CN1865969A - Gas sensor, gas detector, and self-testing and self-correcting method therefor - Google Patents
Gas sensor, gas detector, and self-testing and self-correcting method therefor Download PDFInfo
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- CN1865969A CN1865969A CNA2005100347200A CN200510034720A CN1865969A CN 1865969 A CN1865969 A CN 1865969A CN A2005100347200 A CNA2005100347200 A CN A2005100347200A CN 200510034720 A CN200510034720 A CN 200510034720A CN 1865969 A CN1865969 A CN 1865969A
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Abstract
The related gas sensor for fuel cell comprises: based on traditional device, designing a cell core expansion hole and an air hole, using gel electrolyte instead of common liquid, adding a constant moisture device for sensor. It also uses the sensor to prepare a gas detector with self test and adjust function and free to environment effect and calibration gas source. This invention overcomes defects in prior art.
Description
Technical field
The present invention relates to gas sensing, pick-up unit, more particularly, the fuel cell gas sensor that relates to a kind of life-span length, more reliable performance, the detector of making by this fuel cell gas sensor, and the method for this fuel cell gas detecting device being carried out selftest and self-correction by correspondent peripheral circuit (being software and hardware).
Background technology
Fuel cell, is widely used in the gas sensor in invention in 1839 in recent decades by British William Grove.Usually, the fuel cell gas sensor mainly comprises a working electrode (claiming anode usually) and one to electrode (claiming negative electrode usually), working electrode and to being isolated by electrolyte between the electrode.The electrochemical oxidation of " fuel " gas on working electrode can cause electronics flowing from the anode to the negative electrode, promptly forms electric current.Wherein, strength of current and gas concentration are directly proportional.Representative gases principle of sensors and structure can be referring to U.S. Pat 5,738,773.
The fuel cell gas sensor has following feature: 1) no consumption spare and consumable accessory; 2) move with passive mode; 3) need not the external world and excite, get final product work under the room temperature; 4) good linearity, response speed is fast, and range of dynamic measurement is big; 5) good stability.Because these advantages, be that the detector of core becomes unique available common batteries power supply and the detector that can work long hours basically with the fuel cell gas sensor.Among the present invention, gas sensor refers to and can directly change into the device that can survey electric signal to gas signal; And in the detector except gas sensor, also comprise peripheral circuit (for example signals collecting, processing, storage, output, demonstration, control etc.), and software and hardware device such as man-machine communication.
Typical fuel cell gas sensor uses noble metal such as Pt or Pt alloy eelctro-catalyst as working electrode with to electrode usually, isolates with the matrix of having soaked electrolyte solution between two electrodes.In U.S. Pat 6,638,407B1 and Chinese patent ZL96202178.4 among the ZL95196037.7, disclose use liquid electrolyte liquid storage tank, keep electrolyte humidity/concentration method by soaking into channel.The shortcoming of this method is that sensor is subject to environment temperature, humidity, the influence of pressure and vibration, and liquid electrolyte leaks easily and causes problems such as burn into is dry, water logging, thereby can influence the life-span of sensor.
At present, one of key areas of fuel cell gas sensor application is the on-line monitoring as failure gas in carbon monoxide gas detector and power transformer or other the oil-filled electrical equipment oil.In actual use, because the influence of various external factor, as aging, the loose contact of sensor components and parts or the contamination of electrode surface, the performance of sensor can descend gradually, sensor even meeting are malfunctioning in some cases, but detecting device itself can't be told the user with its current state, though therefore can run into have object gas also detect less than situation take place, the mistake alarm perhaps takes place.
In U.S. Pat 6,200, among the 443B1, a kind of method and apparatus of sensor selftest is disclosed.Wherein fuel cell as a capacitor, make fuel cell charging with a little direct current (DC) voltage (10mV) (1 millisecond) in a very short time, then with the electric signal (voltage) of microprocessor determination sensor in the time of setting.Again the voltage and the predefined normal sensor determination value that record are made comparisons the value that this normal value records when normally sensor dispatches from the factory.The advantage of this method is by two values relatively simply, can judge whether operate as normal of sensor, because when normal operation of sensor, the sensor charging is slowly discharged slower; And when working sensor was undesired, sensor discharged and recharged quickening, and the magnitude of voltage that records can be greater than the sensor values of operate as normal.But this method has following shortcoming: 1) duration of charging very short, the repeatability of electronic switch and sampling is required high, under extremely short time difference, the result of sampling just may be obviously different, so the result's who records accuracy is affected.Must not have object gas (as carbon monoxide) in the surrounding environment of detecting device during 2) with this method, so practicality is affected, can not controls sensor by program at least and realize selftest.Because timing can not guarantee there is not object gas in the environment automatically.3) result is subjected to environment (sensor) Temperature Influence because sensor is tested oneself, so the result that this method records under different temperatures just lacks comparability.
Summary of the invention
At above-mentioned defective of the prior art, the present invention at first will solve the problem that the conventional fuel cell gas sensor electrolyte leakage can take place, is subject to environment temperature and humidity effect serviceable life.
The invention provides a kind of fuel cell gas sensor, comprise battery cover, electrolyte, working electrode and electrode; Wherein, in described battery cover, battery, battery tray and battery cover are housed successively from inside to outside; Described electrolyte is loaded in the center pit of described battery, described working electrode and electrode is positioned at the two ends of described battery center pit, and well contact with described electrolyte; Described battery is loaded on the center pit bottom of described battery tray, and described working electrode is in the face of the center pit of described battery tray; Between described battery cover and battery tray, be equipped with can allow oxygen and detected gas by but the gas-permeable membrane that can stop liquid and dust to pass through, the gas of described battery cover outside can arrive described working electrode through described battery cover, gas-permeable membrane and battery tray center pit, herein electrochemical reaction takes place and exports corresponding electric signal.Described battery cover, battery, battery tray and battery cover material be by PP (polypropylene), one or more compositions of PE (tygon) or ABS (acrylonitrile-butadiene-phenylethylene multipolymer) plastics.
In gas sensor of the present invention, described electrolyte is preferably by liquid electrolyte and solid porous glass or stupalith such as SiO
2The gel electrolyte that evenly mixes.In described gel electrolyte, SiO
2Weight be preferably 4%～40%, described liquid electrolyte preferably concentration is 30%～98% sulfuric acid or phosphoric acid.
In gas sensor of the present invention, the gel electrolyte inflation port that can communicate with it in the sidewall setting of described battery center pit; Pressure compensation opening parallel with described battery center pit and that communicate with described working electrode and to electrode also can be set in described battery.
In gas sensor of the present invention, can in described battery cover, a liquid storing cup be set, described liquid storing cup is positioned at described battery bottom, promptly towards to electrode; The constant humidity agent is housed in described liquid storing cup, the liquid storage bowl cover of band center pit is housed on the top of described liquid storing cup, permeable porous film is housed in described liquid storage bowl cover central hole; Water vapour between the constant humidity agent in described battery and the described liquid storing cup can be communicated with by described liquid storage bowl cover center pit, side opening and permeable porous film.Above-mentioned liquid storing cup, liquid storage bowl cover and permeable porous film also can be replaced by a liquid storing bag made from permeable porous film.Wherein, described constant humidity agent is preferably mixed by proper proportion by saturated metal salt solution and metal salt solid, and described slaine can be one or more in lithium chloride, potassium acetate, magnesium chloride, sal tartari, magnesium nitrate and the sodium chloride.
Relatively poor and can not realize the problem of simple and reliable selftest and self-correction selftest and self-correction for solving traditional detector reliability, the invention provides a kind of detector, comprise working power and microprocessor, also comprise the temperature sensor, gas sensor and the alarm device that are connected with described microprocessor; Wherein, described gas sensor is the fuel cell gas sensor in the aforementioned schemes; The transducing signal of described gas sensor is through signals collecting amplifying circuit and mould/number conversion circuit and be input to described microprocessor.
In detector of the present invention, preferably also comprise the electronic switch that is connected with described microprocessor, the positive pole of described working power is connected electrode by described electronic switch and gas sensor, and described working power negative pole passes through described electronic switch and is connected with the working electrode of gas sensor.Preferably also comprise a button that is connected with described microprocessor, by long by or shortly can realize selftest and self-correction or remove the gas concentration alarm function temporarily by described button.
In addition, the present invention also provides a kind of detector in the aforementioned schemes is carried out the method for selftest and self-correction, it is characterized in that not having under the condition of detected gas, carries out the pressure of baseline concentrations according to the following steps and proofreaies and correct:
(S11) judge whether to receive the signal of importing by manual test and correction trigger button,, otherwise repeat this step if then enter step (S12);
(S12) gather the current gas sensor and the detection signal U of temperature sensor
InitAnd T, and, calculate current concentration PPM according to the signal of being gathered
(cal)
(S13) connect electronic switch, by predetermined voltage and conduction time, to the logical reverse described voltage-stabilizing working power supply in the two poles of the earth of described gas sensor;
(S14) gather the detection signal U that energising finishes the back gas sensor
End, finish energising then;
(S15), calculate the selftest value S of gas sensor according to the detection signal of gained among described step (S12), (S14)
L=(U
End-U
Init) * f (T), wherein f (T) is a temperature compensation coefficient;
(S16) judge the current selftest value S of described sensor
LWith its reference value S
F(S
FSensor selftest value when dispatching from the factory) ratio R between
L/
F=S
L/ S
FWhether in preset range, if then enter described step (S17);
(S17) reset the baseline concentrations of described detecting device, deduct PPM at described step (S12) gained with current basic line concentration
(cal)Difference as new baseline concentrations, get back to described step (S11) then.
In method of the present invention, also comprise and following the step of self-correction is carried out in the sensitivity of detecting device, it is characterized in that no matter whether have detected gas, carry out the self-correction of sensitivity according to the following steps:
(S21) judge whether automatic test and sensitivity correction cycle of reaching predetermined,, otherwise repeat this step if then enter step (S22);
(S22) gather the current gas sensor and the detection signal U of temperature sensor
InitAnd T;
(S23) connect electronic switch, by predetermined voltage and conduction time, to the logical reverse described voltage-stabilizing working power supply in the two poles of the earth of described gas sensor;
(S24) gather the detection signal U that energising finishes the back gas sensor
End, finish energising then;
(S25), calculate the selftest value S of sensor according to the detection signal of gained among described step (S22), (S24)
L=(U
End-U
Init) * f (T), wherein f (T) is a temperature compensation coefficient;
(S26) judge the current selftest value S of described sensor
LWith its reference value S
F(S
FSensor selftest value when dispatching from the factory) ratio R between
L/
F=S
L/ S
FWhether in preset range, if then enter described step (S27);
(S27) with described selftest value S
LWith reference value S
FBetween ratio S
L/ S
FComing calculation correction coefficient C (is C=A*S
L/ S
F+ B, A wherein, B is a constant), reset the sensitivity correction coefficient, get back to described step (S21) then.
In method of the present invention, described sensor selftest value S
LWith reference value S
FBetween ratio R
L/
FPreset range be preferably 1-2; The described voltage-stabilizing working power supply oppositely predetermined voltage range of energising is preferably 2-5V; Oppositely energising scope conduction time is preferably 1-10 second.In addition, if described step (S16) or judged result (S26) are that promptly ratio has not exceeded predetermined value, preferably stop current step and send alarm signal this moment.
By such scheme as can be known, the invention solves the problem that electrolyte leakage can take place the conventional fuel cell gas sensor, simultaneously the serviceable life of having improved sensor by the mode that keeps constant humidity.With this fuel cell gas sensor detector that is core can be accurately the situation of discriminating sensor automatically, be not subjected to whether to have in environment temperature restriction and the environment restriction of detected gas or the existence of other interference gas; And can need not the calibrating gas source by the correction of realization baseline wander of automatic or manual triggering mode and sensitivity.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in the accompanying drawing:
Fig. 1 is the structural representation of fuel cell gas sensor in a preferred embodiment of the invention;
Fig. 2 is the structural representation of the battery core pack zoarium among the preferential embodiment shown in Fig. 1;
Fig. 3 is the structural representation of the liquid storing cup assembly among the preferential embodiment shown in Fig. 1;
Fig. 4 is the theory diagram of the detector in a preferred embodiment of the invention;
Fig. 5 is the process flow diagram when detector normally moves in a preferred embodiment of the invention;
Fig. 6 is the process flow diagram when manual triggers is carried out selftest and baseline correction to gas sensor in a preferred embodiment of the invention;
Fig. 7 triggers the process flow diagram that gas sensor is carried out selftest and sensitivity correction automatically in a preferred embodiment of the invention;
Fig. 8 is the selftest result curve synoptic diagram of gas sensor in a preferred embodiment of the invention;
Embodiment
Below in conjunction with embodiment content of the present invention is described in detail, what it will be appreciated by those skilled in the art that is that the present invention is not limited to following specific embodiment, also can produce multiple different embodiment in the scope of technical solution of the present invention.
Fig. 1 is the structural representation of fuel cell gas sensor in the preferred embodiment of the present invention.In fuel cell gas sensor 1, battery core pack zoarium 11 (its structure sees Fig. 2 for details) is placed in the cavity of battery tray 12, wherein working electrode 114 makes the object gas of coming from center pit directly to arrive on the working electrode 114 in the face of the center pit of battery tray 12.Electrode 115 is faced on the liquid storage bowl cover 151 of liquid storing cup assembly 15 (its structure sees Fig. 3 for details) on the battery core pack zoarium 11.Working electrode 114 contacts with the tight of working electrode conductive lead wire 116, and to electrode 115 and tight contact the to electrodes conduct lead-in wire 117, all is to lock in or similar structures is realized by the battery cover 10 and the machinery of battery cover 13.
As can be seen from Figure 1, a gas-permeable membrane 14 is installed between battery cover 13 and battery tray 12.This gas-permeable membrane 14 can allow object gas and oxygen pass through, but can not allow liquid or outside dust, particle pass through, and can play inhibition to the interchange of water vapor simultaneously.The selection of gas-permeable membrane 14 should be considered the seepage velocity of object gas, to guarantee the detection sensitivity of sensor, will consider that also the penetrating power of hydrone can not be too big simultaneously, to guarantee the constant of sensor internal humidity; Gas-permeable membrane material is preferably used PTFE (teflon), PVDF (polyvinyladine floride), PP (polypropylene) or PE (tygon).In the present embodiment, the thickness of gas-permeable membrane is 0.006mm to 0.050mm.As can be seen from Figure 1, the sealing between battery cover 13 and battery tray 12 and battery cover 10 and the battery tray 12 is realized by O-ring seal 20 and O-ring seal 21 respectively, also can fetch realization by supersonic welding.
From Fig. 1 and Fig. 2 as can be seen, after object gas sees through gas-permeable membrane 14, pass the center pit of battery tray 12, arrive battery core pack zoarium 11 at last, electrochemical reaction takes place on working electrode 114 and produce electric signal, this electric signal passes on the outside testing circuit plate (not drawing in the drawings) by working electrode conductive lead wire 116 and working electrode conductor contact pin 16, and by forming the loop to electrodes conduct lead-in wire 117 with to electrode conductor contact pin 17.Working electrode 114 wherein and are gas-diffusion electrodes to electrode 115 can be coated on conduction carbon paper sintering by eelctro-catalyst and form.In eelctro-catalyst, except that containing noble metal or precious metal alloys eelctro-catalyst, also contain carbon black conductive carrier and hydrophober.Eelctro-catalyst is platinum or platinum alloy noble metal nano powder preferably, and hydrophober preferably uses the PTFE particle.Working electrode conductive lead wire 116 and electrodes conduct lead-in wire 117 preferably used platinum filament or spun gold.
As shown in Figure 2, for fear of electrolytical leakage, use semi-solid gel electrolyte 118 to replace traditional liquid electrolyte in the present embodiment, it places in the center pit of battery 111, the material of battery uses corrosion resistant plastics such as PP, PE, PTFE or ABS, the upper and lower surface of center pit covers (be working electrode 114 and to electrode 115) by gas-diffusion electrode, and there is gel electrolyte inflation port 113 side to adapt to variation of temperature in the sensor.Also have a pressure compensation opening 112 on the limit of center pit, its diameter is less than 1mm, and this equalizing port can play two effects, and the one, balancing battery core two sides, i.e. working electrode 114 and to the pressure of electrode 115; The 2nd, to electrode being provided electrochemical reaction necessary oxygen.In the present embodiment, gel electrolyte 118 is evenly mixed by liquid electrolyte and solid porous SiO2 material, and wherein the weight of SiO2 is 4%～40%, and liquid electrolyte preferably concentration is 30%～98% sulfuric acid or phosphoric acid.The working relative humidity of gel electrolyte 118 can obtain by regulating sulfuric acid or concentration of phosphoric acid, and is as shown in table 1.
The equilibrium relative humidity (ERH) (RH%) of sulfuric acid when showing 1:25 ℃
(Ref.ASTM E104-1991Maintaining Constant Relative Humidity by means of Aqueous Solution)
| Sulfuric acid concentration (%) | RH％ |
| 30 | 75 |
| 45 | 46 |
| 60 | 16 |
Owing to taked said structure, the problem of electrolyte leakage can not take place in the gas sensor of present embodiment when normal the use.
As shown in Figure 3, for the stability and the serviceable life of improving sensor, provide a kind of device that keeps constant humidity in the present embodiment, promptly the liquid storing cup assembly 15.Wherein, constant humidity agent 155 places the bottom of battery cover 10, and by a kind of permeable porous film 154 constant humidity agent and external isolation is come, and this permeable porous film can allow water vapor see through under normal pressure, but can not allow liquid and solid see through.The material of this permeable porous film preferably uses PTFE or PVDF, and its aperture is preferably less than 0.001mm.Constant humidity agent 155 is formulated by a certain percentage by the solid of saturated metal salt solution and this slaine.That is to say, in the constant humidity agent, both contained metal salt solution, also contain undissolved slaine.Spendable slaine is including, but not limited to the listed slaine of table 2.
When showing 2:25 ℃, the equilibrium relative humidity (ERH) of saturated aqueous metal salt (RH%)
(Ref.ASTM E104-1991Maintaining Constant Relative Humidity by means of Aqueous Solution)
| The slaine title | Chemical molecular formula | RH％ |
| Lithium chloride | LiCl.H 2O | 11.3 |
| Potassium acetate | KC 2H 3O 2 | 22.5 |
| Magnesium chloride | MgCl 2·6H 2O | 32.8 |
| Sal tartari | K 2CO 3·2H 2O | 43.2 |
| Magnesium nitrate | Mg(NO 3) 2·6H 2O | 52.9 |
| Sodium chloride | NaCl | 75.3 |
In actual the use, the selection of constant humidity agent 155 will be decided according to used gel electrolyte 118.Constant humidity agent 155 realizes sealing by permeable porous film 154 and liquid storage bowl cover 151 by suitable Design of Mechanical Structure.Have a liquid storing cup center pit 152 on the liquid storage bowl cover 151 and directly face, to guarantee the working relative humidity of battery core pack zoarium electrode 115.Establish a horizontal bleeder vent 153 on the sidewall of liquid storing cup center pit 152, it communicates with the inner chamber of battery tray 12, is used to guarantee the working relative humidity of whole sensor inside.When changing the humidity variation that causes sensor internal owing to external environment condition humidity, this constant humidity agent can absorb unnecessary moisture content effectively or discharge not enough moisture content, thereby can regulate the humidity of sensor internal automatically, guarantee the stability and the serviceable life of operating sensor.
Fig. 4 is the theory diagram of the carbon monoxide gas detector that the aforementioned gas sensor of employing is made in a preferred embodiment of the invention.Under normal detected state, the electric signal that gas sensor 41 produces is handled through signals collecting amplifying circuit 42, is converted to digital signal through mould/number (A/D) converter 43 then, arrives microprocessor 40 at last.Simultaneously, the temperature signal of temperature sensor 44 also is input to microprocessor.Temperature sensor 44 can be a thermal sensing element commonly used such as thermopair, thermistor, will also can be digitized integrated temperature sensor through A/D conversion (not drawing in Fig. 4) when arriving microprocessor.The microprocessor that uses in the present embodiment is MSP430 (Texas Instrument), its inner integrated temperature sensor.Detection signal according to above-mentioned gas sensor and temperature sensor, microprocessor 40 can be converted into gas concentration signal by the mathematical model of prior setting, and itself and the alert settings value that is stored in the microprocessor compared, if gas concentration signal has surpassed the alert settings value and has surpassed the time-delay of setting, then microprocessor 40 can the outputting alarm signals, thereby make hummer 49 send alarm sound, LED lamp 50 sends alerting light and shows corresponding warning information by LCD 51.
In actual use, owing to be subjected to the influence of various external factor, as wearing out of used components and parts, electrically contact deterioration etc., the detection performance of gas sensor can be affected, thereby can influence the precision of detector.Influence factors of accuracy and mainly contain two aspects, the one, the baseline of detecting device, promptly detecting device is at the signal that does not have object gas to divide the period of the day from 11 p.m. to 1 a.m to provide; Another is sensitivity, i.e. the signal that detecting device provides under the unit gas concentration.Certainly, the variation of these two factors may be a process slowly.
Baseline concentrations for detecting device, available manual triggers is carried out self-correction, preferably every 1-6 month once, during concrete operations, need detecting device is placed vent position,, press the manual triggers selftest and the self-correction button 48 of detecting device then to guarantee not having object gas, microprocessor is connected electronic switch 45 to the gas sensor certain hour of oppositely switching on, and by microprocessor the baseline concentrations of detecting device is returned to zero again.
For the sensitivity of detecting device, can directly utilize the coefficient of sensor selftest and need not the calibrating gas source.When reaching predetermined automatic sensitivity correction during the cycle (real-time clock 47), then start selftest and self-correction flow process.Microprocessor is connected electronic switch 45 to the gas sensor certain hour of oppositely switching on.Its concrete steps will be explained hereinafter.
Be the process flow diagram of detecting device when normally moving as shown in Figure 5, wherein:
Step 503 judges whether timer counts down to 0, is then to enter step 504, otherwise continues to wait for.
Step 506 judges that actual gas concentration whether greater than gas concentration alert settings value, if then enter step 507, otherwise gets back to step 502.
Be the process flow diagram that the gas sensor manual triggers is carried out selftest and baseline concentrations timing as shown in Figure 6, wherein:
Step 601 judges whether to receive manual triggers test and correction instruction, is then to enter step 602, otherwise repeats this step.During concrete operations, need detecting device is placed vent position,, press the manual triggers test and the correcting key of detecting device then to guarantee not having object gas.
Step 602 is gathered gas sensor and temperature sensor signal U
InitWith T, and by setting calculated with mathematical model PPM
(cal)
Step 603 starts electronic switch and timer, oppositely connects 3 seconds of 3V D.C. regulated power supply for sensor the two poles of the earth.
Step 604 is gathered collection U again from gas sensor the two poles of the earth
End
Step 605, microprocessor is according to aforementioned U
Init, U
End, T, calculate the test value S of sensor
L, and judge R
L/F=S
L/ S
FWhether in normal range, R
L/FNormal range value generally between 1 to 2, is then to enter step 606, otherwise enters step 607.Wherein:
S
L＝(U
end-U
init)*f(T)
S
FSensor selftest value when dispatching from the factory, i.e. S first for sensor
LValue.
S wherein
LBe the last sensor selftest value; U
InitBe the sensor electrical signal (voltage) before the logical reverse direct supply; U
EndElectric signal (voltage) for sensor behind the logical reverse direct supply; F (T) is a temperature compensation coefficient, and it is an experimental formula, can decide by concrete experiment, for example can be linear function [Eq.1:f (T)=aT+b], or exponential function
(a, b are constant) can both meet the demands in certain temperature range.
If step 606 is S
L/ S
FBe in normal range, then reset baseline Offset, deduct PPM at described step 602 gained with current basic line concentration
(cal)Difference as new baseline concentrations, i.e. Offset=Offset-PPM
(cal), get back to step 601 then.
If step 607 is S
L/ S
FNot in normal range, then stop normally to detect and exporting corresponding warning information, for example emat sensor more.
Be that the gas sensor self-timing is triggered the process flow diagram that carries out selftest and sensitivity correction as shown in Figure 7, wherein:
Step 701 judges whether that the self-timing that reaches predetermined triggers selftest and sensitivity correction cycle, is then to enter step 702, otherwise repeats this step.During concrete enforcement, need to set an automatic calibration cycle in the program of detecting device, for example every work was proofreaied and correct once in 360 hours.
Step 702 is gathered gas sensor and temperature sensor signal U
InitAnd T.
Step 703 starts electronic switch and timer, oppositely connects 3 seconds of 3V D.C. regulated power supply for sensor the two poles of the earth.
Step 704 is gathered collection U again from gas sensor the two poles of the earth
End
S
L＝(U
end-U
init)*f(T)
S
FSensor selftest value when dispatching from the factory, i.e. S first for sensor
LValue.
S wherein
LBe the last sensor selftest value; U
InitBe the sensor electrical signal (voltage) before the logical reverse direct supply; U
EndElectric signal (voltage) for sensor behind the logical reverse direct supply; F (T) is a temperature compensation coefficient, and it is calculated by an experimental formula, can decide by concrete experiment, for example can be linear function f (T)=aT+b, or exponential function
(a, b are constant) can both meet the demands in certain temperature range.
If step 706 is S
L/ S
FBe in normal range, then reset transducer sensitivity correction coefficient C, get back to step 701 then; Wherein:
C=(A*S
L/ S
F+ B), A, B are constant, can obtain by experiment.
If step 707 is S
L/ S
FNot in normal range, then stop normally to detect and exporting corresponding warning information, for example emat sensor more.
Above-mentioned automatic aligning step has following advantage: 1) automatic timing, no matter in the environment not object gas (as carbon monoxide) is arranged, and do not influence the accuracy of test, because test value is a relative value; 2) automatic timing is not subjected to the restriction of temperature, and the result has comparability; 3) conduction time longer relatively, greater than 1 second, therefore control exactly easily, the degree of accuracy of measurement improves; 4). timing need not calibrating gas source or other utility appliance and material.
For the ease of understanding, the front is that Fig. 5, Fig. 6, flow process shown in Figure 7 are described as the program of three independent operatings, when specifically implementing, can be three parallel flow processs, also can carry out each step successively in a main flow.
Fig. 8 is a typical sensor selftest curve.Tested oneself 60 o'clock at start sensor, the electric signal of sensor is U
InitAfter reverse 3 seconds of switching on (3V direct current), promptly in curve location 61, the electric signal of sensor becomes U
EndAfter stopping oppositely energising, sensor returns extensive original state gradually, and during by 3 minutes, promptly curve location 62, returns to normal basically.
Claims (15)
1, a kind of fuel cell gas sensor comprises battery cover, battery, battery tray, battery cover, electrolyte, working electrode and to electrode; It is characterized in that,
In described battery cover, battery, battery tray and battery cover are housed successively from inside to outside;
Described electrolyte is loaded in the center pit of described battery, described working electrode and electrode is positioned at the two ends of described battery center pit, and well contact with described electrolyte;
Described battery is loaded on the center pit bottom of described battery tray, and described working electrode is in the face of the center pit of described battery tray;
Between described battery cover and battery tray, be equipped with can allow oxygen and detected gas by but the gas-permeable membrane that can stop liquid and dust granules to pass through, the gas of described battery cover outside can arrive described working electrode through described battery cover, gas-permeable membrane and battery tray center pit, herein electrochemical reaction takes place and exports corresponding electric signal.
2, fuel cell gas sensor according to claim 1 is characterized in that, described electrolyte is by liquid electrolyte and solid porous SiO
2The gel electrolyte that material evenly mixes; Wherein, SiO
2Weight be 4%～40%, described liquid electrolyte is that concentration is 30%～98% sulfuric acid or phosphoric acid.
3, fuel cell gas sensor according to claim 1 is characterized in that, also is provided with the gel electrolyte inflation port that communicates with it at the sidewall of described battery center pit.
4, fuel cell gas sensor according to claim 1 is characterized in that, also is provided with pressure compensation opening parallel with described battery center pit and that communicate with described working electrode and to electrode in described battery.
5, fuel cell gas sensor according to claim 1 is characterized in that, also is provided with a liquid storing cup in described battery cover, and described liquid storing cup is positioned at described battery bottom; The constant humidity agent is housed in described liquid storing cup, the liquid storage bowl cover is housed, permeable porous film is housed in described liquid storage bowl cover central hole on the top of described liquid storing cup; Water vapour between the constant humidity agent in described battery and the described liquid storing cup can be communicated with by described liquid storage bowl cover center pit, permeable porous film.
6, fuel cell gas sensor according to claim 5 is characterized in that, also establishes a horizontal bleeder vent that communicates with the inner chamber of described battery tray on the sidewall of described liquid storing cup center pit.
7, fuel cell gas sensor according to claim 1, it is characterized in that, in described battery cover, also be provided with a liquid storing bag made from permeable porous film, the constant humidity agent is housed in described liquid storing bag, and the water vapour between the constant humidity agent in described battery and the described liquid storing bag can be communicated with by described permeable porous film.
8, according to each described fuel cell gas sensor among the claim 5-7, it is characterized in that, described constant humidity agent is mixed by proper proportion by saturated metal salt solution and metal salt solid, and described slaine is one or more in lithium chloride, potassium acetate, magnesium chloride, sal tartari, magnesium nitrate and the sodium chloride.
9, a kind of detector comprises voltage-stabilizing working power supply and microprocessor, also comprises the temperature sensor, gas sensor and the alarm device that are connected with described microprocessor; It is characterized in that,
Described gas sensor is each described fuel cell gas sensor among the claim 1-8;
The transducing signal of described gas sensor is through signals collecting amplifying circuit and mould/number conversion circuit and be input to described microprocessor.
10, detector according to claim 9, it is characterized in that, also comprise the electronic switch that is connected with described microprocessor, the positive pole of described voltage-stabilizing working power supply is connected electrode by described electronic switch and gas sensor, and described voltage-stabilizing working power supply negative pole passes through described electronic switch and is connected with the working electrode of gas sensor.
11, detector according to claim 9 is characterized in that, also comprises the button that is connected with described microprocessor, by long by or shortly can realize selftest and self-correction or remove the gas concentration alarm function temporarily by described button.
12, a kind of the described detector of claim 10 is carried out the method for selftest and self-correction, it is characterized in that not having under the condition of detected gas, carry out the pressure of baseline concentrations according to the following steps and proofread and correct:
(S11) judge whether to receive the signal of importing by manual test and correction trigger button,, otherwise repeat this step if then enter step (S12);
(S12) gather the current gas sensor and the detection signal U of temperature sensor
InitAnd T, and, calculate current concentration PPM according to the signal of being gathered
(cal)
(S13) connect electronic switch, by predetermined voltage and conduction time, to the logical reverse described voltage-stabilizing working power supply in the two poles of the earth of described gas sensor;
(S14) gather the detection signal U that energising finishes the back gas sensor
End, finish energising then;
(S15), calculate the selftest value S of gas sensor according to the detection signal of gained among described step (S12), (S14)
L=(U
End-U
Init) * f (T), wherein f (T) is a temperature compensation coefficient;
(S16) judge the current selftest value S of described sensor
LWith its reference value S
F(S
FSensor selftest value when dispatching from the factory) ratio R between
L/
F=S
L/ S
FWhether in preset range, if then enter described step (S17);
(S17) reset the baseline concentrations of described detecting device, deduct PPM at described step (S12) gained with current basic line concentration
(cal)Difference as new baseline concentrations, get back to described step (S11) then.
13, a kind of the described detector of claim 10 is carried out the method for selftest and self-correction, it is characterized in that, according to the following steps the sensitivity of detecting device is carried out from normal moveout correction:
(S21) judge whether automatic sensitivity correction cycle of reaching predetermined,, otherwise repeat this step if then enter step (S22);
(S22) gather the current gas sensor and the detection signal U of temperature sensor
InitAnd T;
(S23) connect electronic switch, by predetermined voltage and conduction time, to the logical reverse described voltage-stabilizing working power supply in the two poles of the earth of described gas sensor;
(S24) gather the detection signal U that energising finishes the back gas sensor
End, finish energising then;
(S25), calculate the selftest value S of sensor according to the detection signal of gained among described step (S22), (S24)
L=(U
End-U
Init) * f (T), wherein f (T) is a temperature compensation coefficient;
(S26) judge the current selftest value S of described sensor
LWith its reference value S
F(S
FSensor selftest value when dispatching from the factory) ratio R between
L/
F=S
L/ S
FWhether in preset range, if then enter described step (S27);
(S27) with described selftest value S
LWith reference value S
FBetween ratio S
L/ S
FComing calculation correction coefficient C (is C=A*S
L/ S
F+ B, A wherein, B is a constant), reset the sensitivity correction coefficient, get back to described step (S21) then.
14, according to claim 12 or 13 described methods, it is characterized in that described sensor selftest value S
LWith reference value S
FBetween ratio R
L/
FPreset range be 1-2; The described voltage-stabilizing working power supply oppositely predetermined voltage range of energising is 2-5V; Oppositely energising scope conduction time is 1-10 second.
15, according to claim 12 or 13 described methods, it is characterized in that, if described step (S16) or judged result (S26) are that promptly ratio has not exceeded predetermined value, then stops current step and sends alarm signal.
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