CN1043488C - Solid polymer electrolyte, capillary type oxygen sensor - Google Patents
Solid polymer electrolyte, capillary type oxygen sensor Download PDFInfo
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- CN1043488C CN1043488C CN 94107055 CN94107055A CN1043488C CN 1043488 C CN1043488 C CN 1043488C CN 94107055 CN94107055 CN 94107055 CN 94107055 A CN94107055 A CN 94107055A CN 1043488 C CN1043488 C CN 1043488C
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Abstract
The present invention discloses a solid polymer electrolyte capillary type oxygen sensor, which belongs to the technical field of electrochemistry. The present invention does not contain flow electrolyte solution, a sensitive electrode (a working electrode) of the present invention is a metal, metal oxide or other catalyst film stuck by polytetrafluoroethene, and the sensitive electrode is combined with a Nafion film by means of a hot-pressing method. A plastic board with capillary holes is closely stuck on the working electrode so as to form gas-phase diffusion mass-transfer control. By means of current electrolysis, the reduction current of oxygen on the working electrode is directly in a direct proportion with the percentage concentration of the oxygen. The capillary tube type oxygen sensor based on a waterproof solid polymer elecrolytes gas diffusion electrode has the characteristics of fast response, small temperature coefficient, long-term stability, etc.
Description
The invention discloses a kind of solid polymer electrolyte, capillary type oxygen sensor, it belongs to technical field of electrochemistry.It is the novel normal-temperature electrochemical gas sensor based on solid polymer electrolyte.
At present, commercial normal temperature electrochemistry oxygen sensor mainly contains Clark type [L.C.Clark, Jr., Trans.Am.Soc.Artif.Intern.Organs, 2 (1956) 41.] and kapillary air--metal primary element lambda sensor [Britain City Univ.A.C.C.Tsueng, unpublished research report].Though they have good precision, owing to contain flowing electrolyte solution, thereby problem such as ubiquity leakage, burn into be dry.Solid polymer electrolyte replaces traditional flowing electrolyte solution owing under the normal temperature good electrical conductivity is arranged with it, can make sensor avoid all disadvantages of mobile electrolytic solution.People such as Japan Miura once reported and utilized the electric potential type lambda sensor [N.Miura, J.Kato, N.Yamazoe and T.Seiyama, Danki Kagaku, 52 (1984) 376] of solid polymer electrolyte Nafion film as ion conductor.Because of its response time oversize (90% response＞30 minutes), so far do not reach practical application.
The core of solid polymer electrolyte sensor is the solid polymer electrolyte gas electrode.The solid polymer electrolyte gas electrode of bibliographical information adopts chemical deposition to be prepared more, promptly uses the electronation deposited catalyst on the Nafion film, as Au, [H.Kita, K.Fujikawa and H.Nakijima, Elcctrochim.Acta such as Pt, 29 (1984) 1721 ,].Though kind electrode has certain activity, activity decay is very fast, and its main cause is due to the moving of reaction zone.
The objective of the invention is to: in order to overcome the deficiency of the sensor, we intend proposing a kind of the do not have high stability of flowing electrolyte solution, the solid polymer electrolyte normal temperature electrochemistry oxygen sensor of fast-response.
For realizing that the technical measures that purpose of the present invention is taked are: one of core technology of the present invention is a Nafion waterproof diffusion gas electrode, and it is by constituting with the lower part: Nafion 117 films (1); Working electrode (9): contrast electrode (15): auxiliary electrode (4,14); Porose plastic plate (5); Capillary plate (13); The bottom center has the sensor cavity and the sensor loam cake (12) of an aperture (6).Therein, working electrode is loaded on the one side of Nafion film, reference electrode and auxiliary electrode be loaded in the Nifion film another and on, capillary plate is fixed on the working electrode surface towards gas phase, porose plastic plate is fixed on the below of cavity.It is at a slice Nafion 117 films (1) (perfluorinated sulfonic acid cation-exchange membrane, E
w=1100 gram/moles, thickness 210 μ m, film diameter 16mm) goes up and carry the tag teflon with pressure sintering and bond catalyst film (can be metal, metal oxide, nonmetal or macrocyclic compound catalyst etc.) respectively as working electrode and contrast electrode [2,3].Over against working electrode is to carry Pt with chemical deposition to deceive as auxiliary electrode (4).The gas electrode that makes thus (working electrode) is solid polymer electrolyte (Nafion) waterproof gas electrode, with compare with the prepared solid polymer electrolyte gas electrode of chemical deposition in the document, it not only has bigger electricity and urges specific activity, and because the water proofing property of electrode, greatly improved the stability of electrode reaction.
The lambda sensor such as the accompanying drawing 2 of combining closely and forming with kind electrode and capillary plate.Because metering function capillaceous, cause the detected sample air flow that arrives on the working electrode to be restricted and form diffusion mass transfer control.The electrode potential that makes working electrode with a little permanent electromotive force instrument is constant in-550mv (contrast electrode relatively), at this moment the oxygen that arrives on the working electrode by the kapillary diffusion is reduced immediately, and provide diffusion limiting current, and directly be directly proportional with oxygen number percent Shen Du in the sample gas.Kapillary directly contacts with working electrode, sample gas directly arrives on the working electrode through kapillary, not resembling has a film at barrier film and working electrode sound the Clark type sensor, and sample gas also will react by just arriving on the working electrode behind the liquid film after by barrier film, thereby the response of this sensor is very fast.Because working electrode carries out the reduction of oxygen in the sensor, then carry out opposite oxygen evolution reaction on the auxiliary electrode, the clean consumption and the accumulation of no material in the whole electrolytic cell do not resemble clean consumption and accumulation that material is arranged the galvanic cell type lambda sensor, so this sensor can be worked for a long time continuously and stably.
Compared with the prior art, the technique effect that reached of the present invention:
Through colleague expert appraisal: the present invention has initiated the current oxygen sensors based on solid polymer electrolyte in the world.Compare with the electrochemistry oxygen sensor that existing other types normal temperature is worked down, its response is fast, the life-span is long, precision is high, and the key technical indexes is in advanced international standard (seeing the following form).
The comparison of the technical indicator of all types of lambda sensors of table 1
| Sensor | Sensing range O 2％ | Fundamental error (full scale relatively) | Working temperature (℃) | Life-span | Response time | Sensor type |
| The 5964-00 5946-10 of U.S. Cole-Parmer company lambda sensor | 0-25 | ±2％ | 0-50 | The 6-8 month | 10 seconds 90% response times | The Clark type |
| The A.C.C.Sueng of Britain City University kapillary primary element lambda sensor | 0-21 | ±1.5％ | Room temperature | June | 80% response time 10-20 second | Kapillary current limliting method galvanic cell type |
| Japan Nafion lambda sensor | 0-12 | 25 | 90% response time was greater than 30 minutes | The solid polymer electrolyte electric potential type | ||
| Lambda sensor of the present invention | 0-25 | ≤±1.5％ | ≤50 | Continuous working was above 1 year | 95% response time≤5 second | The solid polymer electrolyte, capillary type current method |
This sensor technology advanced person, compact conformation, volume is little, and physical strength is good, has less temperature coefficient (0.3%/℃), than the approximately little order of magnitude of the temperature coefficient of Clark type lambda sensor (2%/℃).
Can measure the oxygen percent concentration that isolates in the environment with this sensor, as oxygen determination occasions such as mine, tunnel, warehouse, environmental protection, medical treatment, biotechnology, undersea ship, aerospaces.This sensor is equipped with behind the micro air pump oxygen in the measuring channel and container easily.Oxygen determination is on probation under medical experiment and coal mine shows that this sensor is easy and simple to handle, and signal stabilization is reliable, and favorable reproducibility is for condition has been created in instrumentation, the robotization of oxygen determination work.
Description of drawings:
Fig. 1 is a Nafion gas electrode structure.1-Nafion film wherein; The 2-working electrode; The 3-contrast electrode; The 4-auxiliary electrode.
Fig. 2 is a sensor construction.5-pore (φ=1mm) wherein; The 6-pore (φ=2mm); The 7-Nafion film (φ=16mm); 8,10 O-ring seals; The 9-working electrode; 11-pore (φ=160 μ m, length 1=4mm); 12-sensor loam cake; The 13-capillary plate (φ=16mm, thickness=4mm); 14-auxiliary electrode: 15-contrast electrode.
Fig. 3 is the sensor profile.16-window wherein; 17-sensor external diameter (φ=20mm): 18-sensor height (h=20mm).
Embodiment:
Below in conjunction with accompanying drawing architectural feature of the present invention is described further:
1.Pt the preparation of catalyzer and catalytic membrane thereof.
With 1 gram H
2PtCl
66H
2The dissolving of O adding distil water is diluted to 100 milliliters.Claim 1 gram KBH
4And add the dissolving of 40 ml distilled waters, drip 1 mole of KOH solution then till solution PH=11.Last two kinds of solution cool off (in ice bath) respectively after 0-3 ℃, with KBH
4Solution is once poured H into
2PtCl
6Also stir in the solution and get final product.Pour out top clear liquid after leaving standstill clarification such as solution, adding distil water is washed then, repeatedly for several times till PH=7.To clean that Pt is black to put into baking oven in 80-100 ℃ of oven dry (12 hours), and take out the platinum black of drying and cross 180 mesh sieves and obtain the platinum black powder.
Take by weighing 100 milligrams of platinum black powders, 40 milligram of 60% teflon emulsion mixes stirring, and dry by the fire under infrared lamp to the mud shape back, and taking out then on bitubular roller and rolling (50 ℃) one-tenth area repeatedly is 10cm
2Catalytic membrane (standby).
2. electrode preparation.
1 (the Nafion117 film of φ=16mm) boils in distilled water earlier after 1 hour and takes out, and it is clipped in the centre of a cylindrical reaction cell, one side at the 0.02 mol H that puts into of Nafion film
2PtCl
66 milliliters of solution are put into 0.5 mol KBH at another side
46 milliliters of solution (PH=11) react that to obtain area after 30 minutes be 0.9cm
2Platinum black electrode for making auxiliary electrode (4,14) (this is a chemical deposition in the document).Take off Nafion film that chemistry carries Pt and put into distilled water and boil after 1 hour again and take out, the one side hot pressing a slice area over against auxiliary electrode on bitubular roller is 0.9cm
2, the about 40 μ m of thickness platinum black teflon catalytic membrane (the roller temperature is controlled at 70-90 ℃, the about 100kg/cm of pressure
2) as working electrode (9), meanwhile the same one side at auxiliary electrode is 0.1cm with 1 area of identical method hot pressing
2Platinum black teflon catalytic membrane as contrast electrode (15), then this Nafion electrode is put into 1 mol sulfuric acid soak 24 hours standby.
3. sensor assembling
As shown in Figure 1, the Nafion membrane electrode after the acidifying is put into sensor cavity earlier, put poly (methyl methacrylate) plate (capillary bore φ=160 μ m, capillary pipe length l=4mm) that a slice has pore and tighten the sensor loam cake and get final product pasting then by working electrode one side.
Claims (4)
1. solid polymer electrolyte, capillary lambda sensor, it is characterized in that: it is by constituting with the lower part: Nafion 117 films (1); Working electrode (9); Contrast electrode (15); Auxiliary electrode (4,14); Porose plastic plate (5); Capillary plate (13); The bottom center has the sensor cavity and the sensor loam cake (12) of an aperture (6);
Therein, working electrode is loaded on the one side of Nafion film, and reference electrode and auxiliary electrode are loaded on the another side of Nifion film, and capillary plate is fixed on the working electrode surface towards gas phase, and porose plastic plate is fixed on the below of cavity.
2. method that is used to make the described sensor of claim 1, it is characterized in that: this method may further comprise the steps:
(1) preparation waterproof powder catalyst film;
(2) above-mentioned catalyst film is rolled on the one side of Nafion film lead working electrode;
(3) roll on the another side of Nafion film with same catalyst film and obtain contrast electrode;
(4) precipitate on one side at the contrast electrode of Nafion film with chemical deposition and obtain auxiliary electrode.
3. by the described method of claim 2, it is characterized in that: working electrode is to comprise metal, or metal oxide, or the fine catalyst of nonmetal or macrocyclic compound, mix with teflon, be processed into the teflon catalyst film through rolling, be reprocessed into the solid polymer electrolyte waterproof gas diffused electrode: prepare the platinum black auxiliary electrode (4 that by known chemical deposition, 14), on bitubular roller to a slice teflon catalyst film in the one side hot pressing of auxiliary electrode, constitute working electrode (9), simultaneously, at auxiliary electrode (4,14) with a slice teflon catalyst film in the identical method hot pressing, constitute contrast electrode (15) on the same one side.
4. by the described method of claim 2, it is characterized in that: the electrode that above-mentioned manufacturing is good, in the sensor cavity of packing into after, by working electrode one side, paste and put the plate that a slice has pore, and together electrode and capillary pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94107055 CN1043488C (en) | 1994-06-10 | 1994-06-10 | Solid polymer electrolyte, capillary type oxygen sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94107055 CN1043488C (en) | 1994-06-10 | 1994-06-10 | Solid polymer electrolyte, capillary type oxygen sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1114417A CN1114417A (en) | 1996-01-03 |
| CN1043488C true CN1043488C (en) | 1999-05-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94107055 Expired - Fee Related CN1043488C (en) | 1994-06-10 | 1994-06-10 | Solid polymer electrolyte, capillary type oxygen sensor |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100472209C (en) * | 2000-09-13 | 2009-03-25 | 中国科学院长春应用化学研究所 | Process for preparing full-fluorine sulfornic ions exchange membrane electrode |
| US7258773B2 (en) * | 2003-08-12 | 2007-08-21 | Rae Systems, Inc. | Solid polymer electrolyte oxygen sensor |
| CN1734262B (en) * | 2004-08-13 | 2010-09-01 | 杭州生源医疗保健技术开发有限公司 | Electrochemical sensor with solid polymer electrolyte and gas detection method using the same |
| JP4725494B2 (en) * | 2006-04-27 | 2011-07-13 | 株式会社デンソー | Gas sensor |
| CN102183566A (en) * | 2011-01-05 | 2011-09-14 | 高国强 | Oxygen volume percent concentration sensor based on capillary chemical corrosion method |
| CN102903944B (en) * | 2012-10-24 | 2014-08-20 | 大连交通大学 | New method for depositing Pt nano particles on surface of Nafion proton exchange membrane |
| DE102016003452B4 (en) | 2016-03-23 | 2023-05-11 | Dräger Safety AG & Co. KGaA | Electrochemical gas sensor |
| CN109416337B (en) * | 2016-06-30 | 2021-06-29 | 霍尼韦尔国际公司 | Acrylonitrile detection using biased electrochemical sensors |
| CN110300887A (en) * | 2017-03-14 | 2019-10-01 | 霍尼韦尔国际公司 | Ultra-thin electromechanical gas sensor |
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1994
- 1994-06-10 CN CN 94107055 patent/CN1043488C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1114417A (en) | 1996-01-03 |
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