermittent cycle of the hydrogen sensor output (T
c), sensor current conduction time (TON), cutoff time (TOFF)
), And examined how those values affect the measurement accuracy. The detection accuracy of the hydrogen sensor measures the equilibrium value of the sensor current at each gas concentration, and compares the value for the concentration of the intermediate gas calculated from the values for the zero gas and the span gas with the actually measured value when the intermediate gas is actually passed. I asked for it. Table 2 shows the obtained results.

[0043]

[Table 2] As shown in Table 2, in the case of the hydrogen sensor of the present embodiment, similarly to the case of the oxygen sensor described above, from the results of Tests # 2 to # 5, the TON /
TOFF is 1/3 or more, and it can be seen that the detection accuracy is deteriorated in test # 1 where TON / TOFF is 1/4. Further, in tests # 31 to # 35, the detection accuracy deteriorated because the intermittent cycle was longer than the response speed of the sensor of about 20 seconds.

From the experimental results described above, the intermittent period Tc is less than 1/3 of the response time and the ratio TON /
It is possible to obtain a hydrogen sensor having better detection accuracy with TOFF of 1/3 or more. In this case, compared with the conventional method in which the sensor is driven continuously without interrupting the sensor current, the effect of the present invention can be obtained. The life of the sensor can be significantly extended. On the other hand, if the value of TON / TOFF is too large, the conduction time of the sensor current becomes longer, which departs from the gist of the present invention to extend the life of the sensor. Therefore, TON / TOFF is desirably 4/1 or less.

[0045]

The diaphragm type gas sensor device according to the present invention has the following features.
A diaphragm type gas sensor, a switch unit for turning on and off a sensor detection current circuit, and a time T during which the switch unit is in an on state.
The ratio TON / TOFF between ON and OFF time TOFF is 1
And a switch control unit that controls the switch unit so that the ratio becomes / 3 or more and 4/1 or less. Also,
The operation method according to the present invention uses the switch control unit to set TON / T
The diaphragm type gas sensor device is operated intermittently by controlling the switch unit so that OFF is within the above range.

Thus, the life of the diaphragm type gas sensor can be significantly extended without lowering the detection accuracy as compared with the conventional one.

Further, TON / TOFF is set to 1/3 or more and 4/1
In addition to the following, the intermittent cycle TC, which is the sum of the time TON in which the switch section is in the ON state and the time TOFF in the OFF state, is set to be 1/3 or less of the sensor response time. It is possible to perform long-term measurement using a diaphragm-type gas sensor, and the sensor can be replaced without necessity or at a small frequency.

In addition, the diaphragm-type gas sensor according to the present invention makes it possible to permanently dispose the sensor inside the instrument or the building equipment, to make the maintenance interval of the equipment extremely long, and to use the diaphragm-type gas sensor. It is not necessary to increase the amount of electrode material or the amount of electrolyte to extend the life of the sensor, and the manufacturing cost and shape of the sensor are not increased, and the sensor is small, lightweight and relatively inexpensive. The life of the sensor can be extended without deteriorating the features of the various sensors.

Further, by integrally forming the switch control section and the switch section, the product of the present invention can be mounted without changing the conventional sensor mounting location.

Therefore, the present invention greatly contributes to the industry.

[Brief description of the drawings]

FIG. 1 is a diagram showing a basic configuration of a diaphragm type gas sensor.

FIG. 2 is a diagram showing the operation principle of a diaphragm type gas sensor.

FIG. 3 is a schematic view of a diaphragm type gas sensor device according to the present invention.

FIG. 4 is a diagram showing an output of the diaphragm type gas sensor device according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Diaphragm 2 Working electrode 3 Electrolyte 4 Counter electrode 5 Reference electrode 6 Working electrode side lead wire 7 Counter electrode side lead wire 8 Switch circuit 10 Pulse generator 11 Frequency divider 12 Monostable multivibrator circuit

Continuation of the front page (56) References JP-A-61-76132 (JP, A) JP-A-5-232082 (JP, A)

Claims (4)

(57) [Claims] 1. A diaphragm type gas sensor, a switch section for turning on and off a sensor detection current circuit, and a ratio T between a time TON when the switch section is on and a time TOFF when the switch section is off.
A diaphragm type gas sensor device comprising: a switch control unit that controls a switch unit so that ON / TOFF is equal to or more than １ ／ and equal to or less than 4/1. 2. The diaphragm type gas sensor device according to claim 1, wherein the switch control unit and the switch unit are formed integrally. 3. The switch control section controls the switch section such that the ratio TON / TOFF of the time TON during which the switch section is on and the time TOFF during which the switch section is off is 以上 or more and 4/1 or less. 3. The method according to claim 1, wherein the gas sensor is operated intermittently. 4. An intermittent cycle TC, which is a sum of a time TON in which the switch section is on and a time TOFF in which the switch section is off, is not more than 1/3 of the sensor response time. An operation method of the diaphragm type gas sensor device.