CN101887043B - Renewable solid working electrode for electrochemical analysis - Google Patents
Renewable solid working electrode for electrochemical analysis Download PDFInfo
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- CN101887043B CN101887043B CN2010102294622A CN201010229462A CN101887043B CN 101887043 B CN101887043 B CN 101887043B CN 2010102294622 A CN2010102294622 A CN 2010102294622A CN 201010229462 A CN201010229462 A CN 201010229462A CN 101887043 B CN101887043 B CN 101887043B
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- electrode
- electrode tip
- conductive strips
- electrochemical analysis
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Abstract
The invention discloses a renewable solid working electrode for electrochemical analysis, which consists of an electrode core and an electrode head, wherein the interior of the electrode core comprises a band supply reel for reeling a conductive band, a conductive band take-up reel for rewinding, a main guide shaft capable of moving an electrode band between the band supply reel and the take-up reel, and a driving mechanism for driving a power pair and the main guide shaft. The interior of the electrode head comprises a rubber ring for fixing an electrode area, springs fixed on two sides of the rubber ring, and a pull rod which drives the rubber ring to extrude and leave the conductive band and can move up and down. A lead is led out of the lateral surface of the electrode core; and during measurement, the lead is connected with a corresponding electrochemical analyzer interface. The electrode head is provided with a pore with a diameter of 3 millimeters, and the pore is the exposed working area of the conductive band. A working mode and a resting mode are alternated so as to form the renewable working electrode. The electrode is automatically and mechanically renewed respectively, and can be applied in an automatic on-line electrochemical analyzer.
Description
Technical field
The present invention relates to a kind of renewable solid working electrode that is used for electrochemical analysis, can realize automatic renewal, be used for the repeatedly while replication of multiple composition, be with a wide range of applications at galvanochemistry automatic on-line analysis field.
Background technology
Working electrode is requisite element in the electrochemical analysis.Working electrode commonly used in the electrochemical analysis mainly contains glass-carbon electrode, hanging mercury electrode and noble metal electrodes such as gold electrode, platinum electrode.Before each measurement finishes to measure next time, except that hanging mercury electrode, all to clean, so that the result has reappearance when same solution is measured to these electrodes.These electrodes normally are enclosed in columned glass or the plastic tube admittedly, and receive the restriction of electrode cost, make these electrodes to develop into and exempt from cleaning electrode.So in recent years, the electrochemical analysis worker more and more paid close attention to and was similar to the such disposable electrode sheet of screen printing electrode.This disposable electrode has advantages such as volume is little, cost is low, easy and simple to handle.At present, the extremely successful screen printing electrode of the marketization is exactly the special-purpose blood sugar test paper electrode slice of blood glucose meter.Patented claim 200420091585.4 discloses a kind of electric pole type disposable test strips that can avoid the mensuration blood sugar that material disturbs in the blood.In addition, patented claim 86205046,88217747.8,200520063615.5 has all related to the preparation of disposable electrode.
But above electrode test sheet is independently, isolates, and when measuring, all needs the artificial electrode slice that inserts at every turn, can't realize unmanned on-line monitoring.A kind of web-like electrode and the application aspect battery thereof have been described among patented claim 02154767.X, the 02800194.X, 00102876.6,01136784.9; This web-like electrode is to prepare electrode film earlier; Again the film for preparing is cut into the tape of certain width; And being rolled into electrode group on request, these ways are in order to increase electrode area effectively.At present, ripe membrane preparation technology has chemical vapor deposition (for example patented claim 200610118331.0,98808023.0,88101061,971,160 62.7,200680009747.7,200580019114.6 etc.), physical gas phase deposition technology (for example patented claim 87105946.0,98800304.X, 200910203731.5,200810201997.1,94102085.1,03135578.1 etc.), screen printing technique (for example patented claim 90103106.2,02111330.0,200710070726.2,200710124151.8,200420008929.0,200510025145.8 etc.), curtain coating drying and forming-film (for example patented claim 200680036792.1), hot pressing film forming (for example patented claim 02110569.3), first spin coating, spraying, immersion or casting to carry out electronation or roasting film forming (for example patented claim 200910067707.3) etc. again.This web-like electrode has greatly increased the working area of electrode, and this is very disadvantageous to electrochemical analysis.Because big working area causes big background current, can't measure the ion of low concentration.
Patented claim 02806634.0 discloses a kind of electrode for medical service that is used for the measuring patient human body resistance, relates in particular to a kind of impedance cardiography electrode.This kind band electrode simultaneously has bonding agent, is not suitable as the working electrode that electrochemical analysis is used.
Summary of the invention
The renewable solid working electrode that is used for electrochemical analysis of the height precision of renewableization that technical matters to be solved by this invention provides a kind of electrode during with fixed-area.
A kind of renewable solid working electrode that is used for electrochemical analysis; The butt joint of electrode cores and electrode tip is provided with the driving mechanism that volume send confession roll coil of strip dish and the take-up reel of the described conductive strips of backrush, the capstan that can between described confession roll coil of strip dish and take-up reel, move described electrode band and the pinch roller of conductive strips, power paid described capstan in described electrode cores; The end of described electrode tip is provided with the electrode tip hole; In described electrode tip, be provided with the rubber band of fixed electorde area; Be provided with spring between the both sides of described rubber band and the described electrode tip sidewall; Described electrode tip is provided with tape guide roller, and described conductive strips are between described rubber band and the described electrode tip hole through described angle sheave guiding, and described rubber band is connected with and drives its pull bar that moves up and down; Described pull bar and described driving mechanism are in transmission connection; Described rubber band makes described conductive strips dock or leave with described electrode tip hole under the driving of described pull bar, in described electrode tip, is provided with one and pushes down the conduction pinch roller of described conductive strips with described tape guide roller, and described conduction pinch roller is connected with the terminals of connecting with external circuit.
Described driving mechanism is an automatic electromagnetic ironware spare, and perhaps meshing gear reaches the button that is in transmission connection with described meshing gear.
Described electrode tip is cylindric, and its internal diameter size is 10mm, wall thickness 1mm; Length is 10mm, and described electrode cores is cylindric, and described electrode cores is coaxial with described electrode tip; The internal diameter size of described electrode cores is 30mm, wall thickness 1mm, and length is 100mm.
The width of described conductive strips is 6mm, and thickness is 100 μ m.
Conductive materials on the conductive layer of described conductive strips be graphite, conductive organic matter, metal, metallic compound or nonmetal conductive compound and they respectively with the potpourri of bioactivator enzyme, antibody or DNA.
The soft matrix material of described conductive strips is the fluorine derivative, cellulose diacetate of tygon, PVC, polystyrene, ethene, partly-hydrolysed Triafol T or polyethylene terephthalate.
The conducting film preparation method of described conductive strips adopts chemical vapor deposition, physical vapour deposition (PVD), serigraphy, electroless plating, microelectronic process engineering, printed circuit board technology, curtain coating drying and forming-film or hot pressing film forming.
The diameter of described electrode tip hole is 3mm.
Described electrode tip hole is closed in the bottom that described conduction pinch roller is arranged on described electrode tip.
Adopt the renewable solid working electrode that is used for electrochemical analysis of technique scheme, when being in mode of operation, conductive strips are drawn through supplying roll coil of strip dish, are clipped between pinch roller and the capstan, use tape guide roller to introduce between rubber band and the electrode tip bottom.Rubber band tightly presses together with the bottom owing to receive the pressure of the compression spring that is fixed on electrode tip sidewall and bottom, makes conductive strips only expose the workplace of fixed size, good airproof performance at the electrode tip hole place of electrode tip.Conductive strips are introduced between opposite side pinch roller and the capstan through tape guide roller, and the conductive strips of drawing are fixed on the take-up reel.At this moment, driving mechanism is in rest mode.
When renewable solid working electrode was in rest mode, electrode can upgrade automatically.At this moment, the electrode cores top is a power switch, and what link to each other with capstan is an automatic electromagnetic ironware spare.Regularly actuating mechanism is opened, the energising of automatic electromagnetic ironware spare, and electromagnet produces strong magnetic field; Armature drives pull bar and rubber band, overcomes the force of compression of spring, moves upward; Rubber band separates with conductive strips, starts automatic electromagnetic ironware spare in succession, and capstan begins to rotate; Drive conductive strips and move certain distance, supply the conductive strips on the roll coil of strip dish to reduce, the conductive strips of take-up reel increase.Regularly actuating mechanism is closed then, and renewable electrode gets into mode of operation again.Like this, the mode of operation and the rest mode of renewable solid working electrode hocket, and use up the power supply automatic cutout up to electrode band.
When renewable solid working electrode was in rest mode, electrode can also carry out machinery to be upgraded.At this moment, electrode cores is provided with a button topmost, and button is connecting a meshing gear, and this meshing gear and capstan are installed on the same rotation axis, and the meshing gear side is connecting pull bar.Click button, meshing gear rotates a circle, and drives pull bar and upwards does mechanical motion; Drive capstan simultaneously and rotate, conductive strips are moved forward, after meshing gear one week motion is accomplished; Button is got back to original position again, and renewable working electrode is in mode of operation again.
The present invention draws terminals from the side of electrode cores; These terminals are bridges that the conductive strips in the electrode are linked to each other with the outside; The other end of terminals be be fixed on electrode tip side end angle in the conduction pinch roller link to each other, the conduction pinch roller surface-coated here one deck conductive materials, the conduction pinch roller contact with the conducting surface of electrode band; Therefore; In the actual measurement process, in apparatus of the present invention real acting only be the area that seals admittedly from the electrode tip hole to the electrode band the conduction pinch roller, this has just effectively satisfied the resistance requirement of working electrode.
The present invention adopts the conductive strips that can produce in batches to make renewable solid working electrode; Cost is low; The height precision of renewableization that has realized electrode during with fixed-area; Obtain to upgrade electrode favorable reproducibility, continuous monitoring when different kinds of ions can be realized when carrying out coupling like this with electrochemical analytical instrument.And this electrode is small-sized light and handy, need not complex devices, and is simple in structure, long service life.
Description of drawings
Fig. 1 is a front of the present invention plan view;
Fig. 2 is a bottom view of the present invention;
Fig. 3 is an inner member arrangenent diagram of the present invention;
Fig. 4 is the structure enlarged drawing at electrode tip of the present invention top;
Fig. 5 is that the present invention is 1 * 10
-3Cyclic voltammogram in the mol/L potassium ferricyanide solution;
Fig. 6 is the Zn of the present invention to variable concentrations
2+, Cd
2+, Pb
2+, Cu
2+Linear sweep stripping voltammogram;
Fig. 7 is the Zn of the present invention to 50 μ g/L
2+, Cd
2+, Pb
2+, Cu
2+Twice replicate determination of mixed solution be the stacking diagram as a result.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described further.
Referring to Fig. 1, Fig. 2, Fig. 3 and Fig. 4, electrode cores 2 and electrode tip 3 butt joints, electrode tip 3 is cylindric; Its internal diameter size is 10mm; Wall thickness 1mm, length is 10mm, electrode cores 2 is cylindric; And electrode cores 2 is coaxial with electrode tip 3; The internal diameter size of electrode cores 2 is 30mm, wall thickness 1mm, and length is 100mm; In electrode cores 2, be provided with take-up reel 14 that volume send confession roll coil of strip dish 6 and the backrush conductive strips 7 of conductive strips 7, can the capstan that supplies traveling electrode band 7 between roll coil of strip dish 6 and the take-up reel 14 12 and the meshing gear 15 that is in transmission connection with capstan 12 corresponding first pinch rollers 8 of pressing mutually and second pinch roller 13, with capstan 12 and with the button 1 that meshing gear 15 is in transmission connection, also can adopt automatic electromagnetic ironware spare and capstan 12 to be in transmission connection; The end of electrode tip 3 is provided with electrode tip hole 4; The diameter of electrode tip hole 4 is 3mm; In electrode tip 3, be provided with the rubber band 18 of fixed electorde area; The first spring splint fixation 16 on one side of rubber band 18 is provided with first spring 17 and is located at electrode tip 3 sidewalls is connected; The second spring splint fixation 21 on the opposite side of rubber band 18 is provided with second spring 20 and is located at electrode tip 3 sidewalls is connected; Electrode tip 3 is provided with first tape guide roller 9 and second tape guide roller 10; Conductive strips 7 are between rubber band 18 and the electrode tip hole 4 through first tape guide roller 9 and second tape guide roller, 10 guiding, and rubber band 18 is connected with and drives its pull bar that moves up and down 11, and pull bar 11 is in transmission connection with meshing gear 15; Rubber band 18 makes drive conductive strips 7 dock or leave with electrode tip hole 4 under the driving of pull bar 11; In electrode tip 3, be provided with one and push down the conduction pinch roller 19 of conductive strips 7 with second tape guide roller 10, conduction pinch roller 19 is connected with the terminals of connecting with external circuit 5, and the width of conductive strips 7 is 6mm; Thickness is 100 μ m; Conductive materials on the conductive layer of conductive strips 7 is the potpourri of graphite, conductive organic matter, metal, metallic compound, nonmetal conductive compound and they and bioactivator enzyme, antibody or DNA, and the soft matrix material of conductive strips 7 is the fluorine derivative of tygon, PVC, polystyrene, ethene, cellulose diacetate, partly-hydrolysed Triafol T or polyethylene terephthalate, and the conducting film preparation method of conductive strips 7 adopts chemical vapor deposition, physical vapour deposition (PVD), serigraphy, electroless plating, microelectronic process engineering, printed circuit board technology, curtain coating drying and forming-film or hot pressing film forming.
Embodiment 1: adopt the coating dryer, and preparation one deck carbon film on the polyester tape base, and be involved in confession roll coil of strip dish 6.Supply roll coil of strip dish 6 and take-up reel 14 according to tape path this, be installed in the automation equipment of the present invention, guarantee that conductive strips 7 are local smoothly at each, tighten.The general-purpose electrode is as working electrode, and mercurous chloride electrode and platinum electrode constitute three-electrode system respectively as contrast electrode with to electrode, this three electrode is immersed be equipped with to be measured 1 * 10
-3In the electrochemical investigating pond of mol/L potassium ferricyanide solution.The terminals of renewable electrode, mercurous chloride electrode and platinum electrode are connected with the corresponding interface of electrochemical analyser respectively, open computer and electrochemical analyser, setup parameter: 1 * 10
-3The potassium ferricyanide solution of mol/L carries out cyclic voltammetry scanning, with the test electrode performance, and sweep velocity 50mV/s, sweep limit 600～-100mV.Open the power switch of apparatus of the present invention, get into measuring process, measure three times after, turn off the automatic renewing device power supply.Referring to Fig. 5, the spike potential difference under the laboratory condition in the gained cyclic voltammogram is below 80mV, and the peak shape symmetry explains that the general-purpose electrode performance is better.
Embodiment 2: determinand changes the Zn of 10 μ g/L, 20 μ g/L, 50 μ g/L into
2+, Cd
2+, Pb
2+, Cu
2+Mixed solution, parameter setting: linear sweep stripping voltammetry, accumulating potential-1500mV; Enrichment time 300s, static 30s, with the sweep velocity of 100mV/s from take-off potential-1500mV; Be scanned up to down the 400mV that rations the power supply (closing magnetic stirring apparatus), record stripping volt-ampere curve.All the other operations are all identical with embodiment 1.Visible by Fig. 6, Zn
2+, Cd
2+, Pb
2+, Cu
2+On bismuth film electrode respectively 0.04 ,-0.55 ,-0.8 ,-1.1V produces sensitive current potential stripping peak, peak height is relevant with ion concentration, and the spike potential at several peaks differs bigger, can measure simultaneously by four kinds of ions.
Embodiment 3: determinand is the Zn of 50 μ g/L
2+, Cd
2+, Pb
2+, Cu
2+Mixed solution, the parameter setting is all identical with embodiment 2 with operation of equipment.Visible by Fig. 7, when adopting this general-purpose electrode assembly to carry out electrochemical analysis, the reappearance of measurement result is very good, and the long-pending size of the solid front cover of each electrode is consistent.
Pass through the foregoing description; Explain that the performance that the present invention is used for the renewable solid working electrode of electrochemical analysis is superior to traditional electrode such as glass-carbon electrode, gold electrode; Can satisfy the requirement as the electrochemical analysis working electrode, it is having broad application prospects aspect the working electrode of online electrochemical monitoring instrument.
Claims (7)
1. renewable solid working electrode that is used for electrochemical analysis; It is characterized in that: the butt joint of electrode cores (2) and electrode tip (3) is provided with the driving mechanism that volume send confession roll coil of strip dish (6) and the take-up reel (14) of the described conductive strips of backrush (7), the capstan (12) that can between described confession roll coil of strip dish (6) and take-up reel (14), move described conductive strips (7) and the pinch roller of conductive strips (7), power paid described capstan (12) in described electrode cores (2); The end of described electrode tip (3) is provided with electrode tip hole (4); In described electrode tip (3), be provided with the rubber band (18) of fixed electorde area; Be provided with spring between the both sides of described rubber band (18) and described electrode tip (3) sidewall; Described electrode tip (3) is provided with tape guide roller; Described conductive strips (7) are between described rubber band (18) and the described electrode tip hole (4) through described tape guide roller guiding; Described rubber band (18) is connected with and drives its pull bar that moves up and down (11); Described pull bar (11) is in transmission connection with described driving mechanism; Described rubber band (18) makes described conductive strips (7) dock or leave with described electrode tip hole (4) under the driving of described pull bar (11), in described electrode tip (3), is provided with one and pushes down the conduction pinch roller (19) of described conductive strips (7) with described tape guide roller, and described conduction pinch roller (19) is connected with the terminals of connecting with external circuit (5).
2. the renewable solid working electrode that is used for electrochemical analysis according to claim 1; It is characterized in that: described driving mechanism is an automatic electromagnetic ironware spare, and perhaps meshing gear (15) reaches the button (1) that is in transmission connection with described meshing gear (15).
3. the renewable solid working electrode that is used for electrochemical analysis according to claim 1 and 2 is characterized in that: described electrode tip (3) is cylindric, and its internal diameter size is 10mm; Wall thickness 1mm, length is 10mm, described electrode cores (2) is cylindric; And described electrode cores (2) is coaxial with described electrode tip (3); The internal diameter size of described electrode cores (2) is 30mm, wall thickness 1mm, and length is 100mm.
4. the renewable solid working electrode that is used for electrochemical analysis according to claim 1 and 2 is characterized in that: the width of described conductive strips (7) is 6mm, and thickness is 100 μ m.
5. the renewable solid working electrode that is used for electrochemical analysis according to claim 1 and 2 is characterized in that: the soft matrix material of described conductive strips (7) is the fluorine derivative of tygon, PVC, polystyrene, ethene, cellulose diacetate, partly-hydrolysed Triafol T or polyethylene terephthalate.
6. the renewable solid working electrode that is used for electrochemical analysis according to claim 1 and 2 is characterized in that: the diameter of described electrode tip hole (4) is 3mm.
7. the renewable solid working electrode that is used for electrochemical analysis according to claim 1 and 2 is characterized in that: described conduction pinch roller (19) is arranged on the bottom of described electrode tip (3) and closes on described electrode tip hole (4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102294622A CN101887043B (en) | 2010-07-19 | 2010-07-19 | Renewable solid working electrode for electrochemical analysis |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102294622A CN101887043B (en) | 2010-07-19 | 2010-07-19 | Renewable solid working electrode for electrochemical analysis |
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| Publication Number | Publication Date |
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| CN101887043A CN101887043A (en) | 2010-11-17 |
| CN101887043B true CN101887043B (en) | 2012-11-07 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109884129B (en) * | 2019-03-27 | 2021-11-23 | 爱德森（厦门）电子有限公司 | Device and method for detecting thermite welding quality of steel rail |
| CN110963549A (en) * | 2019-12-31 | 2020-04-07 | 山西和风佳会电化学工程技术股份有限公司 | Electrochemical reaction chamber descaling driving device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3331545A (en) * | 1964-11-10 | 1967-07-18 | Union Carbide Corp | Wire feed assembly |
| US3799340A (en) * | 1970-12-02 | 1974-03-26 | Fuji Photo Film Co Ltd | Refining photoconductive particle |
| CN1969065A (en) * | 2004-06-17 | 2007-05-23 | 埃托特克德国有限公司 | Device and method for electrolytically treating flat work pieces |
| CN101498940A (en) * | 2008-01-31 | 2009-08-05 | 中芯国际集成电路制造(上海)有限公司 | Method and apparatus for protecting bottom electrode component in plasma etching equipment |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT413638B (en) * | 2001-03-13 | 2006-04-15 | Cnsystems Medizintechnik Gmbh | MEDICAL ELECTRODE |
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2010
- 2010-07-19 CN CN2010102294622A patent/CN101887043B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3331545A (en) * | 1964-11-10 | 1967-07-18 | Union Carbide Corp | Wire feed assembly |
| US3799340A (en) * | 1970-12-02 | 1974-03-26 | Fuji Photo Film Co Ltd | Refining photoconductive particle |
| CN1969065A (en) * | 2004-06-17 | 2007-05-23 | 埃托特克德国有限公司 | Device and method for electrolytically treating flat work pieces |
| CN101498940A (en) * | 2008-01-31 | 2009-08-05 | 中芯国际集成电路制造(上海)有限公司 | Method and apparatus for protecting bottom electrode component in plasma etching equipment |
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