CN107576699A - A kind of carbon-based Ag/AgCl electric field electrodes preparation method of high-specific surface area foam - Google Patents
A kind of carbon-based Ag/AgCl electric field electrodes preparation method of high-specific surface area foam Download PDFInfo
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- CN107576699A CN107576699A CN201610524094.1A CN201610524094A CN107576699A CN 107576699 A CN107576699 A CN 107576699A CN 201610524094 A CN201610524094 A CN 201610524094A CN 107576699 A CN107576699 A CN 107576699A
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Abstract
A kind of carbon-based Ag/AgCl electric field electrodes preparation method of high-specific surface area foam, the electrode is used as matrix material by the use of high-specific surface area foamy carbon, it is first that the foamy carbon for connecting carbon plate is shaped, activated, cleaning and drying process, then foamy carbon surface electrochemistry preplating metallic copper or nickel, by the method deposited metal silver of chemical silvering, uniform silver layer is formed by electroplating thickening, recycles method for electrodeposition to generate silver chloride layer in silver surface；Finally the carbon-based Ag/AgCl electrodes of foam are installed in microporous pipe, filler is filled, by the carbon plate extraction wire being connected with foamy carbon, obtains foamy carbon base-height ratio surface area Ag/AgCl electric field electrodes.The electrode has high-specific surface area, high stability and a low potential drift value, and the potential difference between two identical electrodes is small, self noise is low, can be preferably using the monitoring of Yu Haiyang wide frequency domain electric field signal and anti-corrosion of metal field.
Description
Technical field
The present invention relates to a kind of carbon-based Ag/AgCl electric field electrodes preparation method of high-specific surface area foam, and in particular to a kind of
Ocean wide frequency domain electric field signal detection and the carbon-based Ag/AgCl electric field electrode systems of high-specific surface area foam of metal corrosion potential test
Preparation Method.
Background technology
With the progress of science and technology, during ocean exploitation, electric field signal measurement applies valency with important
Value.Electric field signal has obtained important application in the physics electric field on naval vessel and the detection of seabottom geology structure.
Marine water flows, and cutting magnetic field of the earth can produce corresponding induction field, and these electric field signals can reflect ocean
The multiple information of environment.Because naval vessel is mostly different metal structure composition, different types of metal can produce different corrosion electricity
Position, therefore when two kinds of different metals soak in the seawater together, corrosion loop will be formed, produces corrosion current.In addition, in order to
Naval vessel anti-corrosion, it need to manually apply cathodic protection current.These electric currents are eventually because the effect of seawater flows to propeller, then from spiral shell
Rotation oar returns to ship shell, forms loop, due to the rotation of propeller, causes the cyclically-varying of resistance in loop, so as to
Alternating electric field signal is formed in the seawater.In addition, different geologic structures have different electric field responses to electric field signal in seabed.According to
Principle like this, actively launch a kind of known electric field signal to seabed, observe the changing rule of electric field signal after its reflection, you can point
Separate out the geologic structure in seabed.But electric field signal is decayed quickly, and more based on low frequency signal in the seawater, therefore, ocean
The good electrode of monitoring needs high sensitivity, the stability of electric field signal.In corrosion-resistant field, metal material protection is improper easily to be occurred
Corrosion, corrosion can be more violent and serious especially in briny environment, all causes huge economic losses to the world every year.It is accurate to survey
It is most important in corrosion-resistant field with the protection electric current of control corrosion rate guard system to determine material corrosion current potential, this is also required to high stability
And the reference electrode of low self noise.
Type of electrodes currently used for electric field monitoring and corrosion monitoring mainly has：Copper/copper sulfate electrode, lead/lead chloride electricity
Pole, silver/silver chloride electrode etc..The principle of these three electrodes monitoring electric field is identical, relies primarily on different reversible reactions, works as surrounding
Electric field signal when changing, the charged ion in reversible reaction is moved by the effect of electric field, causes reversible reaction
It is broken, causes electrode potential to change.Monitoring electrode potential change counter can push away the situation of change of electric field signal.Wherein copper/sulfuric acid
Copper electrode is larger to, lead/lead chloride electrode pair extreme difference, is mainly used in land electric field monitoring；Silver/silver chloride electrode is mainly led at present
Cross it is powder sintered be made, compared to copper/copper sulfate electrode and lead/chlorination lead electrode, powder sintered silver/silver chloride electrode has electrode
The advantages that stable performance, long service life, but its ohmic internal resistance is big, anti-polarizability is poor, and current potential easily drifts about, and both influences electric field
Measure influences corrosion monitoring again.Expensive in view of silver, cost is high, how can improve electrode stability, reduce noise, again
Cost can be reduced, is always the target that people pursue.Electrode specific surface area is bigger, and electrode stability will significantly improve, and this will
Favourable Yu Haiyang electrical field test and corrosion monitoring, it is significant for the performance of raising whole system.Foam is carbon-based
On the one hand the preparation of Ag/AgCl electric field electrodes uses high, cheap, light weight the foamy carbon of specific surface area as matrix material
Material, on the other hand by foam carbon surface using chemistry and electrochemical method deposition of silver, obtain silver layer in uniform thickness, it is this
Method can be such that the usage amount of silver reduces so as to reduce preparation cost.Meanwhile the carbon-based Ag/AgCl electric field electrodes of foam have high ratio
Surface area, high stability and low noise, thus in ocean wideband electric field signal monitoring and corrosion monitoring field its have it is very high
Application value.
The content of the invention
For problem above, the present invention is prepared for a kind of carbon-based Ag/AgCl electric field electrodes of high-specific surface area foam.To realize
The purpose of the present invention, the carbon-based Ag/AgCl electric field electrodes structure of high-specific surface area foam are as shown in Figure 1.Its preparation method is as follows：
The foamy carbon for connecting carbon plate is shaped.
Pretreatment：Activation, cleaning, dry.
Foam carbon surface electrochemistry preplating metallic copper or nickel first, then surface chemistry is silver-plated, and electroplated thicken is formed
Even silver layer.
Foam carbon surface silver utilizes method for electrodeposition generation silver chloride layer.
The carbon-based Ag/AgCl electrodes of foam are installed in microporous pipe, filler is filled, passes through the carbon plate being connected with foamy carbon
Extraction wire.
Electrode method is prepared to describe it exemplified by foamy carbon electroplate in present invention, with prior art phase
Than gain effect of the invention is：
The carbon-based Ag/AgCl electric field electrodes good conductivity of high-specific surface area foam, surface area are big, significantly improve the stability of electrode.
High-specific surface area foamy carbon makes Ag/AgCl electric field electrodes have higher anti-polarization performance.
Foamy carbon substrate quality is light, reduces electrode weight.
Foamy carbon is cheap, significantly reduces electrode cost.
The carbon-based Ag/AgCl electric field electrodes of high-specific surface area foam have high stability, are advantageous to accurately determine corrosion potential,
Be advantageous to the accurate control to erosion prevention system protection electric current.
The carbon-based Ag/AgCl electric field electrodes of high-specific surface area foam enable the accurate controlling potential of erosion prevention system, extend system
Unite the life-span.
Microporous pipe outside electrode is advantageously implemented exchange of seawater, prevents ocean current from influenceing.
Microporous pipe outside electrode can realize that the carbon-based Ag/AgCl electric field electrodes of foam are kept in dark place.
The carbon-based Ag/AgCl electric field electrodes potential difference of high-specific surface area foam（Extreme difference）Small, stability is high, is advantageous to pairwise testing
External electrical field.
The carbon-based Ag/AgCl electric field electrodes of high-specific surface area foam have high stability, low self noise, to the spirit of extraneous electric field energy
Quick response, be advantageous to improve the precision of electrical field test.
Brief description of the drawings
Fig. 1 is the carbon-based Ag/AgCl electrode structures schematic diagram of high-specific surface area foam
Wherein：1st, wire 2, filler 3, end cap 4, microporous pipe 5, Ag/AgCl layers 6, foamy carbon
Embodiment：
The present invention is further described below according to Figure of description and embodiment, following examples are only used for clearly saying
Bright design of the invention, and can not be limited the scope of the invention with this.
Embodiment 1
As shown in figure 1, the present invention relates to a kind of carbon-based Ag/AgCl electric field electrodes preparation method of high-specific surface area foam, by even
The foamy carbon finished product 6 for connecing carbon plate is processed into the shape that profile is cylinder, and the wherein mm of radius 5, length is 5 cm, activation, cleaning
And after drying process, foam carbon surface carries out electrochemistry preplating metal nickel dam, then deposits one layer of gold by the method for chemical silvering
Category silver, then plating thicken silver layer, recycle the method for electrolytic deposition in the electrolytically generated silver chlorate 5 of silver layer surface, then by foam
Carbon-based Ag/AgCl electrodes are installed in microporous pipe 4, fill quartz sand filler 2, draw silver wire 1.
Embodiment 2
As shown in figure 1, the present invention relates to a kind of carbon-based Ag/AgCl electric field electrodes preparation method of high-specific surface area foam, by even
The foamy carbon finished product 6 for connecing carbon plate is processed into the shape that profile is cylinder, and the wherein mm of radius 10, length is 15 cm, activates, be clear
Wash and drying process after, foam carbon surface carries out electrochemistry preplating metal nickel dam, then deposits one layer by the method for chemical silvering
Argent, then plating thicken silver layer, recycle the method for electrolytic deposition in the electrolytically generated silver chlorate 5 of silver layer surface, then will bubble
The carbon-based Ag/AgCl electrodes of foam are installed in microporous pipe 4, fill quartz sand filler 2, draw silver wire 1.
Embodiment 3
As shown in figure 1, the present invention relates to a kind of carbon-based Ag/AgCl electric field electrodes preparation method of high-specific surface area foam, by even
The foamy carbon finished product 6 for connecing carbon plate is processed into the shape that profile is cylinder, and the wherein mm of radius 15, length is 50 cm, activates, be clear
Wash and drying process after, foam carbon surface carries out electrochemistry preplating metal copper layer, then deposits one layer by the method for chemical silvering
Argent, then plating thicken silver layer, recycle the method for electrolytic deposition in the electrolytically generated silver chlorate 5 of silver layer surface, then will bubble
The carbon-based Ag/AgCl electrodes of foam are installed in microporous pipe 4, fill quartz sand filler 2, draw silver wire 1.
Embodiment 4
As shown in figure 1, the present invention relates to a kind of carbon-based Ag/AgCl electric field electrodes preparation method of high-specific surface area foam, by even
Connect carbon plate foamy carbon finished product 6 be processed into profile be cuboid shape, the wherein mm of length 10, the mm of width 5, height 30 mm,
After activation, cleaning and drying process, foam carbon surface carries out electrochemistry preplating metal copper layer, then is sunk by the method for chemical silvering
Product layer of metal silver, can so electroplate thickening silver layer, recycle the method for electrolytic deposition in the electrolytically generated silver chlorate 5 of silver layer surface,
The carbon-based Ag/AgCl electrodes of foam are installed in microporous pipe 4 again, fill quartz sand filler 2, draw silver wire 1.
Embodiment 5
As shown in figure 1, the present invention relates to a kind of carbon-based Ag/AgCl electric field electrodes preparation method of high-specific surface area foam, by even
The foamy carbon finished product 6 for connecing carbon plate is processed into the shape that profile is cylinder, and the wherein mm of radius 5, length is 50 cm, activates, be clear
Wash and drying process after, foam carbon surface carries out electrochemistry preplating metal copper layer, then deposits one layer by the method for chemical silvering
Argent, then plating thicken silver layer, recycle the method for electrolytic deposition in the electrolytically generated silver chlorate 5 of silver layer surface, then will bubble
The carbon-based Ag/AgCl electrodes of foam are installed in microporous pipe 4, fill tripolite filling material 2, draw silver wire 1.
Embodiment 6
In the corrosion potential experiment of the measure high NiCr alloy coats of 40Cr carbon steels, using LK2005B electrochemical workstations, three electricity
Polar body system, the electrode wherein the 40Cr carbon steels of high NiCr alloy coats are worked, platinum electrode are done to electrode, successively from saturation calomel
Electrode and the carbon-based Ag/AgCl electric field electrodes of foam do reference electrode, test corrosion potential using potentiostatic method, contrast is found, is adopted
When doing reference electrode test with the carbon-based Ag/AgCl electric field electrodes of foam, obtained potential curve is steady, and corrosion potential value is more smart
Really.
Embodiment 7
The carbon-based Ag/AgCl electric field electrodes of foam are put into cuboid glass container inside and fixation to parallel vertically, hold to glass
Natural sea-water is added in device, makes the carbon-based Ag/AgCl electric field electrodes of foam to being completely immersed in seawater；With the voltage of data collecting instrument
Passage records the carbon-based Ag/AgCl electric field electrodes of foam to the voltage change at both ends, have recorded the extreme difference situation of change of 90 hours.
Extreme difference drift value is 18 μ V or so in such a carbon-based Ag/AgCl electric field electrodes of foam 24 hours, has high extreme difference stability.
Embodiment 8
The carbon-based Ag/AgCl electric field electrodes of foam are put into cuboid glass container inside and fixation to parallel vertically, add thereto
Enter natural sea-water, make the carbon-based Ag/AgCl electric field electrodes of foam to being completely immersed in seawater；It is put into emission electrode（Carbon plate）, and with
Signal generator is connected, and emission electrode and the carbon-based Ag/AgCl electricity of foam are recorded respectively with two voltage channels of data collecting instrument
Voltage change of the field plate to both ends.The output signal of signal generator is arranged to：1 mHz, 50 mV.The carbon-based Ag/ of foam
AgCl electric field electrodes are accurately monitored the electric field signal of signal generator transmitting.
Embodiment 9
By the carbon-based Ag/AgCl electric field electrodes of a pair of foams it is vertical it is parallel be placed on it is inside cuboid glass container and fixed, in series connection
Resistance box, dc source is connected, is changed with extreme difference between data logger voltage channel recording electrode pair.Pass through direct current during test
Power supply applies 924.8 nA continuous currents, and polarize 1min.It is computed, the carbon-based Ag/AgCl electric field electrodes of foam are in 924.8 nA
Polarization resistance R caused by 1 min of constant current polarizationPolarizationThe Ω of=△ U/I=25.81, polarization resistance is small, and anti-polarization performance is good.
Embodiment 10
The carbon-based Ag/AgCl electric field electrodes of foam are put into cuboid glass container inside and fixation to parallel vertically, add thereto
Enter natural sea-water, make the carbon-based Ag/AgCl electric field electrodes of foam to being completely immersed in seawater；It is put into emission electrode（Carbon plate）, and with
Signal generator is connected, and emission electrode and the carbon-based Ag/AgCl electricity of foam are recorded respectively with two voltage channels of data collecting instrument
Field plate records the current signal in loop with data logger current channel to the voltage change at both ends.By signal generator
Output signal frequency is arranged to 10 mHz, and amplitude is respectively 1 mV, 5 mV, 10 mV, 50 mV, 100 mV, and its line is calculated
Property degree be less than 0.1%, reflect that the carbon-based Ag/AgCl electric field electrodes of foam can accurately respond electric field signal.
Embodiment 11
By the carbon-based Ag/AgCl electric field electrodes of foam to being placed in parallel into vertically in plastic containers, 3.5%NaCl solution is added, by electrode
Pair it is connected and is put into screened room with low-noise amplifier and data collecting instrument.After electrode pair soaks 24 h, Acquisition Instrument starts
The open-circuit voltage of measuring electrode pair, sample frequency 2kHz, measurement range are the mV of -10 mV~+10, obtain electrode and are with measurement
System overall noise, subtracts measuring system intrinsic noise, can obtain this electric-field sensor in 1Hz frequency power spectrum root mean square noises.Through
Calculate, self noise numerical value is 1.6 nV/@1Hz。
Claims (8)
1. a kind of carbon-based Ag/AgCl electric field electrodes preparation method of high-specific surface area foam, the electrode utilize high-specific surface area foam
Carbon is shaped by the foamy carbon for connecting carbon plate first as matrix material, activated, cleaning and drying process, so
Foamy carbon surface electrochemistry preplating metallic copper or nickel afterwards, by the method deposited metal silver of chemical silvering, electroplated thicken is formed
Uniform silver layer, method for electrodeposition is recycled to generate silver chloride layer in silver surface；Finally the carbon-based Ag/AgCl electrodes of foam are installed
In in microporous pipe, filler is filled, passes through the carbon plate extraction wire being connected with foamy carbon.
2. the carbon-based Ag/AgCl electric field electrodes preparation method of a kind of high-specific surface area foam according to claim 1, its feature
It is：Ag/AgCl electrode base materials are used as by the use of foamy carbon.
3. the carbon-based Ag/AgCl electric field electrodes preparation method of a kind of high-specific surface area foam according to claim 1, its feature
It is：In foam carbon surface deposited metal silver.
4. the carbon-based Ag/AgCl electric field electrodes preparation method of a kind of high-specific surface area foam according to claim 1, its feature
It is：Method for electrodeposition generation silver chloride layer is utilized in foamy carbon silver surface.
5. the method for foam carbon surface deposition of silver according to claim 3, it is characterised in that：First in foam carbon matrix material table
Face preplating metallic copper or nickel.
6. the method for foam carbon surface deposition of silver according to claim 3, it is characterised in that：The metallic copper of foamy carbon preplating or
Nickel surface chemical silvering.
7. the method for foam carbon surface deposition of silver according to claim 3, it is characterised in that：Foamy carbon chemical plating silver layer is through electricity
Plating thickening forms uniform silver layer.
A kind of 8. carbon-based Ag/AgCl electric field electrodes preparation method of high-specific surface area foam according to claim 1, by foam
Carbon-based Ag/AgCl electrodes are installed in microporous pipe, are filled filler, are passed through the carbon plate extraction wire being connected with foamy carbon.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110006813A (en) * | 2019-04-08 | 2019-07-12 | 贵州师范大学 | A kind of production method of amorphous metal strip corroding electrode |
| CN113063995A (en) * | 2021-03-16 | 2021-07-02 | 中国海洋大学 | Carbon-based conductive polymer film underwater electric field sensor |
| CN114481249A (en) * | 2022-01-26 | 2022-05-13 | 中国海洋大学 | Modified carbon material, preparation method and application thereof, ocean electric field sensor electrode and application thereof |
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| CN102608661A (en) * | 2012-03-06 | 2012-07-25 | 中国地质大学（北京） | Electrode device for measuring seabed weak electric field signal and manufacture method of electrode device |
| CN103616529A (en) * | 2013-12-13 | 2014-03-05 | 国家海洋技术中心 | Expendable type electromagnetic ocean current profile measuring probe |
| CN104155532A (en) * | 2014-08-08 | 2014-11-19 | 苏州格林泰克科技有限公司 | Marine electric field measuring device |
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| CN102608661A (en) * | 2012-03-06 | 2012-07-25 | 中国地质大学（北京） | Electrode device for measuring seabed weak electric field signal and manufacture method of electrode device |
| CN103616529A (en) * | 2013-12-13 | 2014-03-05 | 国家海洋技术中心 | Expendable type electromagnetic ocean current profile measuring probe |
| CN104155532A (en) * | 2014-08-08 | 2014-11-19 | 苏州格林泰克科技有限公司 | Marine electric field measuring device |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110006813A (en) * | 2019-04-08 | 2019-07-12 | 贵州师范大学 | A kind of production method of amorphous metal strip corroding electrode |
| CN110006813B (en) * | 2019-04-08 | 2021-09-14 | 贵州师范大学 | Method for manufacturing amorphous metal thin strip corrosion electrode |
| CN113063995A (en) * | 2021-03-16 | 2021-07-02 | 中国海洋大学 | Carbon-based conductive polymer film underwater electric field sensor |
| CN114481249A (en) * | 2022-01-26 | 2022-05-13 | 中国海洋大学 | Modified carbon material, preparation method and application thereof, ocean electric field sensor electrode and application thereof |
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