CN1376916A - Electrochemical sensor of hydrogen in extreme environment - Google Patents
Electrochemical sensor of hydrogen in extreme environment Download PDFInfo
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- CN1376916A CN1376916A CN 02111369 CN02111369A CN1376916A CN 1376916 A CN1376916 A CN 1376916A CN 02111369 CN02111369 CN 02111369 CN 02111369 A CN02111369 A CN 02111369A CN 1376916 A CN1376916 A CN 1376916A
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Abstract
An electrochemical hydrogen sensor used in extreme environmental has a metal electrode and a reference metal/metal oxide electrode. Said metal electrode is a metal ring made of Pt, Pd, Ru, Ir, or Au. Said reference electrode has a metal wire with active oxide film on its surface. Its advantages are small size, high mechanical strength, wide application range and low cost.
Description
Technical field
The present invention relates to sensor, relate in particular to a kind of electrochemical sensor of hydrogen that is applicable to extreme environment.
Background technology
The concentration of solubilised state hydrogen in the aqueous medium is one of most important chemical property of aqueous solution.In industries such as chemistry, chemical industry, medicine, material, electric power, the density of hydrogen in the aqueous medium is the sign that many synthetic reactions are carried out degree on the one hand, and it can reflect the state of equipment on the other hand, and especially whether reaction vessel and pipeline have been subjected to corrosion.In addition, the density of hydrogen in the solution still is the important parameter of knowledge of natural environment environment and geologic function.Hydrogen gas detector in the past can only be worked under lower temperature, pressure mostly, the invention provides a kind of can be to the high temperature condition of high voltage from normal temperature and pressure, the electrochemical sensor of density of hydrogen in real-time detection and the long term monitoring aqueous solution.
Summary of the invention
The purpose of this invention is to provide a kind of electrochemical sensor of hydrogen that is applicable to extreme environment.
It comprises metallic hydrogen electrode and metal/metal oxide contrast electrode; Said metallic hydrogen thickness of electrode is 0.1～0.4 millimeter, and length is 5～12 millimeters, and width is 3～8 millimeters a becket, and the one face down bonding is connected to plain conductor; Said metal/metal oxide contrast electrode has tinsel, and its surface is provided with the activating oxide film.
Advantage of the present invention is, the metallic hydrogen electrode and the metal/metal oxide electrode volume that are proposed are all very little, has very high physical strength and toughness, under the temperature of broadness, pressure condition, has good working performance, and related preparation method's technology is simple, with low cost, be easy to promote.By these two kinds of electrochemical sensors that electrode constitutes, can dynamically monitor the metal corrosion condition of high-temperature high-pressure apparatus in real time, as the reaction vessel of chemosynthesis, geothermal power generation, nuclear power station, thermal power station, reactor core, when pipeline is corroded, the dissolving density of hydrogen can obviously increase in its internal water medium, the electrochemical sensor of hydrogen that the present invention proposes is suitable for the dynamic monitoring of the said equipment.It also is suitable in poisonous and harmful, hot environment the density of hydrogen in the monitoring aqueous medium, stacks dynamic monitoring with treating apparatus as underground nuke rubbish hold-up vessel, bazardous waste.In addition, it also is suitable under extreme conditions such as High Temperature High Pressure, highly acid, hot online detection and long term monitoring being carried out in geologic function and physical environment, as deep-sea detecting and volcano monitoring.Its great advantage is, can use in that highly acid, strong basicity and high-temperature, high pressure fluid are medium-term and long-term, and the hydrogen electrode made from gold wherein, and the metal/metal oxide contrast electrode can also be resisted the dissolving H of high concentration
2The corrosion of S.
Description of drawings
Accompanying drawing is the electrochemical sensor of hydrogen structural representation that is applicable to extreme environment.
Among the figure: 1. metallic hydrogen electrode, 2. pick-up unit, 3. metal/metal oxide contrast electrode, 4. plain conductor and insulation course, 5. becket, 6. tinsel, 7. activating oxide film.
Embodiment
The electrochemical sensor of hydrogen that is applicable to extreme environment comprises metallic hydrogen electrode 1 and metal/metal oxide contrast electrode 3; Said metallic hydrogen thickness of electrode is 0.1～0.4 millimeter, and length is 5～12 millimeters, and width is 3～8 millimeters a becket 5, and the one face down bonding is connected to plain conductor 4; Said metal/metal oxide contrast electrode has tinsel 6, and its surface is provided with activating oxide film 7.
Preparation method's step of said metallic hydrogen electrode is as follows:
1) getting thickness is 0.1～0.4 millimeter sheet metal, and cutting into length is 5～12 millimeters, and width is 3～8 millimeters a strip, is girth with the long limit of above-mentioned sheet metal, and it is curved a becket, plain conductor in the one side weld;
2) with boiling in becket and welding position immersion acetone or the triclene, to remove organic impurities, immerse the hydrochloric acid solution that concentration is 3-6M again, ultrasonic cleaning was taken out the back and cleaned with distilled water more than 1 minute, and is air-dry;
3) soluble polyimide is dissolved in the organic solvent, is configured to concentration and is 5～50% solution, this solution is coated on the plain conductor, air-dry.
The material of above-mentioned becket is a kind of in platinum, palladium, ruthenium, iridium and the gold; The material of plain conductor is a kind of in platinum, gold, silver and the copper;
Preparation method's step of said metal/metal oxide contrast electrode is as follows:
1) cut-off directly is 0.1～1 millimeter a tinsel, polish with schmigel in the surface, to remove original oxidation film, in acetone or triclene, boil then, to remove organic impurities, immerse the hydrochloric acid solution that concentration is 3-6M again, ultrasonic cleaning is more than 1 minute, take out the back and clean with distilled water, air-dry;
2) tinsel after polishing, the cleaning places the corundum crucible that is covered with goldleaf, and cover with the anhydrous carbonate powder, crucible is put into muffle furnace be heated to 850～930 ℃, and constant temperature 1.5～5 hours, after taking-up is chilled to room temperature, with the carbonate solid in the diluted hydrochloric acid dissolution crucible, then with washed with de-ionized water to remove soluble component, insert in 80～120 ℃ of baking ovens dry, its surface coverage thick 15～30 microns uniform oxide layers;
3) scrape off one section oxide layer at an end wiry, the plain conductor of on this end, burn-oning;
4) soluble polyimide is dissolved in the organic solvent, is configured to concentration and is 5～50% solution, this solution is coated on the plain conductor, air-dry.
Above-mentioned material wiry is Ti, Zr, Ir, W, Ru, a kind of among the Pd.Oxide is an oxide of the same race wiry.Carbonate is a kind of in lithium carbonate, sodium carbonate and the sal tartari.
The electrochemical sensor of hydrogen that the present invention proposes is made up of hydrogen electrode and contrast electrode, and from the galvanochemistry angle, sensor can be expressed as:
M
H|H
2，H
+，H
2O|(M|MO
x)
Ref????????????????(1)
M herein
HBe hydrogen electrode, and (M|MO
x)
RefBe the metal/metal oxide electrode, when the electrode pairing of it and other type, can be used as the pH electrode, H
2Detection, (M|MO
x)
RefPlay a part contrast electrode.Under given temperature, pressure, ionic strength conditions, the potential difference (PD) of measuring (Δ E) is dissolving H
2The function of activity, according to this specific rule being expressed as:
R, F and T represent gas law constant, Faraday constant and temperature (° K), aH respectively herein
2O is the activity of water, E °
M|MOx, be M|MO
x, i.e. the normal potential of metal/metal oxide electrode, K
H(mol kg
-1Atm
-1) and γ
H2It is respectively the activity coefficient of henry 's law constant and H2.
The used material of above-mentioned hydrogen electrode is a kind of in platinum, palladium, ruthenium, iridium and the gold foil.Ensureing under the prerequisite of required physical strength, selecting for use thin, the less sheet metal of size to help reducing cost, and dwindle the size of electrode.The size of sheet metal generally should between: thickness is 0.1～0.4 millimeter, and length is 5～12 millimeters, and width is 3～8 millimeters a strip
With the first step that these sheet metals are made hydrogen electrodes, be that the long limit with sheet metal is a girth, it is curved a becket, plain conductor in the one side weld is as circuit and physical connection.Plain conductor is preferably selected platinum or golden lead for use, has improved the overall performance of sensor; Also can use silver and copper conductor, to reduce cost.
Second step was that its surface is thoroughly cleaned, and was divided into organic solvent cleaning and acid solution and cleaned, and the order of the two is unimportant.
Metal/metal oxide electrode material therefor is the stable tinsel of chemical property, as titanium, zirconium, iridium, tungsten, ruthenium and palladium silk.Length wiry can be determined according to the electrode size needs and the two aspect factors that are easy to process, be generally 0.6～1.2 centimeter length.Under the prerequisite that ensures required physical strength, select for use thinner tinsel to help reducing cost, and dwindle the size of electrode.Diameter wiry generally should be between 0.1～1 millimeter.
With the key that these metals are made electrode, be to form the oxidation film that is suitable for electrochemical measurement in wire surface.Studies show that, the oxidation film that wire surface forms naturally, and simply tinsel is heated formed oxidation film in air, all can't be competent at electrochemical gaging.Therefore, as the first step of making electrode, be to remove the original oxidation film of wire surface.The method that the present invention adopts mechanical grinding and chemical cleaning to combine.The former also available blasting treatment, the latter is divided into organic solvent and cleans that (clean with acid solution, the order of the two is unimportant.
Making another key of metal/metal oxide electrode, is will coat one deck in wire surface can see through H
+The activating oxide film of ion.It is the heating of medium that the present invention has adopted with carbonate.Wherein heating-up temperature should be higher than the fusing point of selected carbonate, should guarantee also that simultaneously carbonate does not have tangible decomposition in constant temperature time.The fusing point of three kinds of carbonate and the heating-up temperature of recommendation are respectively:
| Carbonate | Fusing point | Heating-up temperature |
| ????Li 2CO 3 | ????723℃ | ????850-870℃ |
| ????Na 2CO 3 | ????851℃ | ????880-900℃ |
| ????K 2CO 3 | ????891℃ | ????910-930℃ |
The constant temperature time of tinsel in the carbonate melt should be made corresponding adjustment according to the relative chemical activity of different metal.The constant temperature time that the present invention recommends (hour) be:
| Metal | ????Ti | ????????Zr | ?????????Ru | ??????????W | ??????????Pd | ????Ir |
| Time | ????1.5 | ?????1.5-2.0 | ???????3.0-3.5 | ???????3.0-3.5 | ???????4.0-4.5 | ????5.0 |
(PI Polyimide) as the insulating protective layer of plain conductor, is because it is easy to coating, and has heat-resisting quantity preferably that polyimide can be no more than the medium-term and long-term use of 260 ℃ of environment in temperature, and intermittently serviceability temperature can reach 480 ℃ to select polyimide for use.In addition, also can select for use teflon and organosilicon as insulating protective layer.Teflon has good heat-resistance equally, can be under 300 ℃ of temperature use for a long time, but that it molten, insoluble is difficult to it is processed.Organosilicon also has better heat-resisting and stability, uses more convenient.
The performance of electrochemical sensor of hydrogen and suitable environment are relevant with the manufacturing materials of hydrogen electrode.Generally speaking, hydrogen electrode with platinum and palladium making, under normal temperature to 270 ℃ hot conditions, all has good working performance, but its hydrogen sulfide corrosion resistant ability is relatively poor, the concentration of hydrogen sulfide that dissolves in solution is higher, and temperature is when being higher than 100 ℃, and the corrosive attack of sulfuretted hydrogen can cause electrode to poison, and performance descends rapidly.Relatively poor with the hydrogen electrode sensitivity at a lower temperature that gold is made, but more than 200 ℃, its performance and platinum, palladium electrode are equally matched, and the gold electrode hydrogen sulfide corrosion resistant is very competent, still can use for a long time in high temperature, high-concentration hydrogen sulfide solution.With the hydrogen electrode that ruthenium, iridium are made, performance is between platinum electrode and gold electrode.
Below in conjunction with embodiment the present invention is elaborated.
Example 1: make hydrogen electrode with platinum
1) getting thickness is 0.2 millimeter platinum sheet, and cutting into length is 8.5 millimeters, and width is 4.5 millimeters a strip, is girth with the long limit of platinized platinum, it is curved an annulus, golden lead in the one side weld; Boil in acetone then, to remove organic impurities, immerse the hydrochloric acid solution that concentration is 6M again, ultrasonic cleaning was taken out the back and cleaned with distilled water more than 1 minute, and is air-dry;
2) immerse platinum loop and welding position in the acetone and boil, to remove organic impurities, immerse the hydrochloric acid solution that concentration is 6M again, ultrasonic cleaning was taken out the back and cleaned with distilled water more than 1 minute, and is air-dry;
3) soluble polyimide is dissolved in the organic solvent, is configured to concentration and is 30% solution, this solution is coated on the golden lead, air-dry.Can repeat for several times, until the insulating protective layer that forms adequate thickness, so far electrode completes.
Example 2: make hydrogen electrode with palladium
1) getting thickness is 0.2 millimeter palladium metal sheet, and cutting into length is 8.5 millimeters, and width is 4.5 millimeters a strip, is girth with the long limit of palladium sheet, it is curved an annulus, platinum lead in the one side weld;
2) immerse palladium ring and welding position in the triclene and boil, to remove organic impurities, immerse the hydrochloric acid solution that concentration is 3M again, ultrasonic cleaning was taken out the back and cleaned with distilled water more than 1 minute, and is air-dry;
3) soluble polyimide is dissolved in the organic solvent, is configured to concentration and is 30% solution, this solution is coated on the platinum lead, air-dry.Can repeat for several times, until the insulating protective layer that forms adequate thickness, so far electrode completes.
Example 3: make hydrogen electrode with gold
1) getting thickness is 0.25 millimeter gold plaque, and cutting into length is 10 millimeters, and width is 5 millimeters a strip, is girth with the long limit of gold plaque, it is curved an annulus, silver-colored lead in the one side weld;
2) immerse gold ring and welding position in the acetone and boil, to remove organic impurities, immerse the hydrochloric acid solution that concentration is 6M again, ultrasonic cleaning was taken out the back and cleaned with distilled water more than 1 minute, and is air-dry;
3) soluble polyimide is dissolved in the organic solvent, is configured to concentration and is 30% solution, this solution is coated on the silver-colored lead, air-dry.Can repeat for several times, until the insulating protective layer that forms adequate thickness, so far electrode completes.
Example 4: make hydrogen electrode with iridium
1) getting thickness is 0.15 millimeter iridium metals sheet, and cutting into length is 6 millimeters, and width is 2.5 millimeters a strip, is girth with the long limit of iridium sheet, it is curved an annulus, golden lead in the one side weld;
2) immerse iridium ring and welding position in the triclene and boil, to remove organic impurities, immerse the hydrochloric acid solution that concentration is 6M again, ultrasonic cleaning was taken out the back and cleaned with distilled water more than 1 minute, and is air-dry;
3) soluble polyimide is dissolved in the organic solvent, is configured to concentration and is 30% solution, this solution is coated on the golden lead, air-dry.Can repeat for several times, until the insulating protective layer that forms adequate thickness, so far electrode completes.
Example 5: make hydrogen electrode with ruthenium
1) getting thickness is 0.15 millimeter ruthenium sheet metal, and cutting into length is 6 millimeters, and width is 2.5 millimeters a strip, is girth with the long limit of ruthenium sheet, it is curved an annulus, golden lead in the one side weld;
2) immerse ruthenium ring and welding position in the acetone and boil, to remove organic impurities, immerse the hydrochloric acid solution that concentration is 6M again, ultrasonic cleaning was taken out the back and cleaned with distilled water more than 1 minute, and is air-dry;
3) soluble polyimide is dissolved in the organic solvent, is configured to concentration and is 30% solution, this solution is coated on the golden lead, air-dry.Can repeat for several times, until the insulating protective layer that forms adequate thickness, so far electrode completes.
Example 6: make Ti/TiO
2Contrast electrode
1) cut-off directly is 0.3 millimeter a Ti silk, after mechanical grinding is removed oxidation film, is cut into several sections of every section about 1 centimetre length, boil in triclene, take out the Ti silk, drying the back is ultrasonic cleaning 2 minutes in the hydrochloric acid of 3M in concentration, clean with distilled water then, air-dry;
2) the Ti silk after polishing, the cleaning places the corundum crucible that is covered with goldleaf, and covers with the Carbon Dioxide lithium powder; Crucible is placed muffle furnace, be heated to 870 ℃, and constant temperature 1.5 hours, after being chilled to room temperature, with the lithium carbonate solid in the HCl dissolving crucible of 1M concentration, use washed with de-ionized water then, to remove soluble component, it is a dry night in 80 ℃ the baking oven that the Ti silk is moved into temperature, its surface coverage thick about 20 microns uniform oxide layers;
3) scrape off the oxide layer of about 1 millimeters long at an end of Ti silk.The diameter of burn-oning on this end is 0.1 millimeter a golden lead;
4) be that 30% polyimide solution is coated on golden lead and the solder joint position with soft brush with concentration, air-dry, to form insulating protective layer, so far electrode completes.
Example 7: make Zr/ZrO
2Contrast electrode
1) cut-off directly is 0.3 millimeter a Zr silk, after mechanical grinding is removed oxidation film, is cut into several sections of every section about 1 centimetre length, boils in acetone, takes out the Zr silk, and drying the back is ultrasonic cleaning 2 minutes in the hydrochloric acid of 3M in concentration, cleans with distilled water then, air-dry;
2) the Zr silk after polishing, the cleaning places the corundum crucible that is covered with goldleaf, and covers with the natrium carbonicum calcinatum powder; Crucible is placed muffle furnace, be heated to 880 ℃, and constant temperature 2 hours, after being chilled to room temperature, with the sodium carbonate solid in the HCl dissolving crucible of 1M concentration, use washed with de-ionized water then, to remove soluble component, it is a dry night in 80 ℃ the baking oven that the Zr silk is moved into temperature, its surface coverage thick about 20 microns uniform oxide layers;
3) scrape off the oxide layer of about 1 millimeters long at an end of Zr silk.The diameter of burn-oning on this end is 0.1 millimeter a golden lead;
4) be that 30% polyimide solution is coated on golden lead and the solder joint position with soft brush with concentration, air-dry, to form insulating protective layer, so far electrode completes.
Example 8: make W/WO
3Contrast electrode
1) cut-off directly is 0.3 millimeter a W silk, after mechanical grinding is removed oxidation film, is cut into several sections of every section about 1 centimetre length, boils in acetone, takes out the W silk, and drying the back is ultrasonic cleaning 2 minutes in the hydrochloric acid of 3M in concentration, cleans with distilled water then, air-dry;
2) the W silk after polishing, the cleaning places the corundum crucible that is covered with goldleaf, and covers with the natrium carbonicum calcinatum powder; Crucible is placed muffle furnace, be heated to 880 ℃, and constant temperature 3 hours, after being chilled to room temperature, with the sodium carbonate solid in the HCl dissolving crucible of 1M concentration, use washed with de-ionized water then, to remove soluble component, it is a dry night in 80 ℃ the baking oven that the W silk is moved into temperature, its surface coverage thick about 20 microns uniform oxide layers;
3) scrape off the oxide layer of about 1 millimeters long at an end of W silk.The diameter of burn-oning on this end is 0.1 millimeter a silver-colored lead;
4) be that 30% polyimide solution is coated on silver-colored lead and the solder joint position with soft brush with concentration, air-dry, to form insulating protective layer, so far electrode completes.
Example 9: make Ir/IrO
2Contrast electrode
1) cut-off directly is 0.15 millimeter an Ir silk, after mechanical grinding is removed oxidation film, is cut into several sections of every section about 1 centimetre length, boils in acetone, takes out the Ir silk, and drying the back is ultrasonic cleaning 2 minutes in the hydrochloric acid of 3M in concentration, cleans with distilled water then, air-dry;
2) the Ir silk after polishing, the cleaning places the corundum crucible that is covered with goldleaf, and covers with the natrium carbonicum calcinatum powder; Crucible is placed muffle furnace, be heated to 880 ℃, and constant temperature 5 hours, after being chilled to room temperature, with the sodium carbonate solid in the HCl dissolving crucible of 1M concentration, use washed with de-ionized water then, to remove soluble component, it is a dry night in 80 ℃ the baking oven that the Ir silk is moved into temperature, its surface coverage thick about 20 microns uniform oxide layers;
3) scrape off the oxide layer of about 1 millimeters long at an end of Ir silk.The diameter of burn-oning on this end is 0.1 millimeter a platinum lead;
4) be that 30% polyimide solution is coated on the platinum lead and the solder joint position with soft brush with concentration, air-dry, to form insulating protective layer, so far electrode completes.
Example 10: make Ru/RuO
2Contrast electrode
1) cut-off directly is 0.15 millimeter a Ru silk, after mechanical grinding is removed oxidation film, is cut into several sections of every section about 1 centimetre length, boil in triclene, take out the Ru silk, drying the back is ultrasonic cleaning 2 minutes in the hydrochloric acid of 3M in concentration, clean with distilled water then, air-dry;
2) the Ru silk after polishing, the cleaning places the corundum crucible that is covered with goldleaf, and covers with the Carbon Dioxide lithium powder; Crucible is placed muffle furnace, be heated to 870 ℃, and constant temperature 3.5 hours, after being chilled to room temperature, with the lithium carbonate solid in the HCl dissolving crucible of 1M concentration, use washed with de-ionized water then, to remove soluble component, it is a dry night in 80 ℃ the baking oven that the Ru silk is moved into temperature, its surface coverage thick about 20 microns uniform oxide layers;
3) scrape off the oxide layer of about 1 millimeters long at an end of Ru silk.The diameter of burn-oning on this end is 0.1 millimeter a golden lead;
4) be that 30% polyimide solution is coated on golden lead and the solder joint position with soft brush with concentration, air-dry, to form insulating protective layer, so far electrode completes.
Example 11: make the Pd/PdO contrast electrode
1) cut-off directly is 0.15 millimeter a Pd silk, after mechanical grinding is removed oxidation film, is cut into several sections of every section about 1 centimetre length, boil in triclene, take out the Pd silk, drying the back is ultrasonic cleaning 2 minutes in the hydrochloric acid of 3M in concentration, clean with distilled water then, air-dry;
2) the Pd silk after polishing, the cleaning places the corundum crucible that is covered with goldleaf, and covers with the Carbon Dioxide lithium powder; Crucible is placed muffle furnace, be heated to 870 ℃, and constant temperature 4 hours, after being chilled to room temperature, with the lithium carbonate solid in the HCl dissolving crucible of 1M concentration, use washed with de-ionized water then, to remove soluble component, it is a dry night in 80 ℃ the baking oven that the Pd silk is moved into temperature, its surface coverage thick about 20 microns uniform oxide layers;
3) scrape off the oxide layer of about 1 millimeters long at an end of Pd silk.The diameter of burn-oning on this end is 0.1 millimeter a silver-colored lead;
4) be that 30% polyimide solution is coated on silver-colored lead and the solder joint position with soft brush with concentration, air-dry, to form insulating protective layer, so far electrode completes.
Claims (8)
1. an electrochemical sensor of hydrogen that is applicable to extreme environment is characterized in that, it comprises metallic hydrogen electrode [1] and metal/metal oxide contrast electrode [3]; Said metallic hydrogen thickness of electrode is 0.1～0.4 millimeter, and length is 5～12 millimeters, and width is 3～8 millimeters a becket [5], and the one face down bonding is connected to plain conductor [4]; Said metal/metal oxide contrast electrode has tinsel [6], and its surface is provided with activating oxide film [7].
2. a kind of electrochemical sensor of hydrogen that is applicable to extreme environment according to claim 1 is characterized in that, preparation method's step of said metallic hydrogen electrode is as follows:
1) getting thickness is 0.1～0.4 millimeter sheet metal, and cutting into length is 5～12 millimeters, and width is 3～8 millimeters a strip, is girth with the long limit of above-mentioned sheet metal, and it is curved a becket, plain conductor in the one side weld;
2) with boiling in becket and welding position immersion acetone or the triclene, to remove organic impurities, immerse the hydrochloric acid solution that concentration is 3-6M again, ultrasonic cleaning was taken out the back and cleaned with distilled water more than 1 minute, and is air-dry;
3) soluble polyimide is dissolved in the organic solvent, is configured to concentration and is 5～50% solution, this solution is coated on the plain conductor, air-dry.
3. a kind of electrochemical sensor of hydrogen that is applicable to extreme environment according to claim 1 and 2 is characterized in that, the material of said becket is a kind of in platinum, palladium, ruthenium, iridium and the gold;
4. a kind of electrochemical sensor of hydrogen that is applicable to extreme environment according to claim 1 and 2 is characterized in that, the material of said plain conductor is a kind of in platinum, gold, silver and the copper;
5. a kind of electrochemical sensor of hydrogen that is applicable to extreme environment according to claim 1 is characterized in that, preparation method's step of said metal/metal oxide contrast electrode is as follows:
1) cut-off directly is 0.1～1 millimeter a tinsel, polish with schmigel in the surface, to remove original oxidation film, in acetone or triclene, boil then, to remove organic impurities, immerse the hydrochloric acid solution that concentration is 3-6M again, ultrasonic cleaning is more than 1 minute, take out the back and clean with distilled water, air-dry;
2) tinsel after polishing, the cleaning places the corundum crucible that is covered with goldleaf, and cover with the anhydrous carbonate powder, crucible is put into muffle furnace be heated to 850～930 ℃, and constant temperature 1.5～5 hours, after taking-up is chilled to room temperature, with the carbonate solid in the diluted hydrochloric acid dissolution crucible, then with washed with de-ionized water to remove soluble component, insert in 80～120 ℃ of baking ovens dry, its surface coverage thick 15～30 microns uniform oxide layers;
3) scrape off one section oxide layer at an end wiry, the plain conductor of on this end, burn-oning;
4) soluble polyimide is dissolved in the organic solvent, is configured to concentration and is 5～50% solution, this solution is coated on the plain conductor, air-dry.
6. a kind of according to claim 1 or 5 electrochemical sensor of hydrogen that is applicable to extreme environment is characterized in that said material wiry is Ti, Zr, Ir, W, Ru, a kind of among the Pd.
7. a kind of according to claim 1 or 5 electrochemical sensor of hydrogen that is applicable to extreme environment is characterized in that, said oxide is an oxide of the same race wiry.
8. a kind of according to claim 1 or 5 electrochemical sensor of hydrogen that is applicable to extreme environment is characterized in that, said carbonate is a kind of in lithium carbonate, sodium carbonate and the sal tartari.
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| CN100419416C (en) * | 2005-03-21 | 2008-09-17 | 张荣华 | Zr/ZrO2 electrode and producing method thereof and integrated high temperature high-pressure chemical sensor composed by the same |
| CN100445739C (en) * | 2004-02-19 | 2008-12-24 | 株式会社新泻Tlo | Hydrogen gas sensor |
| CN100454012C (en) * | 2006-08-21 | 2009-01-21 | 浙江大学 | Pressure adaptive dissolving carbon dioxide exploring electrode and preparation method |
| CN101467030B (en) * | 2006-04-20 | 2013-02-27 | 应用纳米技术控股股份有限公司 | Hydrogen sensor |
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2002
- 2002-04-12 CN CNB021113696A patent/CN1155820C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445739C (en) * | 2004-02-19 | 2008-12-24 | 株式会社新泻Tlo | Hydrogen gas sensor |
| CN100419416C (en) * | 2005-03-21 | 2008-09-17 | 张荣华 | Zr/ZrO2 electrode and producing method thereof and integrated high temperature high-pressure chemical sensor composed by the same |
| CN101467030B (en) * | 2006-04-20 | 2013-02-27 | 应用纳米技术控股股份有限公司 | Hydrogen sensor |
| CN100454012C (en) * | 2006-08-21 | 2009-01-21 | 浙江大学 | Pressure adaptive dissolving carbon dioxide exploring electrode and preparation method |
| CN104422717A (en) * | 2013-08-19 | 2015-03-18 | 深圳市深安旭传感技术有限公司 | Catalytic element having poison resistance and gas sensor using same |
| CN104422717B (en) * | 2013-08-19 | 2019-12-06 | 深圳市深安旭传感技术有限公司 | Catalytic element with antitoxic property and gas sensor using same |
| CN114072665A (en) * | 2019-07-01 | 2022-02-18 | 东京窑业株式会社 | Solid reference substance and hydrogen sensor |
| CN114072665B (en) * | 2019-07-01 | 2024-03-12 | 东京窑业株式会社 | Solid reference substance and hydrogen sensor |
| WO2021218628A1 (en) * | 2020-04-30 | 2021-11-04 | 深圳安吉尔饮水产业集团有限公司 | Water ph detection sensor and use of ruthenium-iridium electrode as ph sensing material |
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| CN1155820C (en) | 2004-06-30 |
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