CN105334250A - Silver/silver chloride electrode slice and preparation technology thereof - Google Patents
Silver/silver chloride electrode slice and preparation technology thereof Download PDFInfo
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- CN105334250A CN105334250A CN201510691527.8A CN201510691527A CN105334250A CN 105334250 A CN105334250 A CN 105334250A CN 201510691527 A CN201510691527 A CN 201510691527A CN 105334250 A CN105334250 A CN 105334250A
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Abstract
The invention discloses a silver/silver chloride electrode slice and a preparation technology thereof, and belongs to the field of electrochemical sensors. The silver/silver chloride electrode slice comprises a supporting layer, a silver layer, a protection layer and a silver chloride layer. The preparation method for the silver/silver chloride electrode slice comprises plating the silver layer on the supporting layer through a vacuum silver-plating manner, then covering the protection layer on a part of the silver layer, and finally preparing the silver chloride layer through a chemical oxidation process, so as to prepare the silver/silver chloride electrode slice. The prepared silver/silver chloride electrode slice overcomes the disadvantages that a conventional silver/silver chloride electrode slice is low in precision, short in response time, bad in signal stability among batches, not suitable for organic environment and tedious in preparation technology, and the like. The silver/silver chloride electrode slice is stable in electric potential performance, high in precision, low in signal to noise ratio, low in impedance, short in response time, low in production cost, high in production efficiency and suitable for large-scale industrial production.
Description
Technical field
The present invention relates to electrochemical sensor technology field, particularly relate to a kind of silver/silver chloride electrode sheet and preparation technology thereof.
Background technology
Silver/silver chloride (Ag/AgCl) electrode is a kind of common contrast electrode, has that electrode potential is constant, an advantage such as not easily polarization, Low ESR, exchange current density are large.Because it accurately can detect bioelectrical signals, medical midbrain electricity, electrocardio, biochemical analysis dry plate bioelectric signal recording electrode are widely used in.Silver/silver chloride electrode preparation method conventional at present; as the electrically conductive ink of patent CN103192070A silver coating and silver chloride in dielectric substrate; silver/silver chloride electrode is prepared in printing; or as the powder particle mixing pressure sintering of silver and silver chloride is made silver/silver chloride electrode by patent CN101084829A, also have one to be electrochemically obtain silver/silver chloride electrode.
The performance of silver/silver chloride electrode depends on micro interface situation.On micro interface, silver and the size of silver chloride particle, content, uniformity coefficient and density had a significant impact the current potential accuracy of silver/silver chloride electrode, stability and response time.Electrode prepared by method for printing screen, be by silver/silver chloride particle dispersion in a solvent, add appropriate adjuvant and make electrically conductive ink, electrically conductive ink printing post-drying, obtains silver/silver chloride electrode.But this screen printing electrode, purity is not high, and in micromechanism, silver mixes uneven with silver chloride, particle is thick, causes electrical instability, and the signal difference between batch is larger, and screen printing electrode not organic solvent-resistant corrosion, be not suitable for organic solvent environment, usable range is limited.There is electrode stability difference problem in the electrode that in addition prepared by powder sintered electrode and galvanochemistry, and technique is loaded down with trivial details, is unfavorable for producing in enormous quantities too.
The demand of the silver/silver chloride electrode that along with the fast development of medical detection technique, particularly immediately detect the fast development of biochemical analysis dry plate, reliably, fast respond precision, applicability is wide, can be mass-produced increases day by day.
Summary of the invention
Technical matters to be solved by this invention is: overcome the defect that existing silver/silver chloride electrode exists, and provides a kind of silver/silver chloride electrode sheet that can produce in enormous quantities and preparation technology thereof.Silver/silver chloride electrode provided by the invention has tiny, even, fine and close micro interface, potentiometric is stable, precision is high, the response time is fast, impedance is low, greatly improve electrode preparation efficiency, reduce production cost, also can be applicable in addition in the inapplicable organic environment of screen printing electrode.
The invention provides a kind of silver/silver chloride electrode sheet, comprising: supporting layer, silver layer, protective seam, silver chloride layer.
Supporting layer selects the sheet non-conductive polymer material with some strength, and support layer material is selected from polyethylene terephthalate (PET), polyamide (PA), polypropylene (PP), acrylonitrile-butadiene-styrene copolymer (ABS).
Silver layer adopts technique for vacuum coating to be plated on supporting layer, and silver layer shape can use circle, square.Silver thickness is 0.1 ~ 10 μm, and silver layer adopts technique for vacuum coating to be plated on supporting layer, can prepare by vacuum evaporation, vacuum magnetic-control sputtering, vacuum ion plating mode.Silver layer prepared by vacuum plating silver method can be plated to arbitrary plane shape, silver layer and supporting layer adhesion are strong, difficult drop-off, and silver layer surface even compact, grain size and silver thickness deviation are all at below 0.1um, and this adopts serigraphy and powder sintered preparation to be beyond one's reach.
Protective seam is metal or the conductive nonmetal material of the corrosion of protection not oxidized dose of silver layer.Protective seam metal material is selected from nickel, chromium, gold, platinum, copper, nickel-chrome, and protective seam nonmetallic materials are selected from graphite, carbon black, electrically conductive ink.Protective seam can adopt vacuum coating mode or mode of printing preparation, and protective layer thickness is 0.01 ~ 10 μm.The silver layer not needing chlorination to become silver chloride is covered by adding the protective seam that react with oxidant solutions, can available protecting silver layer, reduce the useful area of silver and silver chloride in electrode, minimizing production cost.
Silver chloride layer adopts chemistry or electrochemical method preparation, and described oxidation processes refers to that, by silver layer process 15 ~ 120s in oxidizing agent solution, temperature is 15 ~ 60 DEG C; Oxygenant is selected from iron chloride, potassium dichromate, Peligot salt, potassium permanganate; Silver chloride layer adopts chemistry or electrochemical method preparation.Adopt chemical method prepare silver chloride layer, silver chloride layer surface uniform, response electromotive force stablize, the response time is short, and can simplify preparation technology, shorten the production time, cost-saving, greatly enhance productivity.
The preparation technology of silver/silver chloride electrode sheet, comprises the steps: (1) by supporting layer through Ultrasonic Cleaning post-drying, puts into vacuum chamber and vacuumize; (2) pre-service is carried out to supporting layer: before plated film, be filled with argon gas, nitrogen or oxygen, start radio-frequency power supply and plasma treatment is carried out to supporting layer, time 30 ~ 120s; (3) vacuum plating silver on supporting layer; (4) on silver layer, silver chloride layer part is not needed to prepare layer protective layer; (5) silver layer not being coated with protective seam is carried out oxidation processes, prepare silver chloride layer; (6) silver prepared/silver chloride electrode pure water is cleaned, and under temperature 50 ~ 100 DEG C of environment dry 10 ~ 60min.
Advantage of the present invention: silver of the present invention/silver chloride electrode sheet has that precision is high, the response time is fast, good stability, be suitable for industrial feature in enormous quantities; mainly be derived from the combination that vacuum plating silver process and chemical oxidization method prepare silver chloride technique; key is to plate layer protective layer on the silver layer not needing silver chloride; silver and oxidizing agent solution can be stoped to react, facilitate the preparation of silver chloride layer.The silver prepared by this technique/silver chloride electrode sheet can be any shape, size, dirigibility is strong, and silver provided by the invention/silver chloride electrode sheet has tiny, even, fine and close micro interface, potentiometric is stablized, and precision is high, and the response time is fast, impedance is low, be applicable in any organic or inorganic environment, and greatly can improve the preparation efficiency of electrode, reduce production cost.
Accompanying drawing explanation
Fig. 1 is silver/silver chloride electrode diagrammatic cross-section.
Fig. 2 is that silver/silver chloride electrode mass prepares schematic diagram.
Fig. 3 is silver in 0.1mol/LKCl solution/silver chloride electrode open circuit potential and time diagram.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but the present invention is not only confined to following examples.
As shown in Figure 1, silver/silver chloride electrode comprises: supporting layer, silver layer, protective seam, silver chloride layer.
Concrete implementation step is as follows: by PET through Ultrasonic Cleaning; after plasma surface treatment; adopt vacuum evaporation coating mode on PET sheet, plate the silver layer of 3 μm; then chlorination is needed to become the part of silver chloride with mask plate protection; with magnetron sputtering mode nickel coating 0.3 μm; silver layer after nickel plating is placed in potassium dichromate, hydrochloric acid, Klorvess Liquid; carry out oxidation processes and prepare silver chloride layer; finally will prepare silver/silver chloride electrode pure water to clean up; and it is dry in vacuum drying chamber; time 30min, temperature 50-60 DEG C.
According to above technique, silver/silver chloride electrode can be prepared in batches, after silver/silver chloride layer prepares, just can obtain the silver/silver chloride electrode of suitable dimension through cutting, as shown in Figure 2.
In 0.1mol/LKCl solution, measure silver/silver chloride electrode open circuit potential and time relationship as shown in Figure 3, the inner potential of 10s can be stablized by Fast-Balance, and electrode potential fluctuation range is within ± 0.3mv.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All modifications done according to the Spirit Essence of main technical schemes of the present invention, all should be encompassed within protection scope of the present invention.
Claims (7)
1. silver/silver chloride electrode sheet and a preparation technology thereof, is characterized in that: silver/silver chloride electrode sheet comprises supporting layer, silver layer, protective seam, silver chloride layer; Silver/silver chloride electrode sheet preparation technology concrete steps are as follows: supporting layer through Ultrasonic Cleaning post-drying, is put into vacuum chamber and vacuumized by (1); (2) pre-service is carried out to supporting layer: before silver-plated, be filled with argon gas, nitrogen or oxygen, start radio-frequency power supply and Cement Composite Treated by Plasma is carried out to supporting layer, time 30 ~ 120s; (3) vacuum plating silver on supporting layer; (4) on silver layer, do not need silver chloride layer part to cover layer protective layer; (5) silver layer not covered by the protective layer is carried out oxidation processes, prepare silver chloride layer; (6) silver prepared/silver chloride electrode pure water is cleaned, and dries.
2. supporting layer according to claim 1, it is characterized in that: described supporting layer selects the sheet non-conductive polymer material with some strength, support layer material comprises and is not limited to polyethylene terephthalate (PET), polyamide (PA), polypropylene (PP), acrylonitrile-butadiene-styrene copolymer (ABS).
3. silver layer according to claim 1, it is characterized in that: described silver layer shape comprises and is not limited to circle, square, silver thickness is 0.1 ~ 10 μm, and silver layer adopts technique for vacuum coating to be plated on supporting layer, selects vacuum evaporation, be prepared by the mode of vacuum magnetic-control sputtering or vacuum ion plating.
4. protective seam according to claim 1, is characterized in that: described protective seam adopts the metal or conductive nonmetal material that do not react with the oxidizing agent solution of silver; Vacuum coating mode or mode of printing preparation can be adopted; Protective layer thickness is 0.01 ~ 10 μm.
5. protective seam according to claim 4, is characterized in that: described protective seam metal material comprises and is not limited to nickel, chromium, gold, platinum, copper, nickel-chrome, and the protective seam non-metallic material bed of material comprises and is not limited to graphite, carbon black, electrically conductive ink.
6. silver/silver chloride electrode sheet step of preparation process (5) according to claim 1, is characterized in that: described oxidation processes refers to that, by silver layer process 15 ~ 120s in oxidizing agent solution, temperature is 15 ~ 60 DEG C; Oxygenant comprises and is not limited to iron chloride, potassium dichromate, Peligot salt, potassium permanganate.
7. silver/silver chloride electrode sheet step of preparation process (6) according to claim 1, is characterized in that: described oven dry is at vacuum drying chamber inner drying, baking temperature 50 ~ 100 DEG C, time 10 ~ 60min.
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| CN201510691527.8A CN105334250A (en) | 2015-10-23 | 2015-10-23 | Silver/silver chloride electrode slice and preparation technology thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107228881A (en) * | 2016-03-23 | 2017-10-03 | 华邦电子股份有限公司 | The soft ph value sensor of printing and its manufacture method |
| CN109414210A (en) * | 2016-06-30 | 2019-03-01 | 拓自达电线株式会社 | The forming method of organism electrode and organism electrode |
| CN113647952A (en) * | 2021-08-18 | 2021-11-16 | 北京航空航天大学 | Flexible dry electrode based on silver/silver chloride nanowires and preparation method thereof |
| CN113916954A (en) * | 2021-09-30 | 2022-01-11 | 上海交通大学 | On-chip in-situ micro silver chloride reference electrode and preparation method thereof |
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| US4199412A (en) * | 1978-10-31 | 1980-04-22 | Eastman Kodak Company | Halide ion-selective devices and method |
| US4214968A (en) * | 1978-04-05 | 1980-07-29 | Eastman Kodak Company | Ion-selective electrode |
| CN1036834A (en) * | 1988-01-21 | 1989-11-01 | 电核物理有限公司 | Measure the dry ion-selective electrodes that aqueous medium intermediate ion kind is used |
| US20090159443A1 (en) * | 2004-09-02 | 2009-06-25 | Abbott Point Of Care Inc. | Blood urea nitrogen (bun) sensor |
| CN104614428A (en) * | 2015-03-07 | 2015-05-13 | 西南大学 | Nano-silver ink-based inkjet printing silver/silver chloride reference electrode and preparation method thereof |
-
2015
- 2015-10-23 CN CN201510691527.8A patent/CN105334250A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4214968A (en) * | 1978-04-05 | 1980-07-29 | Eastman Kodak Company | Ion-selective electrode |
| US4199412A (en) * | 1978-10-31 | 1980-04-22 | Eastman Kodak Company | Halide ion-selective devices and method |
| CN1036834A (en) * | 1988-01-21 | 1989-11-01 | 电核物理有限公司 | Measure the dry ion-selective electrodes that aqueous medium intermediate ion kind is used |
| US20090159443A1 (en) * | 2004-09-02 | 2009-06-25 | Abbott Point Of Care Inc. | Blood urea nitrogen (bun) sensor |
| CN104614428A (en) * | 2015-03-07 | 2015-05-13 | 西南大学 | Nano-silver ink-based inkjet printing silver/silver chloride reference electrode and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107228881A (en) * | 2016-03-23 | 2017-10-03 | 华邦电子股份有限公司 | The soft ph value sensor of printing and its manufacture method |
| CN107228881B (en) * | 2016-03-23 | 2019-08-23 | 华邦电子股份有限公司 | The soft ph value sensor of printing and its manufacturing method |
| CN109414210A (en) * | 2016-06-30 | 2019-03-01 | 拓自达电线株式会社 | The forming method of organism electrode and organism electrode |
| CN109414210B (en) * | 2016-06-30 | 2022-03-11 | 拓自达电线株式会社 | Electrode for living body, and method for forming electrode for living body |
| US11490846B2 (en) | 2016-06-30 | 2022-11-08 | Tatsuta Electric Wire & Cable Co., Ltd. | Bioelectrode and method for producing bioelectrode |
| CN113647952A (en) * | 2021-08-18 | 2021-11-16 | 北京航空航天大学 | Flexible dry electrode based on silver/silver chloride nanowires and preparation method thereof |
| CN113916954A (en) * | 2021-09-30 | 2022-01-11 | 上海交通大学 | On-chip in-situ micro silver chloride reference electrode and preparation method thereof |
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Application publication date: 20160217 |