CN101915794A - All-solid-state reference electrode and preparation method thereof - Google Patents
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- CN101915794A CN101915794A CN2010102358906A CN201010235890A CN101915794A CN 101915794 A CN101915794 A CN 101915794A CN 2010102358906 A CN2010102358906 A CN 2010102358906A CN 201010235890 A CN201010235890 A CN 201010235890A CN 101915794 A CN101915794 A CN 101915794A
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Abstract
The invention provides a thick film printing technology-based all-solid-state reference electrode. The all-solid-state reference electrode comprises a substrate, an electrode base system, an electrolyte layer, a reference film and an insulating layer, wherein the electrode base system consists of a reaction electrode and a contact electrode, which are positioned on the substrate, and a lead wire for connecting the reaction electrode and the contact electrode; the electrolyte layer is positioned on the reaction electrode of the electrode base system; the reference film is coated on the electrolyte layer; the insulating layer covers the reference film; the insulating layer is provided with an opening for exposing the reference film; and the opening area is used as a reaction area where the reference film is contacted with solution to be measured in actual measurement. The all-solid-state reference electrode abandons the conventional internal-charged electrolyte, and eliminates adverse factors in the aspects of portability, storage and the like brought by contained liquid components. The invention also provides a preparation method of the all-solid-state reference electrode. The preparation method has the advantages of simple manufacturing process, suitability for mass production and low cost.
Description
Technical field
The present invention relates to the chemical sensor technical field, relate in particular to a kind of all-solid-state reference electrode and preparation method thereof.
Background technology
In electrochemical measurement, the electrode that electrode potential of needs is stable, accurate and its numerical value is known is as reference electrode.The hydrogen electrode device is because its stable performance is commonly used for the one-level reference electrode.But, hydrogen electrode device and adopt the experimentation of this device all more loaded down with trivial details, actual slightly soluble salt electrode commonly used such as mercurous chloride electrode, silver chloride electrode or mereurous sulfate electrode etc. are as the secondary reference electrode, and this class electrode is called contrast electrode.
Electrolyte is meant a class material that can be dissociated into charged ion and have electric conductivity in solution.At present, the electrolyte that detection body fluid and Environmental Water are adopted all is ion-selective electrode (ion selective electrode is called for short ISE).This is that a class utilizes membrane potential to measure the electrochemical sensor of certain specific ion activity in the solution or concentration.Ion-selective electrode and contrast electrode combination need be submerged in the detected solution during measurement, constitute electrochemical cell.Contrast electrode as with reference to relatively, requires its electrode potential stable, and good reappearance is arranged when measuring the electromotive force of ion-selective electrode.
Contrast electrode commonly used has silver/silver chloride contrast electrode and calomel reference electrode.These two kinds of reference electrodes all are to plate the coating of this metal difficulty soluble salt on the corresponding metal surface and make.When measuring, its immersion is had in the identical anionic solution with this metal difficulty soluble salt, its electrode potential changes with the negative ion activity of difficulty soluble salt in the solution.When this negative ion activity remained unchanged in the solution, electrode potential was stablized constant.If but containing the negative ion that other can form difficulty soluble salt with this metal cation (mercury, silver ion) in the solution to be measured, these negative ion can produce the electrode potential of contrast electrode and disturb.
Fill electrolyte because traditional contrast electrode contains in liquid, make it, can not under High Temperature High Pressure, work being subjected to a lot of restrictions aspect transportation, preservation and the use.And all solid state outer contrast electrode can not overcome above-mentioned shortcoming owing to do not contain the liquid part.At present, the research of all solid state outer contrast electrode of quite a few all is based on Ag/AgCl mechanism, just be substrate,, keep the current potential of electrode to stablize by on the Ag/AgCl electrode, applying modes such as the hydrogel contain fixing chlorine ion concentration or high-polymer membrane with Ag/AgCl.But the water loss meeting causes the hydrogel layer volume change in the hydrogel, thereby causes the chlorine ion concentration in the hydrogel to change, and causes the current potential instability.This is a big defective of this type of solid state reference electrode.
Along with conducting polymer be it is found that the characteristic that ionic conduction is converted to electronic conduction gradually, the research that the various conducting polymers of modifying is used for all solid state outer contrast electrode also more and more causes various countries scientist's interest.These conducting polymers have been contained multiple polymeric material with ionic conduction and/or electronic conduction ability, comprising: the 1) conjugated polymer of Can Zaing; 2) redox polymers; 3) synthetic polymer; 4) polymer dielectric.The conductive conjugated polymer that mixes of p type wherein, becomes to be fit to do in contrast electrode solid-state and fills electrolytical material because it possesses the effect that ionic conduction is converted to electronic conduction such as polypyrrole, polyaniline, polythiophene and derivant thereof.Wherein mixed polystyrolsulfon acid (poly (styrenesulfonate), PSS) poly-3,4-enedioxy thiophene (poly (3,4-ethylenedioxythiophene), be the metastable novel conductive polymer of a kind of current potential PEDOT), have O
2And CO
2(pH) insensitive good characteristic, reference electrolyte in being suitable as.By in PEDOT (PSS), introducing the pH buffer system contain sulfo group, make electrode possess the double dominant of conducting polymer solid electrolyte and pH buffer system, thereby reach the stable effect of electrode potential in liquid scope to be measured widely.
Screen printing technique belongs to porous printing, and it is called as four big printing processes with offset printing, protruding seal, gravure.In porous printing, most widely used is serigraphy.Silk, nylon, dacron or stainless steel metal silk screen are stretched tight on screen frame, its tensioning is fixed, adopt manual method of carving paint film or photochemistry plate-making to make screen printing forme.What the modern times more generally used is the photochemistry graphic arts process.The photochemistry plate-making technology is to utilize photosensitive material to make screen printing forme by photomechanical method, and making the silk screen hole of picture and text part on the screen printing forme is penetrating hole, and the screen mesh of non-graphic part is plugged.Serigraphy is put into screen frame with slurry (printing ink), and pressurizeing in screen frame with the rubber sdueegee scrapes, and slurry is transferred on the stock by the mesh of picture and text part, forms the picture and text the same with original copy.This technology belongs to the thick film film technique.Screen printing apparatus is simple, easy to operate, and it is simple and easy and with low cost, easy to operate to print, make a plate, and adaptability is strong.The forming thin film technology is utilized the principle of high temperature evaporation or plasma sputtering, makes material be deposited in substrate surface and forms film, compares with serigraphy, and film forming is even, but price is higher.
Summary of the invention
The invention provides a kind of plate all solid state contrast electrode, can measure ion concentration in body fluid and the ambient water quality with ion-selective electrode pairing.The present invention also provides the preparation method of this all-solid-state reference electrode, has simplified the making flow process, is fit to produce in enormous quantities.
A kind of all-solid-state reference electrode comprises substrate, electrode basement system, dielectric substrate, reference film and insulation course;
Described electrode basement system is made up of the lead-in wire that is positioned at reaction electrode, the contact electrode on the described substrate and is connected these two electrodes;
Described dielectric substrate is positioned on the reaction electrode of electrode basement system, is covered with reference film on the dielectric substrate;
Described insulation course coats reference film, and insulation course is provided with the opening that makes reference film exposed, the conversion zone that the open area comes in contact as reference film in the actual measurement and solution to be measured.
The preparation method of above-mentioned all-solid-state reference electrode may further comprise the steps:
(1) adopts method for printing screen to go up printing conductive serigraphy material, form reaction electrode, contact electrode and the conductive lead wire that is connected these two electrodes at high-molecular organic material substrate (as polypropylene, polyester, tygon or Polyvinylchloride etc.);
Reaction electrode can adopt the more stable conductive materials of character such as carbon, gold, platinum or titanium to make, conductive lead wire and contact electrode can adopt materials such as silver, carbon, gold, platinum or titanium to make, the electrochemical properties instability of silver, but electric conductivity is good, dying generally is not used for making reaction electrode, and can be used to make contact electrode and conductive lead wire;
Also can adopt the film evaporation technology with above-mentioned conductive material as the coating by vaporization of coating by vaporization material on substrate; Or with above-mentioned conductive material as target, it is splashed to forms reaction electrode, contact electrode and conductive lead wire on the substrate.
(2) use surfactant solution that pre-service is carried out on the reaction electrode surface, be used for the cleaning activity electrode surface, and the water wettability of intensified response electrode, strengthen the adhesion between reaction electrode and the solid-state electrolyte layer.
It is 1 ‰～1% sodium carboxymethyl cellulose (CMC) solution or sodium hydroxyethyl cellulose (HEC) solution that surfactant solution can adopt mass percent;
(3) conducting polymer is dispersed in forms suspending liquid in the water, configuration proportion is a conducting polymer: water=1: 99～5: 95, total amount in suspending liquid, in suspending liquid, add mass percent and be 0.1～1 ‰ treating agent and mass percent and be 1.5～5.0% CMC or HEC, be mixed with electrolyte slurry, with the method for a spray, spin coating or serigraphy this electrolyte slurry is covered and to be coated in the reaction electrode surface, the lucifuge drying forms dielectric substrate.
Described conducting polymer is selected from a kind of in polypyrrole that the P type mixes and derivant, polyaniline and derivant thereof, polythiophene and the derivant thereof.
Preferably, conducting polymer is selected the poly-3 of mixed polystyrolsulfon acid (PSS) for use, 4-enedioxy thiophene (hereinafter to be referred as PEDOT/PSS), and this conducting polymer is to the O in the solution
2And CO
2(pH) insensitive, make contrast electrode in various types of solution to be measured, keep electrode potential stable.
Described treating agent can adopt the different octyl phenol ether of polyethylene glycol (Triton X-100), and treating agent can make dielectric substrate and reaction electrode better bonding;
(4) with the lipophilicity macromolecular substances, the non-conductive polymer polymer dissolution forms potpourri in plastifier, in the potpourri gross mass, the mass percent of lipophilicity macromolecular substances is 1.1～2.6%, the lipophilicity macromolecular substances comprises two kinds of lipophilicity negative ion macromolecular substances and lipophilic cation macromolecular substances, wherein the ratio of the quality of lipophilicity negative ion macromolecular substances and lipophilic cation macromolecular substances is 0.8: 1～1.2: 1, the mass percent of non-conductive polymer polymkeric substance is 32.0～38.0%, and the mass percent of plastifier is 58.0～66.0%; This potpourri is dissolved in tetrahydrofuran or the cyclohexanone solvent, be mixed with reference film liquid, making the concentration of non-conductive polymer polymkeric substance in solution is 46.8～72.6mg/mL, reference film liquid covered by the method for a spray, spin coating or serigraphy be coated in the dielectric substrate surface, the lucifuge drying forms solid-state hydrophobic reference film.Reference film can be protected by the relatively poor dielectric substrate of the mechanical property of its covering, makes dielectric substrate keep current potential stable in measurement.
Described lipophilicity negative ion macromolecular substances is selected from one or more in tetraphenylboron sodium, tetrachlorobenzene boronation potassium, four [3,5-two (the three fluoro methyl) phenyl] potassium borate.The lipophilic cation macromolecular substances adopts methyl dotriacontyl ammonium chloride.The lipophilicity macromolecular substances can be got rid of the interference of lipophilicity ion in the solution to be measured (as long-chain fatty acid, chain alkyl sulfonate or long-chain dialkyl group phosphate etc.) to reference film, and can reduce the resistance of electrode.
Described non-conductive polymer polymkeric substance is selected from one or more in Polyvinylchloride (PVC), polyurethane (PU), polyvinyl acetate (PVA), the polymethylmethacrylate (PMMA).
Described plastifier one or more in dibutyl sebacate, dioctyl adipate, hexane diacid two (1-butyl pentane) ester, dinitro benzene Octyl Ether, decanedioic acid di-sec-octyl, maleic acid diethyl monooctyl ester, dioctyl fumarate.Plastifier can improve the plasticity of potpourri, is convenient to become in follow-up serigraphy mould.
(5) method by serigraphy is printed insulation course on substrate, and insulation course covers reference film, and is provided with the exposed opening of reference film, and this open area is the conversion zone that actual measurement reference film and solution to be measured come in contact, and promptly makes all-solid-state reference electrode.
In order to make contrast electrode reach better effect, before carrying out above-mentioned (4) step, dielectric substrate on substrate part was soaked 12～24 hours in sulfosalicylic acid (SSA) damping fluid of 0.1mol/L, the lucifuge drying, it is 7 that the sulfosalicylic acid damping fluid must transfer to the pH value of solution with NaOH.This step is carried out modification to electrode, by in PEDOT/PSS, introducing the pH buffer system that contains sulfo group group, make electrode possess the double dominant of conducting polymer solid electrolyte and pH buffer system, keeping the stable effect of electrode potential in the liquid scope to be measured widely thereby reach.
When actual measurement, will make the combination of all-solid-state reference electrode and ion-selective electrode, be submerged in the detected solution, constitute electrochemical cell.Contrast electrode is connected with external measurement mechanism by the contact electrode on the substrate.Conducting polymer in the dielectric substrate has the function of electron acceptor, ionic conduction can be converted to electronic conduction, and its process can be write:
Wherein, M
+Oxidized conducting polymer unit in the expression dielectric substrate; E is an electronics; M represents neutral conducting polymer unit; A
-Electronegative doping composition in the expression conducting polymer.Because M in conducting polymer
+The ratio of/M is constant, so make the current potential of solid-state electrolyte layer keep constant, has played the effect of traditional contrast electrode.Conducting polymer is as a kind of electronic conductive material, make between dielectric substrate and the reaction electrode and form Ohmic contact, effectively reduce the resistance of electrode, with the detected effects of ion conversion of signals to be measured of reference film is electronic signal, and detects for external test circuit by reaction electrode, conductive lead wire, contact electrode.In the actual measurement, it is stable that the electrode potential of contrast electrode keeps, for ion-selective electrode provides stable reference potential.
All-solid-state reference electrode of the present invention adopts and fills electrolyte in solid-state, has abandoned and has filled electrolytic solution in traditional, eliminated since contain that liquid component brings carry, the unfavorable factor of aspect such as preservation.Simultaneously, flat structure of the present invention has been realized the contrast electrode microminiaturization, shortens the reaction time of contrast electrode, and can measure under High Temperature High Pressure.
Description of drawings
Fig. 1 is the structural representation of all-solid-state reference electrode;
Fig. 2 is the vertical view of all-solid-state reference electrode shown in Figure 1;
Fig. 3 is the potential response of embodiment 1 prepared all-solid-state reference electrode in variable concentrations NaCl solution;
Fig. 4 is the potential response of embodiment 1 prepared all-solid-state reference electrode in variable concentrations KCl solution;
Fig. 5 is that embodiment 2 prepared all-solid-state reference electrodes are at variable concentrations CaCl
2Potential response in the solution;
Fig. 6 is the potential responses of embodiment 2 prepared all-solid-state reference electrodes in the Tris-HCl of different pH damping fluid.
Embodiment
As shown in Figure 1, a kind of all-solid-state reference electrode comprises substrate 1, electrode basement system, dielectric substrate 3, reference film 4 and insulation course 5;
The electrode basement system is made up of with the lead-in wire 2b that is connected these two electrodes the reaction electrode 2a, the contact electrode 2c that are positioned on the substrate 1; Found out that by Fig. 2 reaction electrode 2a and contact electrode 2c are rectangle, the lead-in wire 2b that connects these two electrodes is a strip, and such shape makes in adopting the method for printing screen preparation process, makes the making of screen printing forme more easy;
A kind of preparation of all-solid-state reference electrode may further comprise the steps:
(1) with the carbon printing material by screen printing technique on the polypropylene substrate, form reaction electrode, contact electrode and the lead-in wire that is connected these two electrodes;
(2) the service property (quality) mark is that 3 ‰ CMC aqueous solution is cleaned the reaction electrode surface, then wiped clean.
(3) PEDOT/PSS (adopting the Clevios P of German H.C.Starck company, CAS No.155090-83-8) is dispersed in forms suspending liquid in the water, allocation ratio is PEDOT/PSS: H
2O=1: 99, the Triton X-100 of adding 0.5 ‰ and 2% HEC in suspending liquid, the electrolyte slurry of formation certain viscosity.Method with serigraphy is printed on the electrolyte slurry that makes on the reaction electrode, forms dielectric substrate after the lucifuge drying, and the thickness of dielectric substrate is about 20 μ m.Used web plate 150 orders, net are apart from 1mm, scraper velocity 8mm/s, pressure 1.8kg/cm
2
(4) the dielectric substrate zone on the polypropylene substrate was soaked 12 hours in the sulfosalicylic acid solution of 0.1mol/L, it is 7 that sulfosalicylic acid solution must transfer to its pH value with NaOH;
(5) add 33.9mg tetrachlorobenzene boron sodium, 35.1mg methyl dotriacontyl ammonium chloride and 1120mg macromolecule PVC in the 1.2mL dibutyl sebacate, shake after 1 minute, add the 8mL cyclohexanone, the concussion dissolving obtains the homogeneous transparent viscous fluid.Method by serigraphy is printed on this viscous fluid on the dielectric substrate, forms reference film after the lucifuge drying.Used web plate 150 orders, net are apart from 1mm, scraper velocity 8mm/s, pressure 1.8kg/cm
2
(6) adopt the method for serigraphy to print insulation course, the circular open that insulation course is provided with diameter 1mm makes reference film partly exposed.The material of insulation course adopts the insulation dyestuff SS8391 that Co., Ltd produces in the Baohua Industries Co..
The all-solid-state reference electrode that mensuration makes is with respect to the electrode potential of Ag/AgCl| (3mol/LKCl) standard reference electrode in the standard solution of various different ions concentration, potential value during record 15s, with the ion concentration is transverse axis, and the response potential value is the longitudinal axis, and its result is respectively shown in Fig. 3,4.
Fig. 3 is the potential response of prepared all-solid-state reference electrode in the solution NaCl (containing 1mmol/LCaCl2 and 4mmol/LKCl back-ground electolyte in this solution) of variable concentrations, and the potential fluctuation scope that records is 199.5 ± 0.7mV.
Fig. 4 (contains 140mmol/LNaCl and 1mmol/LCaCl for prepared all-solid-state reference electrode at the KCl of variable concentrations solution in this solution
2Back-ground electolyte) potential response in, the potential fluctuation scope that records is 109.4 ± 0.6mV.
Embodiment 2
A kind of preparation of all-solid-state reference electrode may further comprise the steps:
(1) the carbon printing material is printed on the polypropylene substrate by screen printing technique, forms reaction electrode, conductive lead wire and contact electrode;
(2) the service property (quality) mark is that 2 ‰ HEC aqueous solution is cleaned the reaction electrode surface, then wiped clean;
(3) PEDOT/PSS (product adopts the Clevios P of German H.C.Starck company, CAS No.155090-83-8) is dispersed in forms suspending liquid in the water, allocation ratio is PEDOT/PSS: H
2O=1: 99, the Triton X-100 of adding 0.5 ‰ and 2% HEC in suspending liquid, form the electrolyte slurry of certain viscosity, method with serigraphy is printed on the reaction electrode surface with this electrolyte slurry, forms dielectric substrate after the lucifuge drying, and the thickness of dielectric substrate is about 20 μ m, used web plate is 150 orders, net is apart from 1mm, scraper velocity 8mm/s, pressure 1.8kg/cm
2
(4) tetrachlorobenzene boronation potassium, 1.1mg methyl dotriacontyl ammonium chloride, 17mg PVA and the 68mg PU of adding 0.9mg in 56.2 μ L hexane diacids two (1-butyl pentane) ester, shake after 1 minute, add 300 μ L cyclohexanone, the concussion dissolving obtains the reference film liquid of homogeneous transparent thickness, the reference film liquid of getting 0.5 μ L covers it by the method for a spray and is coated in the dielectric substrate surface, forms reference film after the lucifuge drying;
(5) adopt the method for serigraphy to print insulation course, insulation course is provided with 2 * 2cm
2Square aperture make reference film partly exposed.The material of insulation course adopts the insulation dyestuff SS8391 that Co., Ltd produces in the Baohua Industries Co..
With the all-solid-state reference electrode that makes CaCl at variable concentrations
2Measure its potential response in the solution (containing 140mmol/LNaCl and 4mmol/LKCl back-ground electolyte in this solution), the result as shown in Figure 5, calcium ion concentration is in 0.1～5mmol/L scope, and the all-solid-state reference electrode potential fluctuation scope that records is 182.7 ± 0.5mV.
The all-solid-state reference electrode that makes is measured its potential response in trishydroxymethylaminomethane-hydrochloric acid (Tris-HCl) damping fluid of different pH, the result as shown in Figure 6, the pH of Tris-HCl damping fluid is 5.91～8.67, and the all-solid-state reference electrode potential fluctuation scope that records is 182.7 ± 0.5mV.
By above experimental result as can be seen, all-solid-state reference electrode of the present invention is in different ionic types, different ion concentration, different potential of hydrogen solution, and its electrode potential can both keep current potential stable, has good operation stability.
Claims (10)
1. an all-solid-state reference electrode comprises substrate, electrode basement system, dielectric substrate, reference film and insulation course;
Described electrode basement system is made up of the lead-in wire that is positioned at reaction electrode, contact electrode and coupled reaction electrode and contact electrode on the described substrate;
Described dielectric substrate is positioned on the reaction electrode of electrode basement system, is covered with reference film on the dielectric substrate;
Described insulation course coats reference film, and insulation course is provided with the opening that makes reference film exposed.
2. the preparation method of all-solid-state reference electrode according to claim 1 is characterized in that, comprising:
(1) on the high-molecular organic material substrate, covers and be coated with conductive material and form reaction electrode, contact electrode and conductive lead wire;
(2) use water phase surfactant mixture that pre-service is carried out on the reaction electrode surface;
(3) conducting polymer is dispersed in forms suspending liquid in the water, configuration proportion is a conducting polymer: water=1: 99～5: 95, in the suspending liquid total amount, in suspending liquid, add mass percent and be 0.1～1 ‰ treating agent and mass percent and be 1.5～5.0% sodium carboxymethyl cellulose or sodium hydroxyethyl cellulose, be mixed with electrolyte slurry, this electrolyte slurry covered be coated in the reaction electrode surface, form dielectric substrate;
(4) lipophilicity negative ion macromolecular substances, lipophilicity negative ion macromolecular substances, non-conductive polymer polymer dissolution are formed potpourri in plastifier, in the potpourri gross mass, the macromolecular mass percent of lipophilicity is 1.1～2.6%, lipophilicity negative ion macromolecular substances is 0.8: 1～1.2: 1 with the ratio of the quality of lipophilic cation macromolecular substances, the mass percent of non-conductive polymer polymkeric substance is 32.0～38.0%, and the mass percent of plastifier is 58.0～66.0%;
This potpourri is dissolved in tetrahydrofuran or the cyclohexanone solvent, is mixed with reference film liquid, this film liquid is covered be coated in dielectric substrate surface and form reference film;
(5) print insulation course on substrate, insulation course covers reference film, and insulation course is provided with the opening that makes reference film exposed.
3. the preparation method of all-solid-state reference electrode according to claim 2, it is characterized in that, described carboxymethylcellulose sodium solution or the sodium hydroxyethyl cellulose solution that pretreated water phase surfactant mixture is a massfraction 0.1～1% is carried out on the reaction electrode surface.
4. the preparation method of all-solid-state reference electrode according to claim 2 is characterized in that, described conducting polymer is selected from a kind of in polypyrrole and derivant, polyaniline and derivant thereof, polythiophene and the derivant thereof.
5. the preparation method of all-solid-state reference electrode according to claim 2 is characterized in that, the described treating agent that adds in conducting polymer suspending liquid adopts the different octyl phenol ether of polyethylene glycol.
6. the preparation method of all-solid-state reference electrode according to claim 2 is characterized in that, described non-conductive polymer polymkeric substance is selected from one or more in Polyvinylchloride, polyurethane, polyvinyl acetate, the polymethylmethacrylate.
7. the preparation method of all-solid-state reference electrode according to claim 2, it is characterized in that, described lipophilicity negative ion macromolecular substances is selected from tetraphenylboron sodium, tetrachlorobenzene boronation potassium, four [3,5-two (three fluoro methyl) phenyl] in the potassium borate one or more, lipophilicity negative ion macromolecular substances is selected methyl dotriacontyl ammonium chloride for use.
8. the preparation method of all-solid-state reference electrode according to claim 2 is characterized in that, the concentration of the non-conductive polymer polymkeric substance in described step (4) the reference film liquid is 46.8～72.6mg/mL.
9. the preparation method of all-solid-state reference electrode according to claim 2 is characterized in that, described conducting polymer is selected the poly-3 of polystyrene doped sulfonic acid, 4-enedioxy thiophene for use.
10. the preparation method of all-solid-state reference electrode according to claim 2, it is characterized in that, carrying out step (4) before, dielectric substrate on substrate part was soaked 12～24 hours in the sulfosalicylic acid damping fluid of 0.1mol/L, the lucifuge drying, it is 7 that the sulfosalicylic acid damping fluid transfers to the pH value of solution with NaOH.
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| CN102980926A (en) * | 2012-11-28 | 2013-03-20 | 清华大学 | Preparation method of flexible double-faced full-solid ion concentration detection sensor |
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| CN105021682A (en) * | 2015-07-02 | 2015-11-04 | 浙江大学 | Needle-like chlorine ion sensor and preparation method thereof |
| CN105067684A (en) * | 2015-07-02 | 2015-11-18 | 浙江大学 | Needle-shaped potassium ion sensor and preparation method thereof |
| CN105092668A (en) * | 2015-06-03 | 2015-11-25 | 浙江大学 | Full-solid-state acetylcholine sensor and preparation method thereof |
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