CN1227524C - Full solid state reference electrode - Google Patents
Full solid state reference electrode Download PDFInfo
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- CN1227524C CN1227524C CN 03138856 CN03138856A CN1227524C CN 1227524 C CN1227524 C CN 1227524C CN 03138856 CN03138856 CN 03138856 CN 03138856 A CN03138856 A CN 03138856A CN 1227524 C CN1227524 C CN 1227524C
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Abstract
The present invention relates to a fully solid state reference electrode which is provided with an electrode cavity, wherein an electrode core is arranged in the cavity, an electrode cap is arranged at the upper part of the electrode cavity, and the electrode core is connected with a conducting wire. The present invention is characterized in that the electrode core is composed of the materials of the weight ratio: 1 part of nanometer level silver chloride powders, 0.1 to 0.8 part of pure silver powders, and 0.01 to 0.1 part of a modification and decoration object. The electrode core of the present invention can be molded through powder pressing so as to be used in a system of which the pressure is as high as 10000 kilograms per square centimeter. Inner reference liquid does not exist in the electrode, and the electrode directly comes into contact with liquid (seawater) to be measured so as to form the silver / silver chloride reference electrode of the present invention. A nanometer material has a large specific surface; consequently, the area of a three phase interface can be greatly increased, the electrode can not be easily polarized, the electrode stability is obviously enhanced to avoid a sintering process, and the preparing technology of the electrode is simplified. A pressure buffer cavity contains a water permeable membrane and a solid filler; consequently, disassembly and cleaning can be easily realized, and maintenance can be conveniently carried out.
Description
Technical field
The present invention relates to a kind of contrast electrode, particularly relate to a kind of all solid state contrast electrode that contains nano material.
Technical background
Contrast electrode commonly used when carrying out electrochemical measurement at present in seawater has mercurous chloride electrode, silver/silver chloride electrode, copper/copper sulfate eletrode, high purity zinc electrode etc.And in the electrochemical measurement of deep-sea corrosion, because the pressure of seawater depths can reach tens atmospheric pressure even higher, traditional silver/silver chloride electrode and mercurous chloride electrode, frangible because its shell mostly is glass, thereby be not suitable under elevated pressures, using; Except shell can not because contrast electrode contains interior reference liquid, also must add special pressure-resistant apparatus with the glass, this makes electrode structure become complicated, not only there is the liquid junction potential that is difficult to estimate, also needs often to replenish reference liquid, use extremely inconvenient.Also there is similar problem in copper/copper sulphate contrast electrode.Zinc electrode is a metal electrode, and its long-time stability are not really desirable.In recent years, bibliographical information is crossed many solid state reference electrodes, and great majority are relevant with silver/silver chloride electrode, the good reversibility of silver/silver chloride electrode, and stability is high, favorable reproducibility, its preparation method has thermoelectric solution, powder platen press etc.Though wherein the electrode performance of thermal electrolysis method preparation is good, the preparation trouble, the electrode that a suitable size is little has deposited silver layer and adheres to not firmly, and long-time stability are poor, and shortcoming such as not high pressure resistant, thereby are unsuitable for long period of soaking in seawater.
Summary of the invention
The purpose of this invention is to provide a kind of improved all-solid-state reference electrode, it can overcome the above-mentioned shortcoming of existing contrast electrode.
A kind of all-solid-state reference electrode, electrode chamber is arranged, in this cavity electrode cores is housed, two electrode caps are arranged at electrode chamber top, be connected to lead on the electrode cores, it is characterized in that described electrode cores is made up of nanoscale silver chloride powder, fine silver powder, modification and trim, their weight ratio is 1: 0.1-0.8: 0.01-0.1; Be equipped with a detachable buffering cavity in addition.
Electrode cores of the present invention through powder is molded can be at pressure up to 10000 kilograms per centimeter
2System in use.Reference liquid in not having in the electrode directly contacts formation silver/silver chloride contrast electrode with the liquid to be measured (seawater) that contains chlorion.The performance of kind electrode core depends on the size of silver-silver chloride-electrolyte three phase boundary, because the nano material specific surface area is big, can significantly increase the area of three phase boundary, make electrode be difficult for polarization, can obviously improve the stability of electrode and can avoid sintering process, simplify the manufacture craft of electrode.The pressure buffer cavity contains water permeability barrier film and solid filling, and quick detachable and cleaning is convenient to safeguard.
Description of drawings
Accompanying drawing 1 is the structural representation of all-solid-state reference electrode main part.
Accompanying drawing 2 is the structural representation of detachable buffering cavity.
Embodiment
This all-solid-state reference electrode has an electrode chamber 2, in this cavity 2 electrode cores 1 is housed, electrode cap 4 and electrode cap 6 are arranged at electrode chamber 2 tops, be connected to lead 5 on the electrode cores 1, it is characterized in that described electrode cores 1 is made up of nanoscale silver chloride powder, fine silver powder, modification and trim, their weight ratio is 1: 0.1-0.8: 0.01-0.1; Be equipped with a detachable buffering cavity 7 in addition.
When making electrode cores 1, at first prepare nanoscale silver chloride powder, adopt indoor temperature solid phase method with silver nitrate and potassium chloride according to identical mixed in molar ratio, fully grind the 0.5h reaction after, through washing and filtering, vacuum drying a few hours promptly get white silver chloride powder.Transmission electron microscope scanning shows that this powder diameter is about 50nm.Then 10g silver chloride powder and 5g 200 purpose fine silver powder are mixed, and add 0.5g modification and trim, the molded electrode cores 1 of making of powder.This electrode cores 1 pressing pressure is 1000 kilograms per centimeter
2To 15000 kilograms per centimeter
2,, can adopt bigger pressing pressure for improving intensity as far as possible.The modification that can select and trim are silver salt such as silver bromide, silver iodide or silver sulfide.Electrode cores 1 is that the copper conductor 5 of fine silver silk picks out by the bottom, to avoid the influence of bimetallic corrosion to electrode stability.
The present invention is owing to its special environment for use, and the material of electrode chamber 2 must be corrosion-resistant, high voltage bearing high molecular polymer, is good so adopt teflon class material.
Detachable buffering cavity 7 has a water permeability barrier film 8, and solid filler 9 is housed in the cavity 7.Water permeability barrier film 8 can be biscuit ware film, perfluoroethylene-propylene film, polyvinylidene fluoride film, fluororubber film etc., and its effect is to allow seawater freely pass through, and oarse-grained impurity in the while insulating sea water is to avoid the surface of contaminated electrode core 1.Solid filler 9 can be zeolite, ceramic oxide or zeyssatite, and its effect is the impurity in the further filtering sea, reduces the direct pressure of seawater to electrode cores 1 simultaneously, prolongs the serviceable life of electrode in the deep-sea.Be provided with the netted base plate 10 of placing solid filler 9 in the buffering cavity 7.Because the seawater after process purifies can freely pass through to arrive the surface of electrode cores 1 in buffering cavity 7, so the use of buffering cavity 7 can not cause the increase of electrode internal resistance, also can not influence the performance of electrode.As required, in the laboratory or shallow sea when using, this buffering cavity can not installed and not used yet.The material of netted base plate 10 can adopt teflon or poly-trifluoro-ethylene.
Claims (5)
1, a kind of all-solid-state reference electrode, electrode chamber (2) is arranged, electrode cores (1) is housed in this cavity (2), two electrode caps (4,6) are arranged at electrode chamber (2) top, be connected to lead (5) on the electrode cores (1), it is characterized in that described electrode cores (1) is made up of nanoscale silver chloride powder, fine silver powder, modification and trim, their weight ratio is 1: 0.1-0.8: 0.01-0.1; Be equipped with a detachable buffering cavity (7) in addition.
2, contrast electrode as claimed in claim 1 is characterized in that described detachable buffering cavity (7) has a water permeability barrier film (8), and solid filler (9) is housed, and is provided with the netted base plate (10) of placing solid filler (9) in the buffering cavity (7).
3, contrast electrode as claimed in claim 1 is characterized in that described modification and trim are silver bromide, silver iodide or silver sulfide.
4, contrast electrode as claimed in claim 2 is characterized in that described water permeability barrier film (8) is biscuit ware film, perfluoroethylene-propylene film, polyvinylidene fluoride film or fluororubber film.
5, contrast electrode as claimed in claim 2 is characterized in that described solid filler (9) is zeolite, ceramic oxide or zeyssatite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03138856 CN1227524C (en) | 2003-07-24 | 2003-07-24 | Full solid state reference electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03138856 CN1227524C (en) | 2003-07-24 | 2003-07-24 | Full solid state reference electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1514235A CN1514235A (en) | 2004-07-21 |
| CN1227524C true CN1227524C (en) | 2005-11-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03138856 Expired - Fee Related CN1227524C (en) | 2003-07-24 | 2003-07-24 | Full solid state reference electrode |
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| CN (1) | CN1227524C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101308111B (en) * | 2008-04-07 | 2011-12-21 | 中国船舶重工集团公司第七二五研究所 | Hot dip silver coating /silver halides reference electrode and method for making same |
| CN101915794B (en) * | 2010-07-23 | 2013-07-24 | 浙江大学 | Preparation method of all-solid-state reference electrode |
| CN102169103B (en) * | 2010-12-07 | 2013-05-29 | 北京科技大学 | Solid Ag/AgCl electrode core and preparation method and applications thereof |
| CN102368059A (en) * | 2011-10-26 | 2012-03-07 | 天津大学 | Method for preparing reference electrode with Ag/AgCl solid powder |
| CN102608661B (en) * | 2012-03-06 | 2013-03-20 | 中国地质大学（北京） | Electrode device for measuring seabed weak electric field signal and manufacture method of electrode device |
| CN102967639A (en) * | 2012-07-11 | 2013-03-13 | 哈尔滨工程大学 | Long-life reference electrode suitable for deep-sea high hydrostatic pressure environment |
| CN103604852B (en) * | 2013-11-29 | 2016-09-28 | 中国科学院海洋研究所 | A kind of method preparing the Ag/Agcl working electrode being applicable to monitoring chlorine ion concentration |
| CN103969306B (en) * | 2014-04-18 | 2016-08-24 | 中国科学院海洋研究所 | A kind of silver/silver chloride electrode being applicable to deep-sea and preparation method thereof |
| CN104287714A (en) * | 2014-11-10 | 2015-01-21 | 青岛柏恩鸿泰电子科技有限公司 | Silver/ silver chloride powder electrode |
| CN105021682B (en) * | 2015-07-02 | 2017-09-08 | 浙江大学 | A kind of needle-like chlorion sensor and preparation method thereof |
| CN106291015B (en) * | 2016-07-28 | 2019-08-30 | 青岛科技大学 | A kind of deep-sea long-life electric-field sensor |
| RU2637195C1 (en) * | 2016-08-19 | 2017-11-30 | Федеральное государственное бюджетное учреждение науки Институт Механики УрО РАН | Electrode device |
| CN112387973A (en) * | 2020-10-29 | 2021-02-23 | 江苏集萃脑机融合智能技术研究所有限公司 | Preparation process of powder electrode |
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