CN113588757B - Method for measuring service life of electrochemical sensor by pulse excitation - Google Patents
Method for measuring service life of electrochemical sensor by pulse excitation Download PDFInfo
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- 230000005284 excitation Effects 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000005070 sampling Methods 0.000 claims abstract description 18
- 238000001514 detection method Methods 0.000 claims abstract description 16
- 230000036541 health Effects 0.000 claims abstract description 13
- 230000004044 response Effects 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 108700041286 delta Proteins 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 22
- 238000005259 measurement Methods 0.000 abstract description 8
- 238000003745 diagnosis Methods 0.000 abstract description 6
- 239000003245 coal Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 238000012544 monitoring process Methods 0.000 abstract description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 238000004092 self-diagnosis Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 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
- G01N27/416—Systems
- G01N27/4163—Systems checking the operation of, or calibrating, the measuring apparatus
Abstract
The invention relates to a method for measuring the service life of an electrochemical gas sensor by pulse excitation, which belongs to the technical field of sensor service life detection. The pulse excitation key parameters comprise the voltage amplitude UI and the pulse width T1 of the pulse, and the pulse response specific parameters comprise the voltage amplitudes D1 and D2 … … DN of N times of sampling measurement, and the maximum value DB1, the next-largest value DB2, the median DB0 and the electrochemical sensor health degree alpha. The invention can rapidly and effectively evaluate the service life of the electrochemical sensor and perform fault diagnosis on the electrochemical sensor, thereby integrally improving the working reliability and stability of a sensor system comprising the electrochemical sensor and ensuring the accuracy of monitoring toxic and harmful gases in the coal mine safety production environment.
Description
Technical Field
The invention belongs to the field of sensor life detection, and relates to a method for measuring the life of an electrochemical sensor by pulse excitation.
Background
The electrochemical gas sensor has good linear output and measurement accuracy, low power consumption and high resolution, and is widely applied in the industrial field and the coal mine field, particularly the detection of toxic and harmful gases such as carbon monoxide, hydrogen sulfide and the like, and the sensors of other detection principles cannot realize miniaturized high-resolution gas detection, so that the electrochemical gas sensor has important functions for industrial and coal mine safety environment detection application.
Through development for over 20 years, the electrochemical gas sensor has more and more simplified and scientific signal processing circuit, and can be suitable for signal processing of various gas elements. However, electrochemical sensors generally have the problem of short service life, generally the service life is 1-2 years, and too much or too little ambient humidity can reduce the service life of the sensor. Therefore, the service life of the sensor needs to be evaluated and diagnosed in real time, so that the stability and the reliability of the operation of the sensor are ensured, and the sensor system is prevented from influencing the coal mine safety production due to the fact that the sensor exceeds the service life to detect failure or false alarm and the like.
In the prior art, only a life diagnosis hardware circuit of an electrochemical sensor is researched, and a life evaluation diagnosis method of the sensor has no related technical scheme. The evaluation and diagnosis algorithm needs a large number of sensor failure samples to analyze, so that the characteristic parameters of the key judgment basis of life diagnosis are obtained, and the corresponding software algorithm is obtained. The invention discloses performance indexes of key characteristic parameters of the service life of the sensor and an acquisition method thereof, thereby improving the service life of the sensor and the self-diagnosis technical level of faults and filling the blank of an electrochemical sensor service life diagnosis software algorithm.
Disclosure of Invention
Therefore, the invention aims to disclose the performance index and the acquisition method of the key characteristic parameters of the service life of the sensor, thereby improving the service life of the sensor and the self-diagnosis technical level of faults, filling the blank of the service life diagnosis software algorithm of the electrochemical sensor, and scientifically guiding the daily maintenance and use of the electrochemical sensor.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method of pulse excitation for measuring the lifetime of an electrochemical sensor comprising the steps of:
s1: analyzing an electrochemical sensor sample, and setting a voltage amplitude UI and a pulse width T1 of a pulse excitation key parameter;
s2: the microprocessor controls the D/A conversion module and the constant voltage circuit to output constant voltage UR between the reference electrode R and the counter electrode C of the electrochemical sensor, the detection electrode S of the electrochemical sensor outputs a current signal, the current signal outputs voltage UO after passing through the signal processing circuit, the UO enters the A/D conversion circuit, and the microprocessor reads the A/D conversion result D0 in real time;
s3: the microprocessor starts a timer, simultaneously controls the D/A conversion module and the constant voltage circuit to send excitation pulses to the position between the reference electrode R and the counter electrode C of the electrochemical sensor, the pulse amplitude is UI, the detection electrode S of the electrochemical sensor outputs pulse response signals, the signals enter the A/D conversion circuit after passing through the signal processing circuit, and the microprocessor reads the A/D conversion result in real time at intervals of sampling time T2;
s4: after the T1 time, the microprocessor co-samples to obtain N A/D conversion results, namely D1 and D2 … … DN respectively, stops the timer and clears; the microprocessor controls the D/A conversion module and the constant voltage circuit to output constant voltage UR between the reference electrode R and the counter electrode C of the electrochemical sensor, the electrochemical sensor detection electrode S outputs a current signal, the signal enters the A/D conversion circuit after passing through the signal processing circuit, and the microprocessor reads the A/D conversion result in real time at intervals of sampling time T2 within the time length of T3;
s5: comparing N data of D1 and D2 … … DN, wherein the maximum value is DB1, the next-largest value is DB2, and the median value is DB0;
introducing an impulse response confidence value delta 1; if DB1-DB2 is larger than delta 1, D1 and D2 … … DN sampling is invalid, the microprocessor controls the D/A conversion module and the constant voltage circuit to output constant voltage UR between the reference electrode R and the counter electrode C of the electrochemical sensor, and the holding time length is T3; returning to the step S2;
if DB1-DB2 is less than or equal to delta 1, D1 and D2 … … DN sampling is effective, setting the life expectancy coefficient of the electrochemical sensor as gamma, and if (D1+D2+D3+ … +DP) is less than or equal to gamma and N is less than or equal to DB1, the life of the electrochemical sensor is ended and the electrochemical sensor cannot be used continuously; if (D1+D2+D3+ … +DP) > gamma N DB1, if DB1-DB0 is less than or equal to delta 1, the health degree alpha of the electrochemical sensor is 100%; if DB1-DB0 > Δ1, the electrochemical sensor health α is the smaller of (d1+d2+d3+ … +dp)/(N DB 1) or (dp+ … +dn)/(N DB 1); returning to step S2, the process loops.
Further, in step S1, the pulse amplitude UI is not less than 1mv and not more than 20mv; t1 is not less than 100ms and not more than 500ms.
Further, in step S2, the constant voltage UR is related to the characteristics of the electrochemical sensor, the output voltage UO is related to the concentration of the gas to be measured, and the higher the concentration of the gas to be measured is, the larger the output voltage UO is.
Further, in step S3, the sampling interval time is more than or equal to 0.01ms and less than or equal to T2 and less than or equal to 10ms, the smaller T2 is, the more accurate the measurement of the health degree and the service life is, but too small can increase the operation load of the microprocessor and affect the overall performance.
Further, in step S4, T3 is more than 5min; t1=n×t2, N is 10-50000, and the greater N, the more accurate the measurement of health and life, but too large increases the microprocessor computational load, affecting overall performance.
Further, in step S5, 3.ltoreq.Δ1.ltoreq.10; P=N/2, if N is odd, rounding up, 0.6.ltoreq.gamma.ltoreq.0.95.
The invention has the beneficial effects that: the method for measuring the service life of the electrochemical sensor can quickly and effectively evaluate the service life of the electrochemical sensor and perform fault diagnosis on the electrochemical sensor, so that the working reliability and stability of a sensor system comprising the electrochemical sensor are integrally improved, and the accuracy of monitoring toxic and harmful gases in a coal mine safety production environment is ensured.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in the following preferred detail with reference to the accompanying drawings, in which:
FIG. 1 is a block diagram of an electrochemical sensor life measurement circuit.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be noted that the illustrations provided in the following embodiments merely illustrate the basic idea of the present invention by way of illustration, and the following embodiments and features in the embodiments may be combined with each other without conflict.
Wherein the drawings are for illustrative purposes only and are shown in schematic, non-physical, and not intended to limit the invention; for the purpose of better illustrating embodiments of the invention, certain elements of the drawings may be omitted, enlarged or reduced and do not represent the size of the actual product; it will be appreciated by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
The same or similar reference numbers in the drawings of embodiments of the invention correspond to the same or similar components; in the description of the present invention, it should be understood that, if there are terms such as "upper", "lower", "left", "right", "front", "rear", etc., that indicate an azimuth or a positional relationship based on the azimuth or the positional relationship shown in the drawings, it is only for convenience of describing the present invention and simplifying the description, but not for indicating or suggesting that the referred device or element must have a specific azimuth, be constructed and operated in a specific azimuth, so that the terms describing the positional relationship in the drawings are merely for exemplary illustration and should not be construed as limiting the present invention, and that the specific meaning of the above terms may be understood by those of ordinary skill in the art according to the specific circumstances.
Referring to fig. 1, the present invention proposes a method for measuring the lifetime of an electrochemical gas sensor by pulse excitation, which is to send pulse excitation to the electrochemical gas sensor to measure specific parameters of impulse response output by the sensor, thereby predicting the lifetime and performance of the electrochemical gas sensor. The pulse excitation key parameters comprise the voltage amplitude UI and the pulse width T1 of the pulse, and the pulse response specific parameters comprise the voltage amplitudes D1 and D2 … … DN of N times of sampling measurement, and the maximum value DB1, the next-largest value DB2, the median DB0 and the electrochemical sensor health degree alpha.
S1: by analyzing a large number of samples of the electrochemical sensor, the voltage amplitude UI and the pulse width T1 of the key pulse excitation parameters are set.
S2: the microprocessor controls the D/A conversion module and the constant voltage circuit to output constant voltage UR between the reference electrode (R) and the counter electrode (C) of the electrochemical sensor, the electrochemical sensor detects the electrode (S) to output a current signal, the current signal outputs voltage UO after passing through the signal processing circuit, the UO enters the A/D conversion circuit, and the microprocessor reads the A/D conversion result D0 in real time.
S3: the microprocessor starts a timer, simultaneously controls the D/A conversion module and the constant voltage circuit to send excitation pulses between the reference electrode (R) and the counter electrode (C) of the electrochemical sensor, the pulse amplitude is UI, the detection electrode (S) of the electrochemical sensor outputs impulse response signals, the signals enter the A/D conversion circuit after passing through the signal processing circuit, and the microprocessor reads the A/D conversion result in real time every sampling time T2.
S4: after the T1 time, the microprocessor co-samples to obtain N A/D conversion results, which are D1 and D2 … … DN respectively, stops the timer and clears. The microprocessor controls the D/A conversion module and the constant voltage circuit to output constant voltage UR between the reference electrode (R) and the counter electrode (C) of the electrochemical sensor, the electrochemical sensor detection electrode (S) outputs a current signal, the signal enters the A/D conversion circuit after passing through the signal processing circuit, and the microprocessor reads the A/D conversion result in real time every sampling time T2 within the time length of T3.
S5: comparing N data of D1 and D2 … … DN, wherein the maximum value is DB1, the next maximum value is DB2, the median value is DB0, an impulse response confidence value delta 1 is introduced, and if DB1-DB2 is larger than delta 1, D1 and D2 … … DN sampling is invalid, the microprocessor controls the D/A conversion module and the constant voltage circuit to output constant voltage UR between the reference electrode (R) and the counter electrode (C) of the electrochemical sensor. Step S2 is then performed.
S6: if DB1-DB2 is less than or equal to delta 1, D1 and D2 … … DN sampling is effective, setting the life expectancy coefficient of the electrochemical sensor as gamma, and if (D1+D2+D3+ … +DP) is less than or equal to gamma and N is less than or equal to DB1, the life of the electrochemical sensor is ended and the electrochemical sensor cannot be used continuously; if (D1+D2+D3+ … +DP) > gamma N DB1, if DB1-DB0 is less than or equal to delta 1, the health degree alpha of the electrochemical sensor is 100%; if DB1-DB0 > Δ1, the electrochemical sensor health α is the smaller of (d1+d2+d3+ … +dp)/(N DB 1) or (dp+ … +dn)/(N DB 1); returning to step S2, the process loops.
Wherein:
in step S1, the pulse amplitude UI should be not less than 1mv and should be not more than 20mv. T1 should not be less than 100ms and should not be greater than 500ms.
In step S2, the constant voltage UR is related to the characteristics of the electrochemical sensor, the output voltage UO is related to the concentration of the gas to be measured, and the higher the concentration of the gas to be measured, the higher the output voltage UO.
In step S3, the sampling interval time T2 should be not less than 0.01ms and should be not more than 10ms. The smaller T2, the more accurate the measurement of health and life, but too small will increase the microprocessor computational load, affecting overall performance.
In step S4, t1=n×t2. N is more than or equal to 10 and less than or equal to 50000, and the greater N is, the more accurate the measurement of the health degree and the service life is, but the excessive N can increase the operation load of the microprocessor and affect the overall performance. T3 is greater than 5 minutes.
In the step S5, the delta 1 is more than or equal to 3 and less than or equal to 10.
In step S6, p=n/2, and if N is an odd number, the whole is rounded up. The gamma value is generally not less than 0.6 and not more than 0.95.
Embodiment one:
the GTH1000 type mining carbon monoxide sensor adopts a carbon monoxide gas sensor with an electrochemical principle as a sensitive element. By analyzing a large number of samples, setting the voltage amplitude UI of the key pulse excitation parameters to be 3mV and the pulse width T1 to be 100ms; the microprocessor controls the constant voltage UR between the reference electrode (R) and the counter electrode (C) of the electrochemical sensor to be 1100mV, the output current signal of the detection electrode (S) of the electrochemical sensor is 150nA, the output voltage UO of the current signal is 1101.5mV after passing through the signal processing circuit, the UO enters the A/D conversion circuit, and the microprocessor reads the A/D conversion result D0 to be 1503 in real time to measure the concentration of the carbon monoxide gas.
The microprocessor starts a timer, sends excitation pulses, and reads the A/D conversion result in real time at intervals of 0.5 ms. After 100ms, the microprocessor samples 200 a/D conversion results, namely 1520, 1545, 1572, 1578, 1577, 1579, 1578, … …, 1577 and … …, which are omitted as 190 values with random fluctuation of 1577, 1578 and 1579, respectively, and stops the timer and clears the timer. The microprocessor controls and outputs constant voltage 1100mV, reads the A/D conversion result at intervals of 0.5ms in 5min, and measures the concentration of the carbon monoxide gas.
Comparing 200 data of 1520, 1545, 1572, 1578, 1577, 1579, 1578, … … and 1577, wherein the maximum value DB1 is 1579, the next-largest value DB2 is 1578, the median DB0 is 1578, the incoming impulse response confidence value delta 1 is 3, and DB1-DB 2=1 is calculated, so that DB1-DB2 is less than or equal to delta 1, D1 and D2 … … DN are effectively sampled, the expected life coefficient gamma of the electrochemical sensor is set to be 0.6, P=N/2=100, (1520+1545+1572+ … +1578) >
0.6X10X11579 and DB1-DB 0.ltoreq.Δ1, the electrochemical sensor health α is 100%.
Embodiment two:
the GTH1000 type mining carbon monoxide sensor adopts a carbon monoxide gas sensor with an electrochemical principle as a sensitive element. By analyzing a large number of samples, setting the voltage amplitude UI of the key pulse excitation parameters to be 3mV and the pulse width T1 to be 100ms; the microprocessor controls the constant voltage UR between the reference electrode (R) and the counter electrode (C) of the electrochemical sensor to be 1100mV, the output current signal of the detection electrode (S) of the electrochemical sensor is 150nA, the output voltage UO of the current signal is 1101.5mV after passing through the signal processing circuit, the UO enters the A/D conversion circuit, and the microprocessor reads the A/D conversion result D0 to be 1503 in real time to measure the concentration of the carbon monoxide gas.
The microprocessor starts a timer, sends excitation pulses, and reads the A/D conversion result in real time at intervals of 0.5 ms. After 100ms, the microprocessor samples to obtain 200A/D conversion results, 1508, 1509, 1510, 1511, 1512, 1513, 1514, respectively 1515, … … 1577, 1578, 1577, 1579, 1578, 1577, … …, 1578, the first … … omitted the 135 nearly uniformly increasing values from 1516 to 1577, and the second … … omitted the 40 values 1577, 1578, 1579 randomly fluctuating. The timer is stopped and cleared. The microprocessor controls and outputs constant voltage 1100mV, reads the A/D conversion result at intervals of 0.5ms in 5min, and measures the concentration of the carbon monoxide gas.
Pairs 1508, 1509, 1510, 1511, 1512, 1513, 1514, 1515 … …, 1578, 1577, 1579, 1578, 1577, … …, 1578 of 200 data are compared, the maximum DB1 is 1579, the next-largest DB2 is 1578, the median DB0 is 1554, the incoming impulse response confidence value Δ1 is 3, calculating DB1-DB 2=1, if DB1-DB2 is equal to or less than Δ1, D1, D2 … … DN sampling is effective, setting the life expectancy coefficient γ of the electrochemical sensor to 0.6, p=n/2=100, (1508+1508+1509+ … +1554) = 153100,0.6 ×200×1579= 189480, (d1+d2+d3+ … +dp) is equal to or less than γ×n×db1, and the life of the electrochemical sensor is terminated and can not be used continuously.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.
Claims (6)
1. A method for measuring the life of an electrochemical sensor by pulse excitation, which is characterized by comprising the following steps of: the method comprises the following steps:
s1: analyzing an electrochemical sensor sample, and setting a pulse amplitude UI and a pulse width T1 of a pulse excitation key parameter;
s2: the microprocessor controls the D/A conversion module and the constant voltage circuit to output constant voltage UR between the reference electrode R and the counter electrode C of the electrochemical sensor, the detection electrode S of the electrochemical sensor outputs a current signal, the current signal outputs voltage UO after passing through the signal processing circuit, the UO enters the A/D conversion circuit, and the microprocessor reads the A/D conversion result D0 in real time;
s3: the microprocessor starts a timer, simultaneously controls the D/A conversion module and the constant voltage circuit to send excitation pulses to the position between the reference electrode R and the counter electrode C of the electrochemical sensor, the pulse amplitude is UI, the detection electrode S of the electrochemical sensor outputs pulse response signals, the signals enter the A/D conversion circuit after passing through the signal processing circuit, and the microprocessor reads the A/D conversion result in real time at intervals of sampling time T2;
s4: after the T1 time, the microprocessor co-samples to obtain N A/D conversion results, namely D1 and D2 … … DN respectively, stops the timer and clears; the microprocessor controls the D/A conversion module and the constant voltage circuit to output constant voltage UR between the reference electrode R and the counter electrode C of the electrochemical sensor, the electrochemical sensor detection electrode S outputs a current signal, the signal enters the A/D conversion circuit after passing through the signal processing circuit, and the microprocessor reads the A/D conversion result in real time at intervals of sampling time T2 within the time length of T3;
s5: comparing N data of D1 and D2 … … DN, wherein the maximum value is DB1, the next-largest value is DB2, and the median value is DB0;
introducing an impulse response confidence value delta 1; if DB1-DB2 is larger than delta 1, D1 and D2 … … DN sampling is invalid, the microprocessor controls the D/A conversion module and the constant voltage circuit to output constant voltage UR between the reference electrode R and the counter electrode C of the electrochemical sensor, and the holding time length is T3; returning to the step S2;
if DB1-DB2 is less than or equal to Δ1, D1, D2 … … DN sampling is effective, setting the life expectancy coefficient of the electrochemical sensor to be γ, if (d1+d2+d3+ … +dp) is less than or equal to γ N DB1, the life of the electrochemical sensor is terminated and cannot be used continuously, p=n/2, if N is an odd number, rounding up; if (D1+D2+D3+ … +DP) > gamma N DB1, if DB1-DB0 is less than or equal to delta 1, the health degree alpha of the electrochemical sensor is 100%; if DB1-DB0 > Δ1, the electrochemical sensor health α is the smaller of (d1+d2+d3+ … +dp)/(N DB 1) or (dp+ … +dn)/(N DB 1); returning to step S2, the process loops.
2. The method for measuring the life of an electrochemical sensor by pulse excitation according to claim 1, wherein: in the step S1, the pulse amplitude UI is not less than 1mv and not more than 20mv; t1 is not less than 100ms and not more than 500ms.
3. The method for measuring the life of an electrochemical sensor by pulse excitation according to claim 1, wherein: in step S2, the constant voltage UR is related to the characteristics of the electrochemical sensor, the output voltage UO is related to the concentration of the gas to be measured, and the higher the concentration of the gas to be measured, the higher the output voltage UO.
4. The method for measuring the life of an electrochemical sensor by pulse excitation according to claim 1, wherein: in the step S3, the sampling interval time is more than or equal to 0.01ms and less than or equal to T2 and less than or equal to 10ms.
5. The method for measuring the life of an electrochemical sensor by pulse excitation according to claim 1, wherein: in step S4, T3 > 5min, t1=n×t2, 10.ltoreq.n.ltoreq.50000.
6. The method for measuring the life of an electrochemical sensor by pulse excitation according to claim 1, wherein: in the step S5, delta 1 is more than or equal to 3 and less than or equal to 10; gamma is more than or equal to 0.6 and less than or equal to 0.95.
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