CN203287345U - Electrochemical hydrogen sulfide sensor - Google Patents
Electrochemical hydrogen sulfide sensor Download PDFInfo
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- CN203287345U CN203287345U CN2013202175514U CN201320217551U CN203287345U CN 203287345 U CN203287345 U CN 203287345U CN 2013202175514 U CN2013202175514 U CN 2013202175514U CN 201320217551 U CN201320217551 U CN 201320217551U CN 203287345 U CN203287345 U CN 203287345U
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 114
- 229910052697 platinum Inorganic materials 0.000 claims description 56
- 239000007789 gas Substances 0.000 claims description 23
- 239000012528 membrane Substances 0.000 claims description 22
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Abstract
The utility model discloses an electrochemical hydrogen sulfide sensor. The electrochemical hydrogen sulfide sensor mainly comprises a housing, as well as a working electrode, a reference electrode, an offset counter electrode and an electrolyte storage area which are sequentially superposed in the housing and mutually insulated, and further comprises three conductive metal wires respectively used for leading out current generated by the working electrode, the reference electrode and the offset counter electrode, wherein the three conductive metal wires are respectively connected with the surfaces of the working electrode, the reference electrode and the offset counter electrode in a gluing manner. The electrochemical hydrogen sulfide sensor overcomes the defects of high manufacture difficulty, low conductive contact reliability, high manufacturing cost and the like in the prior art, and achieves the advantages of low manufacturing difficulty, high conductive contact reliability and low manufacturing cost.
Description
Technical field
The utility model relates to sensor technical field, particularly, relates to a kind of galvanochemistry hydrogen sulfide sensor.
Background technology
Therefore sulfuretted hydrogen (chemical formula is H2S) is the extremely strong gas of a kind of toxicity, is very important being easy to contact the concentration that detects H2S in the environment of H2S.Have for detection of the sensor of H2S concentration a variety of, as H2S sensor, galvanochemistry type H2S sensor, optical-fiber type H2S gas sensor and the catalytic combustion-type H2S sensor of semi-conductor type.
In the sensor, electrochemical gas sensor, because it is accurate, sensitive, reliable and stable, the response rapid, has become international main flow sensor, at present mainly for detection of 1,000,000/(ppm) concentration level hydrogen sulfide gas.But the structural requirement of electrochemical sensor is very accurate, and manufacture difficulty is quite large, only has at present seldom several countries and company to produce.
The similar fuel cell of the basic functional principle of electrochemical gas sensor, as electrode, the metallic catalyst of electrode surface also plays conduction with the porous diffusion film that contains noble metal (as platinum black, the superfine powder of metal platinum is black, so be platinum black).It is working electrode, contrast electrode and to electrode that sensor has three electrodes usually.The working electrode catalytic decomposition diffuses into the interior gas of sensor, electron gain, electron stream to electrode is formed current return, and this electric current is directly proportional to the gas concentration in entering sensor.The advantage of electrochemical gas sensor can be summarized as: the linearity that (1) is fabulous; (2) good repeatability; (3) good selectivity; (4) extremely low power consumption (milliwatt level); (5) electrochemical sensor is highly sensitive, and is most for detection of ppm level gas.
Typical electrochemical poison gas sensor is by working electrode, form electrode and contrast electrode, and by a thin electrolyte layers, separates (referring to Fig. 1).In Fig. 1, this electrochemical poison gas sensor comprises plastic casing 9, parallel be arranged on ventilated membrane 2 within plastic casing 9, working electrode 3, contrast electrode 4 and with one heart to electrode 5, be arranged on the O type circle 11 between ventilated membrane 2 and working electrode 3, be separately positioned between working electrode 3 and contrast electrode 4 and contrast electrode 4 and concentric on the barrier film 10 between electrode 5, and be arranged on concentric electrolytic solution storage area to electrode 5 belows, can add a cover electrolytic solution storage cap 6 on the electrolytic solution storage area.Roof at plastic casing 9 offers gas diffusion paths 1, the diapire of plastic casing 9 offer with electrolytic solution storage cap 6 on the liquid injection port 8 that is complementary of opening., in the bottom outside of plastic casing, be provided with respectively and working electrode 3, contrast electrode 4 and concentric three metal pins 7 that electrode 5 is connected.
At first gas see through sensor top aperture (as gas diffusion paths 1), diffuse to hydrophobic barrier (as ventilated membrane 2), final working electrode 3 surfaces that arrive, working electrode 3 catalytic decomposition diffuse into the interior gas of sensor, electron gain, electron stream to electrode 5 is formed current returns, this electric current is directly proportional to the gas concentration in entering sensor, measures this electric current and can determine gas concentration.The catalytic reaction that working electrode 3 occurs the electrode material that designs for tested gas can be oxidation mechanism, can be also reduction mechanism.
Be marked with electrolyte solution (mostly being caustic acid, alkali or salt solusion) in the cavity of sensor, three electrodes only have abundant infiltration in electrolytic solution, and above-mentioned electrochemical reaction could normally occur.Contrast electrode is arranged on and the working electrode close position, working electrode need to remain on to be stablized under constant potential, contrast electrode can keep this stable voltage on working electrode, but contrast electrode self has electric current, does not flow through, and electric current is to flow through between to electrode and working electrode.
Three electrodes of sensor are working electrode (as working electrode 3), contrast electrode (as contrast electrode 4) and electrode (as with one heart to electrode 5) order are successively overlayed in the plastic casing of sensor, by a dielectric film, they separated between electrode.The electric current that electrode produces exports to pin (as metal pins 7 by three thin platinum flat filaments (as the first platinum filament 13, the second platinum filament 14 and the 3rd platinum filament 15) that are close to the membrane electrode surface, respectively with three of the inside of three metal pins 7 electrode is connected), its structure is as shown in Fig. 2 a, Fig. 2 b and Fig. 2 c.Platinum filament will have enough length, can guarantee that like this itself and electrode surface have sufficient surface of contact, to guarantee good electric conductivity.
In Fig. 2 a, Fig. 2 b and Fig. 2 c, the non-conductive surface of being with 17, the first platinum filaments 13 to be close to the first conductive strips 18 that working electrode 3 comprises the first conductive strips 18 and is positioned at the first conductive strips 18 peripheries; The non-conductive surface of being with 17, the second platinum filaments 15 to be close to the second conductive strips 19 that with one heart electrode 5 is comprised the second conductive strips 19 and is positioned at the second conductive strips 19 peripheries.
The sensor of prior art, that (diameter is identical or approaching with size with the same profile of working electrode (circle) with one, diameter is usually between 5～30mm) electrode, with a circular hollow drift, the concentrically ringed mode of using is downcut two electrodes from the electrode upper punch: little electrode wafer is as contrast electrode, the concentric ring electrode conduct is to electrode, as shown in Fig. 2 a, Fig. 2 b and Fig. 2 c.
In the prior art, in order to allow platinum filament and to abundant contact is arranged between the electrode surface conductive layer, the 3rd platinum filament 15 must long enough, and platinum filament can pass electrode intermediate gaps part like this, with the right and left conductive surface of annulus, contacts.
But in Practical manufacturing, the applicant finds, (usually only have 1～3mm) because the width to the electrode annulus is very little, as long as the placement location of platinum filament has displacement slightly, just be easy to cause the left side conductive strips loose contact phenomenon of platinum filament and annulus, thereby affect the overall performance of sensor, as fixed in unstability of base line, the phenomenons such as the response time is elongated, response curve torsional deformation.
In addition, rare metal platinum is expensive, and international market has reached 60000 dollars/kilogram (being roughly equal to 380,000 Renminbi/kilograms) at present, and whole world reserves are limited, the annual production of whole world platinum is only had an appointment 180 tons, and China is the country of platinum scarcity of resources, and annual production only has 4 tons.Platinum has accounted for approximately more than 70% in the manufacturing cost of electrochemical sensor.Therefore,, in order to reduce the manufacturing cost of sensor, save the use of platinum, must find from each parts the new technology of possible minimizing platinum use amount.
In realizing process of the present utility model, the inventor finds in prior art to exist at least that manufacture difficulty is large, the conductive contact reliability of platinum filament and annulus is low and the defect such as manufacturing cost height.
Summary of the invention
The purpose of this utility model is,, for the problems referred to above, proposes a kind of galvanochemistry hydrogen sulfide sensor, to realize that manufacture difficulty is little, the conductive contact reliability is high and the advantage of low cost of manufacture.
For achieving the above object, the technical solution adopted in the utility model is: a kind of galvanochemistry hydrogen sulfide sensor, mainly comprise shell, be stacked in successively working electrode, the contrast electrode, eccentric to electrode and electrolytic solution storage area of described enclosure and insulation each other, and be used for drawing respectively described working electrode, contrast electrode and eccentric three conductive wires to the electrode generation current; Described three conductive wires, the formula that pastes respectively are connected to described working electrode, contrast electrode and eccentric surface to electrode.
Further, described bias comprises eccentric ring electrode to electrode, and described eccentric ring electrode comprises the conductive strips that formed by conductive ring;
Described conductive strips are distributed in the width of eccentric annular center lines of electrodes right side part, are distributed in the width of eccentric annular center lines of electrodes left part greater than conductive strips.
Further, described conductive strips are distributed in the width of eccentric annular center lines of electrodes right side part, are 1.5 times of the conductive strips width that is distributed in eccentric annular center lines of electrodes left part at least.
Further, described eccentric ring electrode, also comprise the non-conductive band that is positioned at described conductive strips periphery.
Further, the width of the non-conductive band of described eccentric ring electrode, greater than 0mm and be less than or equal to 10mm.
Further, above-described galvanochemistry hydrogen sulfide sensor, also comprise the ventilated membrane that is positioned at described enclosure and is arranged on described working electrode top.
Further, between described ventilated membrane and working electrode, coordinate the O RunddichtringO is installed.
Further, above-described galvanochemistry hydrogen sulfide sensor, also comprise and be separately positioned between described working electrode and contrast electrode and contrast electrode and eccentric to the dielectric film between electrode.
Further, at the roof of described shell, offer for the gas diffusion paths to the ventilated membrane injecting gas, and/or, the diapire of described shell offer with the electrolytic solution storage area below the liquid injection port that is complementary of opening; And/or, in the bottom wall outer of described shell, and three metal pins that are connected with three conductive wires respectively.
Further, described conductive wire, comprise platinum filament.
The galvanochemistry hydrogen sulfide sensor of each embodiment of the utility model, owing to mainly comprising shell, be stacked in successively working electrode, the contrast electrode, eccentric to electrode and electrolytic solution storage area of enclosure and insulation each other, and be used for drawing respectively working electrode, contrast electrode and eccentric three conductive wires to the electrode generation current; Three conductive wires, the formula that pastes respectively are connected to described working electrode, contrast electrode and eccentric surface to electrode; Can both guarantee that bias has good contacting and electric conductivity to electrode with corresponding conductive wire, had saved again the conductive wire use amount, and has improved the properties of sensor; Thereby can overcome the defect that in prior art, manufacture difficulty is large, the conductive contact reliability is low and manufacturing cost is high, to realize that manufacture difficulty is little, the conductive contact reliability is high and the advantage of low cost of manufacture.
Other features and advantages of the utility model will be set forth in the following description, and, partly become apparent from instructions, perhaps by implementing the utility model, understand.
Below by drawings and Examples, the technical solution of the utility model is described in further detail.
Description of drawings
Accompanying drawing is used to provide further understanding of the present utility model, and forms the part of instructions, with embodiment one of the present utility model, is used from explanation the utility model, does not form restriction of the present utility model.In the accompanying drawings:
Fig. 1 is the inner structure schematic diagram of electrochemical poison gas sensor;
Fig. 2 a is the syndeton schematic diagram of sensor internal membrane electrode (working electrode) and platinum filament (the first platinum filament);
Fig. 2 b is the syndeton schematic diagram of sensor internal membrane electrode (contrast electrode) and platinum filament (the second platinum filament);
Fig. 2 c is the syndeton schematic diagram of sensor internal membrane electrode (to electrode) and platinum filament (the 3rd platinum filament);
Fig. 2 d is a kind of syndeton schematic diagram of the utility model galvanochemistry hydrogen sulfide sensor internal membrane electrode (to electrode) and platinum filament (the 4th platinum filament);
Fig. 3 in the utility model galvanochemistry hydrogen sulfide sensor is punched to a circular electrode contrast electrode and bias die-cut schematic diagram that concerns to electrode;
Fig. 4 a is the another kind of syndeton schematic diagram of the utility model galvanochemistry hydrogen sulfide sensor internal membrane electrode (working electrode) and platinum filament (the first platinum filament);
Fig. 4 b is the another kind of syndeton schematic diagram of the utility model galvanochemistry hydrogen sulfide sensor internal membrane electrode (to electrode) and platinum filament (the 4th platinum filament);
Fig. 4 c is a kind of structural representation (m is the straight line in the center of circle by eccentric ring electrode and electrode circular hole) of the utility model galvanochemistry hydrogen sulfide sensor internal membrane electrode (eccentric to electrode);
Fig. 4 d is the another kind of structural representation (m is the straight line in the center of circle by eccentric ring electrode and electrode circular hole) of the utility model galvanochemistry hydrogen sulfide sensor internal membrane electrode (eccentric to electrode);
Fig. 5 is the performance test results schematic diagram of the utility model galvanochemistry hydrogen sulfide sensor.
By reference to the accompanying drawings, in the utility model embodiment, Reference numeral is as follows:
The 1-gas diffusion paths; The 2-ventilated membrane; The 3-working electrode; The 4-contrast electrode; 5-is with one heart to electrode; 6-electrolytic solution storage cap; 7-metal pins (respectively with three of inside electrode is connected); The 8-liquid injection port; The 9-plastic casing; The 10-barrier film; 11-O type circle; 12-bias is to electrode; 13-the first platinum filament; 14-the second platinum filament; 15-the 3rd platinum filament; 16-the 4th platinum filament; The non-conductive band of 17-; 18-the first conductive strips; 19-the second conductive strips; 20-the 3rd conductive strips.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present utility model is described, should be appreciated that preferred embodiment described herein only is used for description and interpretation the utility model, and be not used in restriction the utility model.
According to the utility model embodiment, as Fig. 2 a, Fig. 2 b, Fig. 2 d, Fig. 3, Fig. 4 a, Fig. 4 b, Fig. 4 c, Fig. 4 d and shown in Figure 5, a kind of galvanochemistry hydrogen sulfide sensor is provided, be mainly for detection of the stink damp body burden, the safety detection, environment monitoring and the production run that are widely used in the industries such as petroleum gas production, chemical plant, chemical fertilizer production, communal facility, wastewater treatment, papermaking (slurry) factory, pharmacy, food and drink, automobile, electroplating processes, mining, military affairs are controlled.
The galvanochemistry hydrogen sulfide sensor of the present embodiment, mainly comprise shell, be stacked in successively working electrode, the contrast electrode, eccentric to electrode and electrolytic solution storage area of enclosure and insulation each other, and be used for drawing respectively working electrode, contrast electrode and eccentric three conductive wires (as platinum filament) to the electrode generation current; Three conductive wires, the formula that pastes respectively are connected to working electrode, contrast electrode and eccentric surface to electrode.
The galvanochemistry hydrogen sulfide sensor of above-described embodiment, also comprise the ventilated membrane that is positioned at enclosure and is arranged on the working electrode top, is separately positioned between working electrode and contrast electrode and contrast electrode and eccentric to the dielectric film between electrode.Between ventilated membrane and working electrode, coordinate the O RunddichtringO is installed.Roof at shell offers for the gas diffusion paths to the ventilated membrane injecting gas, and/or, the diapire of shell offer with the electrolytic solution storage area below the liquid injection port that is complementary of opening; And/or, in the bottom wall outer of shell, and three metal pins that are connected with three conductive wires respectively.
Preferably, in the galvanochemistry hydrogen sulfide sensor of above-described embodiment, described bias comprises eccentric ring electrode to electrode, and eccentric ring electrode comprises the conductive strips that formed by conductive ring; Conductive strips are distributed in the width of eccentric annular center lines of electrodes right side part, are distributed in the width of eccentric annular center lines of electrodes left part greater than conductive strips.Conductive strips are distributed in the width of eccentric annular center lines of electrodes right side part, are 1.5 times of the conductive strips width that is distributed in eccentric annular center lines of electrodes left part at least.Eccentric ring electrode, also comprise the non-conductive band that is positioned at described conductive strips periphery, and the width of the non-conductive band of eccentric ring electrode, greater than 0mm and be less than or equal to 10mm.
In the galvanochemistry hydrogen sulfide sensor of above-described embodiment, the new method that the applicant has used a kind of prior art not adopt first: referring to Fig. 3, with the circular electrode of and the same profile of working electrode and size (can referring to the working electrode 3 in Fig. 3), with a circular hollow drift, die-cut from the position of departing from the center of circle, thereby form two electrodes: electrode wafer (can referring to the contrast electrode 4 in Fig. 3) is as contrast electrode, and Eccentric Circular Ring electrode (can referring to the bias in Fig. 3 to electrode 12) is as to electrode.
The galvanochemistry hydrogen sulfide sensor of the present embodiment, used a bias to electrode (namely eccentric to electrode 12).owing to electrode (namely eccentric to electrode 12), being the annulus of a bias, the right-hand component of conductive strips is wider than left-hand component greatly, so as long as with a shorter platinum filament (as the 4th platinum filament 16), be fitted on the wider the right conductive strips of electrode (namely eccentric to electrode 12), just can guarantee good surface of contact and electric conductivity between electrode (namely eccentric to electrode 12) and platinum filament (as the 4th platinum filament 16) with producing effect, and platinum filament (as the 4th platinum filament 16) though the storing position slightly be shifted and also can not affect platinum filament (as the 4th platinum filament 16) and to the good contact of electrode (namely eccentric to electrode 12).Referring to Fig. 4 c and Fig. 4 d.
The profile form of two kinds of bias of this shown in Fig. 4 c and Fig. 4 d to electrode, can occur in actual applications.Pass through simultaneously bias to the center of circle of electrode and the center of circle of electrode circular hole if draw straight line m, the length left and right along this root straight line m conductive strips is asymmetric, and the length a on conductive strips the right is greater than the length b on the conductive strips left side; Because the length of b can be zero, thus a/b can be defined in 1.5 between infinity (remarks: as a/b=1 or near 1 the time, be donut to electrode, this is the utility model prior art that will overcome just).
In the galvanochemistry hydrogen sulfide sensor of the present embodiment, electrode stacks and a kind of syndeton of electrode and platinum filament, referring to Fig. 2 a, Fig. 2 b and Fig. 2 d.In Fig. 2 a, Fig. 2 b and Fig. 2 d, the non-conductive surface of being with 17, the first platinum filaments 13 to be close to the first conductive strips 18 that working electrode 3 comprises the first conductive strips 18 and is positioned at the first conductive strips 18 peripheries; The eccentric non-conductive surface of being with 17, the four platinum filaments 16 to be close to the 3rd conductive strips 20 that electrode 12 is comprised the 3rd conductive strips 20 and is positioned at the 3rd conductive strips 20 peripheries.
In the galvanochemistry hydrogen sulfide sensor of the present embodiment, electrode stacks and the another kind of syndeton of electrode and platinum filament, referring to Fig. 4 a, Fig. 2 b and Fig. 4 b.In Fig. 4 a, Fig. 2 b and Fig. 4 b, working electrode 3 includes only the first conductive strips 18 and does not comprise that electrical insulator, the first platinum filament 13 are close to the surface of the first conductive strips 18; Eccentric electrode 12 is comprised the 3rd conductive strips 20 and do not comprise non-conductive band, the 4th platinum filament 16 is close to the surface of the 3rd conductive strips 20.
Fig. 5 can show the performance test results with above-described embodiment galvanochemistry hydrogen sulfide sensor.As shown in Figure 5, property indices such as response time, baseline value, response sensitivity etc. are all very good, meet performance standard.
In the galvanochemistry hydrogen sulfide sensor of above-described embodiment, bias can be defined as electrode: the wider limit of ring electrode is narrower more than 1.5 times of limit; The narrower hem width degree of ring electrode can be between 0 millimeter to 10 millimeters.
Compare with prior art, the galvanochemistry hydrogen sulfide sensor of the utility model above-described embodiment, use a bias to electrode (namely bias is to electrode 12), both having guaranteed has good contacting and electric conductivity to electrode (namely eccentric to electrode 12) with platinum filament (as the 4th platinum filament 16), save again the platinum filament use amount, and improved the properties of sensor.
It should be noted that finally: the foregoing is only preferred embodiment of the present utility model, be not limited to the utility model, although with reference to previous embodiment, the utility model is had been described in detail, for a person skilled in the art, it still can be modified to the technical scheme that aforementioned each embodiment puts down in writing, and perhaps part technical characterictic wherein is equal to replacement.All within spirit of the present utility model and principle, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection domain of the present utility model.
Claims (10)
1. galvanochemistry hydrogen sulfide sensor, it is characterized in that, mainly comprise shell, be stacked in successively working electrode, the contrast electrode, eccentric to electrode and electrolytic solution storage area of described enclosure and insulation each other, and be used for drawing respectively described working electrode, contrast electrode and eccentric three conductive wires to the electrode generation current; Described three conductive wires, the formula that pastes respectively are connected to described working electrode, contrast electrode and eccentric surface to electrode.
2. galvanochemistry hydrogen sulfide sensor according to claim 1, is characterized in that, described bias comprises eccentric ring electrode to electrode, and described eccentric ring electrode comprises the conductive strips that formed by conductive ring;
Described conductive strips are distributed in the width of eccentric annular center lines of electrodes right side part, are distributed in the width of eccentric annular center lines of electrodes left part greater than conductive strips.
3. galvanochemistry hydrogen sulfide sensor according to claim 2, is characterized in that, described conductive strips are distributed in the width of eccentric annular center lines of electrodes right side part, is 1.5 times of the conductive strips width that is distributed in eccentric annular center lines of electrodes left part at least.
4. galvanochemistry hydrogen sulfide sensor according to claim 2, is characterized in that, described eccentric ring electrode also comprises the non-conductive band that is positioned at described conductive strips periphery.
5. galvanochemistry hydrogen sulfide sensor according to claim 4, is characterized in that, the width of the non-conductive band of described eccentric ring electrode, greater than 0mm and be less than or equal to 10mm.
6. the described galvanochemistry hydrogen sulfide sensor of any one according to claim 1-5, is characterized in that, also comprises the ventilated membrane that is positioned at described enclosure and is arranged on described working electrode top.
7. galvanochemistry hydrogen sulfide sensor according to claim 6, is characterized in that, between described ventilated membrane and working electrode, coordinates the O RunddichtringO is installed.
8. the described galvanochemistry hydrogen sulfide sensor of any one according to claim 1-5, is characterized in that, also comprises and be separately positioned between described working electrode and contrast electrode and contrast electrode and eccentric to the dielectric film between electrode.
9. the described galvanochemistry hydrogen sulfide sensor of any one according to claim 1-5, it is characterized in that, roof at described shell offers for the gas diffusion paths to the ventilated membrane injecting gas, and/or, the diapire of described shell offer with the electrolytic solution storage area below the liquid injection port that is complementary of opening; And/or, in the bottom wall outer of described shell, and three metal pins that are connected with three conductive wires respectively.
10. the described galvanochemistry hydrogen sulfide sensor of any one according to claim 1-5, is characterized in that, described conductive wire is platinum filament.
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| CN2013202175514U CN203287345U (en) | 2013-04-18 | 2013-04-18 | Electrochemical hydrogen sulfide sensor |
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| CN2013202175514U CN203287345U (en) | 2013-04-18 | 2013-04-18 | Electrochemical hydrogen sulfide sensor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104749231A (en) * | 2015-04-01 | 2015-07-01 | 合肥工业大学 | Electrochemical sensor and application thereof in rapid detection for hydrogen sulphide |
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| CN104749231A (en) * | 2015-04-01 | 2015-07-01 | 合肥工业大学 | Electrochemical sensor and application thereof in rapid detection for hydrogen sulphide |
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Granted publication date: 20131113 Termination date: 20170418 |