CN101881749A - All-solid state dissolved oxygen sensor and preparation method thereof - Google Patents
All-solid state dissolved oxygen sensor and preparation method thereof Download PDFInfo
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- CN101881749A CN101881749A CN 201010211482 CN201010211482A CN101881749A CN 101881749 A CN101881749 A CN 101881749A CN 201010211482 CN201010211482 CN 201010211482 CN 201010211482 A CN201010211482 A CN 201010211482A CN 101881749 A CN101881749 A CN 101881749A
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000001301 oxygen Substances 0.000 title claims abstract description 104
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 104
- 239000007787 solid Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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Abstract
The invention provides an all-solid state dissolved oxygen sensor, which comprises a substrate, and reference electrode, a counter electrode and a working electrode parallelly positioned on the substrate, wherein the reference electrode consists of a reactive electrode, a silver/silver chloride electrode positioned on the reactive electrode and a lead wire connected with the reactive electrode; the counter electrode and the working electrode consist of reactive electrodes and lead wires connected with the reactive electrodes; an insulating layer capable of exposing the silver/silver chloride electrode, the reactive electrode of the counter electrode and the working electrode covers on the substrate; an electrolytic layer covers on the silver/silver chloride electrode, the reactive electrode of the counter electrode and the reactive electrode of the working electrode; and an oxygen permeable membrane covers on the electrolytic layer. In the all-solid state dissolved oxygen sensor, three electrodes of the conventional dissolved oxygen sensor are integrated on one substrate so as to realize the miniaturization of the dissolved oxygen sensor, and the all-solid state dissolved oxygen sensor has the advantages of convenient carrying, simple operation and quick response. The invention also provides a preparation method for the all-solid state dissolved oxygen sensor, which has the advantages of simplifying a manufacturing process, reducing manufacturing cost, and being suitable for mass production.
Description
Technical field
The present invention relates to the electrochemical sensor technical field, relate in particular to a kind of all-solid state dissolved oxygen sensor and preparation method thereof.
Background technology
Physiology oxygen is human metabolic neccessary composition, sucks sufficient oxygen, makes to have enough dissolved oxygen DOs in the arterial blood, and is most important to earning a bare living.Clinically, the blood dissolves oxygen saturation is an important physical signs of human body, uses the oxygen saturation measurement accuracy height of traditional blood gas analysis method and spectrophotometric method, but the measuring process complexity is loaded down with trivial details, the cost height, required time is longer, and often detecting with this needs several hrs consuming time.When needs detected blood oxygen concentration to first-aid patients, can bring life danger so long detection time to patient.
1956, Clark proposed film and has covered the oxygen electrode technology, and had produced the syringe-type lambda sensor that is used for the dissolved oxygen concentration measurement.In this lambda sensor, see through the working electrode surface generation electrochemical reaction of dissolved oxygen DO in being immersed in electrolyte solution of oxygen permeation membrane, the size of current that electrochemical reaction produced is directly proportional with dissolved oxygen concentration.
Traditional Clark formula dissolved oxygen electrode is a column structure, by working electrode (gold or platinum electrode), and the Ag/AgCl contrast electrode, electrolytic solution, oxygen permeation membrane, contact conductor and electrode sleeve constitute.The traditional electrode volume is big, the cost height, and needed sample solution is many, and therefore, microminiaturization becomes the development trend of Clark electrode.At the beginning of the nineties at the end of the eighties in last century, Japanese scientist I.Karube and S.Suzuki take the lead in the microminiaturization of Clark formula oxygen electrode and industrialization are launched research.They successfully are incorporated into the conductor etching technology in the manufacturing process of Clark formula oxygen electrode.Microminiaturized Clark formula oxygen electrode has reduced cost, has simplified the dissolved oxygen sensing relevant device, helps Industry Promotion.
Along with the development of sensor processing technology, serigraphy in recent years, Laser mark technology and gluing technology increasingly mature, the research and development that utilizes these modes to make microsensor has good prospects, and than the conductor etching method, this technology is more simple and convenient, cost is lower, and efficient is higher.
Laser mark technology adopts High Power Laser Pulses to shine the workpiece to be processed surface, and the energy of laser light wave is absorbed by workpiece, and the local temperature of workpiece material is raise rapidly, and the irradiation area instant vaporization with workpiece reaches processing purpose.Than the common process technology, laser index carving processing degree of freedom is big, to the workpiece not damaged, and precision height, efficient height.
Serigraphy belongs to porous printing, is silk fabrics, synthetic fabrics or wire gauze are stretched tight on screen frame, adopts manual method of carving paint film or photochemistry plate-making to make screen printing forme.Modern screen printing technique then is to utilize photosensitive material by photomechanical method, the silk screen hole partly of picture and text on the screen printing forme is become through hole, and the silk screen hole of non-graphic part is plugged.By the extruding of scraper plate, printing ink is transferred on the stock by the mesh of picture and text part during printing, formed the picture and text the same with original copy.Screen printing apparatus is simple, easy to operate, and it is simple and easy and with low cost to print, make a plate, and adaptability is strong.
Centrifugation when even glue technology is utilized high speed rotating makes membrane material form the layer of even film on base material, and the big I of film thickness is controlled according to rotational time and speed, is a kind of conveniently film technique.
Summary of the invention
The invention provides a kind of microminiaturized all solid state Clark formula dissolved oxygen sensor of three-electrode structure, can measure the blood oxygen concentration in the blood of human body fast and accurately.
A kind of all-solid state dissolved oxygen sensor comprises substrate, is positioned at contrast electrode on the substrate, to electrode, working electrode, dielectric substrate, insulation course and oxygen permeation membrane;
Described contrast electrode is made up of with the lead-in wire that links to each other with reaction electrode reaction electrode, silver/silver chloride electrode of being positioned on the reaction electrode;
Described electrode is made up of with the lead-in wire that links to each other with reaction electrode reaction electrode;
Described working electrode is made up of with the lead-in wire that links to each other with reaction electrode reaction electrode;
Described insulation course is overlying on contrast electrode, on electrode and the working electrode, insulation course is provided with silver/silver chloride electrode of making contrast electrode and lead-in wire, to the reaction electrode and the exposed opening of lead-in wire of the reaction electrode of electrode and lead-in wire, working electrode; Contrast electrode, exposed region that electrode and working electrode are gone between separately link to each other with external proving installation in measurement, and dissolved oxygen sensor is applied corresponding current potential;
Described dielectric substrate is with the silver/silver chloride electrode of contrast electrode, cover the reaction electrode of electrode and the reaction electrode of working electrode;
Described oxygen permeation membrane covers dielectric substrate, and described oxygen permeation membrane is selected the oxygen permeability filmogen for use, and the oxygen permeability filmogen can be selected single-component silicon glue, teflon, cellulose acetate or Polyvinylchloride for use.
Preferably, the lead-in wire of described contrast electrode, the lead-in wire of electrode and the lead-in wire of working electrode are parallel to each other, can simplify external proving installation.
Preferably, the reaction electrode of described contrast electrode, the reaction electrode of the reaction electrode of electrode and working electrode is positioned at the same side of lead-in wire separately, can make the opening minimum on the insulation course like this, thereby make the dielectric substrate area minimum that covers the insulation course opening, save material.
The preparation method of above-mentioned all-solid state dissolved oxygen sensor may further comprise the steps:
(1) contrast electrode that on the macromolecular material that is covered with one deck conductive metal foil (as polypropylene, polyester, tygon and Polyvinylchloride etc.) substrate, adopts the laser index carving method to etch to be parallel to each other, to electrode and working electrode, the conductive metal foil on the substrate can be selected goldleaf, silver foil, aluminium foil, Copper Foil, platinum foil, titanium foil etc. for use;
(2) print last layer silver slurry with the method for serigraphy on the reaction electrode on the contrast electrode, the lucifuge drying forms one deck silverskin;
(3) print insulation course with the method for serigraphy, and the lucifuge drying, insulation course is provided with opening, and this opening makes silverskin, the reaction electrode of electrode and the reaction electrode of working electrode is exposed;
(4) silverskin is immersed in the saturated potassium chloride solution, adopt electric plating method that the chlorion in silver ion and the saturated potassium chloride solution is reacted, generate silver chloride attached on the silverskin, after finishing, reaction electrode is washed with deionized water or pure water, the lucifuge drying makes the silver/silver chloride electrode of contrast electrode;
(5) the configuration electrolyte slurry prints electrolyte slurry with the method for serigraphy on substrate, and electrolyte slurry covers silver/silver chloride electrode, to the reaction electrode of electrode and the reaction electrode of working electrode, lucifuge drying, formation dielectric substrate;
The collocation method of described electrolyte slurry is: potassium chloride is dissolved in forms electrolyte solution in the deionized water, add Pehanorm and hydrochloric acid as damping fluid at electrolyte solution, make the PH=8 of electrolyte solution, the concentration of potassium chloride in electrolyte solution is 1mol/L;
Described damping fluid also can be selected the damping fluid of other type for use, for example phosphate buffer, potassium dihydrogen phosphate-sodium hydrate buffer solution or barbiturates damping fluid etc.;
Electrolyte solution can not also need add an amount of thickening agent and defoamer directly as the slurry of serigraphy in electrolyte solution.Thickening agent can increase the viscosity of electrolyte solution, makes it to become the gel state material, could be as the slurry of electrolyte solution.Thickening agent adopts polyvinylpyrrolidone (PVP) and sodium carboxymethyl cellulose (CMC), polyvinylpyrrolidone and sodium carboxymethyl cellulose join in the electrolyte solution according to the ratio that is roughly 2.5: 1, whenever get the 100ml electrolyte solution and need add about 50g polyvinylpyrrolidone and 20g sodium carboxymethyl cellulose.Issuable bubble when defoamer can be eliminated printing makes the electrolyte slurry printing even, and defoamer adopts the polyether type defoamer, and dosage is about 2%～5% (massfraction) of electrolyte solution.
(6) coating is insoluble to electrolyte solution, molecule aperture and oxygen molecule fit, can makes dissolved molecular oxygen and hydrone infiltrate into the oxygen permeability filmogen of dielectric substrate on dielectric substrate, and dry back forms oxygen permeation membrane, makes dissolved oxygen sensor.
Described oxygen permeability filmogen can be selected single-component silicon glue, polytetrafluoroethylene (PTFE), cellulose acetate (CA) or Polyvinylchloride (PVC) for use.
Silica gel and teflon can directly be sprayed on it and form oxygen permeation membrane on dielectric substrate.
If select for use cellulose acetate as oxygen permeation membrane, acetate and cellulose be dissolved in according to 1: 4 mass ratio make the serigraphy slurry in the ethylene acetate, adopt the method for serigraphy on dielectric substrate, to stamp cellulose acetate membrane then, the formation oxygen permeation membrane.
If select for use Polyvinylchloride as oxygen permeation membrane, polyvinyl chloride powder is dissolved in organic solvent, as making the serigraphy slurry in cyclohexanone or the tetrahydrofuran, adopt the method for serigraphy on dielectric substrate, to stamp the PVC film then, form oxygen permeation membrane.
The dissolved oxygen sensor for preparing is inserted in the concentration of dissolved oxygen solution to be measured, contrast electrode, the lead-in wire of electrode, working electrode is connected external proving installation respectively, form current return.Dissolved molecular oxygen in the solution to be measured can be penetrated in the gelatinous dielectric substrate by oxygen permeation membrane (when measuring blood oxygen concentration, oxygen permeation membrane can also stop other materials in the blood to enter dielectric substrate and influence the measurement of oxygen concentration), and further be diffused into working electrode and to electrode by dielectric substrate.
In the course of reaction, as anode, dissolved oxygen DO obtains electronics on the reaction electrode surface to electrode and is reduced to electrode, and the electrochemical reaction of generation is: 2O
2+ 2H
2O+4e
-→ 4OH
-Working electrode is as negative electrode, and the electrochemical reaction that takes place on the reaction electrode of working electrode is: 4OH
-→ 2O
2+ 2H
2O+4e
-Contrast electrode provides stable benchmark voltage for whole current return; The passage that dielectric substrate moves at working electrode with between to electrode, exchanges as ion.
The electric current that forms in the electrode reaction is received by external proving installation by the lead-in wire of three electrodes.The linear correlationship of dissolved oxygen concentration in this size of current and the solution to be measured obtains the response current of dissolved oxygen sensor thus, extrapolates the oxygen concentration in the solution to be measured.
The present invention has following outstanding advantage:
1, biology sensor of the present invention adopts three-electrode structure, can effectively avoid the galvanochemistry cross reaction, in the three-electrode structure, contrast electrode with electrode is separated, oxidized on to electrode at hydroxyl that working electrode surface generates, avoided the pollution of hydroxyl, prolonged the serviceable life of sensor the electrode environment.By contrast, in two electrode structures, generated hydroxyl or hydrogen peroxide can exert an influence to electrode at working electrode surface, pile up a certain amount of after, the electrode measurement instability, electrode life is shorter;
2, three electrodes with dissolved oxygen sensor are integrated on the substrate, and the microminiaturization of realization sensor and integrated is easy to carry, easy and simple to handle, the response time of dissolved oxygen sensor is shortened greatly, and the response time was particularly useful for clinical medical blood oxygen concentration and detects less than 10 minutes;
3, adopt methods such as serigraphy, laser index carving to make, simplified the making flow process, reduce cost of manufacture, be fit to produce in enormous quantities.
Description of drawings
Fig. 1 is the structural representation of all-solid state dissolved oxygen sensor of the present invention;
Fig. 2 is an A-A sectional view among Fig. 1;
Fig. 3 is a B-B sectional view among Fig. 1;
Fig. 4 is a C-C sectional view among Fig. 1;
Fig. 5 is the current-responsive curve of embodiment 1 prepared dissolved oxygen sensor to dissolved oxygen DO solution;
Fig. 6 is the current-responsive curves of embodiment 2 prepared dissolved oxygen sensors to dissolved oxygen DO solution.
Embodiment
As shown in Figure 1, a kind of all-solid state dissolved oxygen sensor comprises substrate 1, is positioned at contrast electrode 2 on the substrate 1, to electrode 3, working electrode 4, insulation course 5, dielectric substrate 6 and oxygen permeation membrane 7;
Fig. 2 is an A-A sectional view among Fig. 1, i.e. the structural representation of contrast electrode 2, and as shown in Figure 2, contrast electrode 2 is made up of with the lead-in wire 202a that links to each other with reaction electrode 201a reaction electrode 201a, silver/silver chloride electrode 203 of being positioned on the reaction electrode 201a;
Fig. 3 is a B-B sectional view among Fig. 1, promptly to the structural representation of electrode 3, as shown in Figure 3, electrode 3 is made up of with the lead-in wire 302b that links to each other with reaction electrode 301b reaction electrode 301b;
Fig. 4 is a C-C sectional view among Fig. 1, i.e. the structural representation of working electrode 4, and as shown in Figure 4, working electrode 4 is made up of with the lead-in wire 402c that links to each other with reaction electrode 401c reaction electrode 401c;
A kind of preparation of all-solid state dissolved oxygen sensor may further comprise the steps:
(1) etches the contrast electrode, working electrode of shape as shown in Figure 1 and to electrode being covered with on the polypropylene substrate of one deck goldleaf, wherein contrast electrode, working electrode and the reaction electrode of electrode is the rectangle of long 18mm, wide 4mm with the laser index carving method;
(2) print one deck silver with the method for serigraphy on the reaction electrode of contrast electrode and starch, used screen cloth is 420 orders, and net is apart from 1.5mm, 80 ° of scraper plate hardness, 64.3 ° of blade angle, scraper velocity 8mm/s, scraper plate pressure 4kg/cm
2, finishing printing the dry 2min of substrate lucifuge in baking oven, 50 ℃ of oven temperatures form silverskin;
(3) in substrate, print insulating material, insulating material covers contrast electrode, working electrode and to the outer peripheral portion of electrode zone, and make the reaction electrode of silverskin, working electrode and exposed to the reaction electrode of electrode, used screen cloth is 420 orders, net is apart from 1.5mm, 80 ° of scraper plate hardness, 64.3 ° of blade angle, scraper velocity 8mm/s, scraper plate pressure 4kg/cm
2, the dry 4min of lucifuge in baking oven, 50 ℃ of oven temperatures form insulation course; The material of insulation course adopts the insulation dyestuff SS8391 that Co., Ltd produces in the Baohua Industries Co.;
(4) partly immerse silverskin in the saturated potassium chloride solution, lead-in wire and platinum electrode and constant pressure source formation loop with contrast electrode add 1.5V voltage between contrast electrode and platinum electrode, form silver/silver chloride electrode behind the energising 60s, and clean up natural lucifuge drying with deionized water;
(5) get the potassium chloride of 27.275g, the Pehanorm of 3.029g, 1220 μ l mass concentrations are that 36% concentrated hydrochloric acid and deionized water are settled to 500ml in volumetric flask.Get this solution 40ml, add 20g polyvinylpyrrolidone and 8g sodium carboxymethyl cellulose, add about 1ml defoamer with liquid-transfering gun, defoamer adopts the DC1520 product of Dow Corning Corporation, fully stirs, and makes electrolyte slurry; Utilize method for printing screen that electrolyte slurry is being printed on the substrate, electrolyte slurry is covered with the reaction electrode of silver/silver chloride electrode, working electrode with to the reaction electrode of electrode, air dry forms dielectric substrate; Used screen cloth 420 orders, net are apart from 1.5mm, 55 ° of scraper plate hardness, 64.3 ° of blade angle, scraper velocity 8mm/s, scraper plate pressure 4kg/cm
2
(6) spin coating one deck single component silica gel is as oxygen permeation membrane on dielectric substrate to use sol evenning machine, and silica gel adopts the KE3475 model silica gel of Japan XINYUE, even glue time 10s, and rotating speed 5000r/min promptly makes dissolved oxygen sensor after dry ten minutes.
The dissolved oxygen sensor that makes is immersed in the sample solution, at external proving installation respectively with contrast electrode, working electrode, the lead-in wire of electrode is connected to form test loop, and at working electrode with add the constant voltage of 0.7V between to electrode.After applying voltage 300s, current stabilization is measured working electrode and to the current value between the electrode, is the stable response current value of this dissolved oxygen sensor.Testing the current value of the sample solution of different dissolved oxygen dividing potential drop respectively, is that transverse axis, current value are the longitudinal axis with the dissolved oxygen DO dividing potential drop, draws the response characteristics figure of dissolved oxygen sensor, and its result as shown in Figure 5.
A kind of preparation of all-solid state dissolved oxygen sensor may further comprise the steps:
(1) etches the contrast electrode, working electrode of shape as shown in Figure 1 and to electrode being covered with on the polypropylene substrate of one deck goldleaf, wherein contrast electrode, working electrode and the reaction electrode of electrode is the rectangle of long 18mm, wide 4mm with the laser index carving method;
(2) print one deck silver with the method for serigraphy on the reaction electrode of contrast electrode and starch, used screen cloth is 420 orders, and net is apart from 1.5mm, 80 ° of scraper plate hardness, 64.3 ° of blade angle, scraper velocity 8mm/s, scraper plate pressure 4kg/cm
2, the dry 2min of lucifuge in baking oven, 50 ℃ of oven temperatures form silverskin;
(3) in substrate, print insulating material, insulating material covers contrast electrode, working electrode and to the outer peripheral portion of electrode zone, and makes the reaction electrode of silverskin, working electrode and exposed to the reaction electrode of electrode, and used screen cloth is 420 orders, net is apart from 1.5mm, 80 ° of scraper plate hardness, 64.3 ° of blade angle, scraper velocity 8mm/s, scraper plate pressure 4kg/cm2, the dry 4min of lucifuge in baking oven, 50 ℃ of oven temperatures form insulation course; The material of insulation course adopts the insulation dyestuff SS8391 that Co., Ltd produces in the Baohua Industries Co.;
(4) partly immerse silverskin in the saturated potassium chloride solution, lead-in wire and platinum electrode and constant pressure source formation loop with contrast electrode add 1.5V voltage between contrast electrode and platinum electrode, form silver/silver chloride electrode behind the energising 60s, and clean up natural lucifuge drying with deionized water;
(5) get the potassium chloride of 27.275g, the potassium dihydrogen phosphate of 13.69g, 4.4g NaOH and deionized water are settled to 500ml in volumetric flask.Get this solution 40ml, add 20g polyvinylpyrrolidone and 8g sodium carboxymethyl cellulose, add about 1ml defoamer with liquid-transfering gun, defoamer adopts the DC1520 product of Dow Corning Corporation, fully stirs, and makes electrolyte slurry; Utilize method for printing screen that electrolyte slurry is being printed on the substrate, electrolyte slurry is covered with the reaction electrode of silver/silver chloride electrode, working electrode with to the reaction electrode of electrode, air dry, form dielectric substrate, used screen cloth is 420 orders, and net is apart from 1.5mm, 55 ° of scraper plate hardness, 64.3 ° of blade angle, scraper velocity 8mm/s, scraper plate pressure 4kg/cm
2
(6) spin coating one deck single component silica gel is as oxygen permeation membrane on dielectric substrate to use sol evenning machine, and silica gel adopts the KE4895 model silica gel of Japan XINYUE, even glue time 10s, and rotating speed 4500r/min promptly makes dissolved oxygen sensor after dry half an hour.
The dissolved oxygen sensor that makes is immersed in the sample solution, at external proving installation respectively with contrast electrode, working electrode, the lead-in wire of electrode is connected to form test loop, and at working electrode with add the constant voltage of 0.7V between to electrode.After applying voltage 300s, current stabilization is measured working electrode and to the current value between the electrode, is the stable response current value of this dissolved oxygen sensor.Testing the current value of the sample solution of different dissolved oxygen dividing potential drop respectively, is that transverse axis, current value are the longitudinal axis with the dissolved oxygen DO dividing potential drop, draws the response characteristics figure of dissolved oxygen sensor, and its result as shown in Figure 6.
Claims (10)
1. all-solid state dissolved oxygen sensor comprises substrate (1), is positioned at contrast electrode (2) on the substrate (1), to electrode (3), working electrode (4), dielectric substrate (6), insulation course (5) and oxygen permeation membrane (7), it is characterized in that:
Described contrast electrode (2) is made up of with the lead-in wire (202a) that links to each other with reaction electrode (201a) reaction electrode (201a), silver/silver chloride electrode (203) of being positioned on the reaction electrode (201a);
Described electrode (3) is made up of with the lead-in wire (302b) that links to each other with reaction electrode (301b) reaction electrode (301b);
Described working electrode (4) is made up of with the lead-in wire (402c) that links to each other with reaction electrode (401c) reaction electrode (401c);
Described insulation course (5) is overlying on contrast electrode (2), on electrode (3) and the working electrode (4), insulation course (5) is provided with silver/silver chloride electrode (203) of making contrast electrode (2) and lead-in wire (202a), to reaction electrode (301b) and lead-in wire (302b), the reaction electrode (401c) of working electrode (4) and (402c) the exposed opening that goes between of electrode (3);
Described dielectric substrate (6) is with the silver/silver chloride electrode (203) of contrast electrode (2), cover the reaction electrode (301b) of electrode (3) and the reaction electrode (401c) of working electrode (4);
Described oxygen permeation membrane (7) covers dielectric substrate (6).
2. all-solid state dissolved oxygen sensor according to claim 1 is characterized in that described oxygen permeation membrane is selected the oxygen permeability filmogen for use.
3. all-solid state dissolved oxygen sensor according to claim 2 is characterized in that, described oxygen permeability filmogen is selected single component silica gel, teflon, cellulose acetate or Polyvinylchloride for use.
4. all-solid state dissolved oxygen sensor according to claim 1 is characterized in that, the lead-in wire (202a) of described contrast electrode (2), the lead-in wire (302b) of electrode (3) and the lead-in wire (402c) of working electrode (4) is parallel to each other.
5. all-solid state dissolved oxygen sensor according to claim 1, it is characterized in that, the reaction electrode (201a) of described contrast electrode (2), the reaction electrode (401c) of the reaction electrode (301b) of electrode (3) and working electrode (4) is positioned at the same side of lead-in wire separately.
6. the preparation method of all-solid state dissolved oxygen sensor according to claim 1 is characterized in that, comprising:
(1) be covered with on the macromolecular material substrate of conductive metal foil adopt the laser index carving method etch contrast electrode, to electrode and working electrode;
(2) printing one deck silver slurry on the reaction electrode on the contrast electrode, the lucifuge drying forms silverskin;
(3) on substrate, print insulation course, the lucifuge drying, insulation course is provided with opening, and this opening makes silverskin, the reaction electrode of electrode and the reaction electrode of working electrode is exposed;
(4) silverskin is immersed in the saturated potassium chloride solution, adopt electric plating method on silverskin, to make the silver/silver chloride electrode of contrast electrode, and use washed with de-ionized water, the lucifuge drying;
(5) the configuration electrolyte slurry prints electrolyte slurry on substrate, and electrolyte slurry covers silver/silver chloride electrode, to the reaction electrode of electrode and the reaction electrode of working electrode, and the lucifuge drying forms dielectric substrate;
(6) apply the oxygen permeability filmogen on dielectric substrate, dry back forms oxygen permeation membrane, makes dissolved oxygen sensor.
7. the preparation method of all-solid state dissolved oxygen sensor according to claim 4 is characterized in that, the collocation method of the electrolyte slurry described in the described step (5) is:
Potassium chloride is dissolved in forms electrolyte solution in the deionized water, add Pehanorm and hydrochloric acid as damping fluid at electrolyte solution, make the PH=8 of electrolyte solution, the concentration of potassium chloride in electrolyte solution is 1mol/L, in electrolyte solution, add thickening agent and defoamer, mix and stir, make electrolyte slurry.
8. the preparation method of all-solid state dissolved oxygen sensor according to claim 5 is characterized in that, described thickening agent is selected polyvinylpyrrolidone and sodium carboxymethyl cellulose for use, and the ratio of polyvinylpyrrolidone and sodium carboxymethyl cellulose is 2.5: 1.
9. the preparation method of all-solid state dissolved oxygen sensor according to claim 5 is characterized in that, described defoamer adopts the polyether type defoamer.
10. the preparation method of all-solid state dissolved oxygen sensor according to claim 5 is characterized in that, described damping fluid is selected phosphate buffer, potassium dihydrogen phosphate-sodium hydrate buffer solution or barbiturates damping fluid for use.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103353474A (en) * | 2013-04-28 | 2013-10-16 | 苏州天和自动化系统有限公司 | Dissolved oxygen sensor |
| CN109001275A (en) * | 2018-08-09 | 2018-12-14 | 北京化工大学 | A kind of three-electrode electro Chemical dissolved oxygen sensor |
| CN110887885A (en) * | 2019-11-28 | 2020-03-17 | 北京乐普医疗科技有限责任公司 | Dissolved oxygen electrochemical sensor for micro-fluidic chip and preparation method |
| CN113647952A (en) * | 2021-08-18 | 2021-11-16 | 北京航空航天大学 | Flexible dry electrode made of silver/silver chloride nanowires and preparation method thereof |
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| CN114660136A (en) * | 2022-03-17 | 2022-06-24 | 浙江清华柔性电子技术研究院 | Electrochemical dissolved oxygen sensor and preparation method thereof |
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| CN116106390A (en) * | 2023-01-17 | 2023-05-12 | 天津大学 | Continuous arterial blood oxygen detection chip based on microfluidic technology and preparation process thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051624A (en) * | 1990-11-23 | 1991-05-22 | 浙江大学 | Detect the multielectrode sensor of dissolved oxygen DO |
| CN1060560A (en) * | 1990-09-28 | 1992-04-22 | 罗斯蒙德公司 | Matrix immobilized electrolyte |
| JPH09127045A (en) * | 1995-10-26 | 1997-05-16 | Nok Corp | Dissolved oxygen sensor |
| JP2000214125A (en) * | 1999-01-28 | 2000-08-04 | Fuji Elelctrochem Co Ltd | Oxygen sensor |
| JP2001208720A (en) * | 2000-01-25 | 2001-08-03 | Toyota Central Res & Dev Lab Inc | Oxygen sensor |
| CN101042365A (en) * | 2007-04-11 | 2007-09-26 | 浙江大学 | Dissolved oxygen electrochemical sensor |
-
2010
- 2010-06-25 CN CN 201010211482 patent/CN101881749B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060560A (en) * | 1990-09-28 | 1992-04-22 | 罗斯蒙德公司 | Matrix immobilized electrolyte |
| CN1051624A (en) * | 1990-11-23 | 1991-05-22 | 浙江大学 | Detect the multielectrode sensor of dissolved oxygen DO |
| JPH09127045A (en) * | 1995-10-26 | 1997-05-16 | Nok Corp | Dissolved oxygen sensor |
| JP2000214125A (en) * | 1999-01-28 | 2000-08-04 | Fuji Elelctrochem Co Ltd | Oxygen sensor |
| JP2001208720A (en) * | 2000-01-25 | 2001-08-03 | Toyota Central Res & Dev Lab Inc | Oxygen sensor |
| CN101042365A (en) * | 2007-04-11 | 2007-09-26 | 浙江大学 | Dissolved oxygen electrochemical sensor |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103353474A (en) * | 2013-04-28 | 2013-10-16 | 苏州天和自动化系统有限公司 | Dissolved oxygen sensor |
| CN103353474B (en) * | 2013-04-28 | 2015-03-04 | 苏州天和自动化系统有限公司 | Dissolved oxygen sensor |
| CN109001275A (en) * | 2018-08-09 | 2018-12-14 | 北京化工大学 | A kind of three-electrode electro Chemical dissolved oxygen sensor |
| CN109001275B (en) * | 2018-08-09 | 2022-04-19 | 北京化工大学 | Three-electrode electrochemical dissolved oxygen sensor |
| CN110887885A (en) * | 2019-11-28 | 2020-03-17 | 北京乐普医疗科技有限责任公司 | Dissolved oxygen electrochemical sensor for micro-fluidic chip and preparation method |
| CN113647952A (en) * | 2021-08-18 | 2021-11-16 | 北京航空航天大学 | Flexible dry electrode made of silver/silver chloride nanowires and preparation method thereof |
| CN113804627A (en) * | 2021-09-14 | 2021-12-17 | 广东中图半导体科技股份有限公司 | Semiconductor photoelectrochemical sensor and preparation method thereof |
| CN114660136A (en) * | 2022-03-17 | 2022-06-24 | 浙江清华柔性电子技术研究院 | Electrochemical dissolved oxygen sensor and preparation method thereof |
| CN115586234A (en) * | 2022-12-12 | 2023-01-10 | 艾康生物技术(杭州)有限公司 | Biosensor and preparation method thereof |
| WO2024125392A1 (en) * | 2022-12-12 | 2024-06-20 | 利多(香港)有限公司 | Biosensor for measuring partial pressure of oxygen, and preparation method therefor |
| CN116106390A (en) * | 2023-01-17 | 2023-05-12 | 天津大学 | Continuous arterial blood oxygen detection chip based on microfluidic technology and preparation process thereof |
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