CN114481249A - Modified carbon material, preparation method and application thereof, ocean electric field sensor electrode and application thereof - Google Patents

Modified carbon material, preparation method and application thereof, ocean electric field sensor electrode and application thereof Download PDF

Info

Publication number
CN114481249A
CN114481249A CN202210091046.3A CN202210091046A CN114481249A CN 114481249 A CN114481249 A CN 114481249A CN 202210091046 A CN202210091046 A CN 202210091046A CN 114481249 A CN114481249 A CN 114481249A
Authority
CN
China
Prior art keywords
carbon material
electrode
electric field
carbon
modified carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210091046.3A
Other languages
Chinese (zh)
Other versions
CN114481249B (en
Inventor
付玉彬
许嘉威
侯晓帆
胡承儒
宰学荣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ocean University of China
Original Assignee
Ocean University of China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ocean University of China filed Critical Ocean University of China
Priority to CN202210091046.3A priority Critical patent/CN114481249B/en
Publication of CN114481249A publication Critical patent/CN114481249A/en
Application granted granted Critical
Publication of CN114481249B publication Critical patent/CN114481249B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/02—Electrolytic coating other than with metals with organic materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01V—GEOPHYSICS; GRAVITATIONAL MEASUREMENTS; DETECTING MASSES OR OBJECTS; TAGS
    • G01V3/00—Electric or magnetic prospecting or detecting; Measuring magnetic field characteristics of the earth, e.g. declination, deviation
    • G01V3/08—Electric or magnetic prospecting or detecting; Measuring magnetic field characteristics of the earth, e.g. declination, deviation operating with magnetic or electric fields produced or modified by objects or geological structures or by detecting devices

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Remote Sensing (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Electromagnetism (AREA)
  • Inorganic Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Geophysics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

The invention relates to the technical field of ocean electric field sensors, in particular to a modified carbon material, a preparation method and application thereof, an ocean electric field sensor electrode and application thereof. The preparation method provided by the invention comprises the following steps: carrying out heat treatment on the carbon material to obtain a high-temperature treated carbon material; electrolyzing the high-temperature treated carbon material serving as an anode, a platinum sheet serving as a cathode and a saturated calomel electrode serving as a reference electrode in an electrolyte to obtain the modified carbon material; the electrolyte includes dicyandiamide. According to the description of the embodiment, the specific capacitance of the modified carbon material prepared by the preparation method disclosed by the invention reaches 9.368F/g; the charge transfer resistance and the low-frequency capacitive reactance are obviously reduced; self-noise is
Figure DDA0003489199710000011
The potential drift amount is 0.24mV/d, and the low-frequency weak electric field signals of 1mHz and 0.01V/m can be normally responded, so that the response sensitivity and the accuracy of the electrode are obviously improved.

Description

Modified carbon material, preparation method and application thereof, ocean electric field sensor electrode and application thereof
Technical Field
The invention relates to the technical field of ocean electric field sensors, in particular to a modified carbon material, a preparation method and application thereof, an ocean electric field sensor electrode and application thereof.
Background
With the development of modern ship technology, the stealth capability of ships in the sea is higher and higher, and the requirement of national defense safety is difficult to support by only the traditional acoustic detection means. Ships inevitably produce electric field signals in the ocean, and the ocean electric field detection technology is more and more paid attention as an important supplementary means of acoustic detection. However, seawater has a strong absorption effect on high-frequency electromagnetic waves, so that low-frequency weak electric field signals are mainly used in the ocean, and the electric field sensor serving as a core device for ocean detection needs to have high signal response accuracy and sensitivity.
Electrodes of marine electric field sensors are generally divided into two categories, i.e. reversible electrodes and inert electrodes. The reversible electrode comprises Ag/AgCl and Hg/Hg2Cl2、Pb/PbCl2Electrodes, and the like, such insoluble metal salt electrodes being non-polarizable electrodes. Inert electrodes include carbon fiber, tantalum electrodes, graphite, carbon aerogel electrodes, and the like, which are polarizable electrodes. At present, the preparation and research of the reversible electrode are mature in China, and the Ag/AgCl electrode is widely applied to the field of ocean electric field detection.
The carbon electrode is used as a substitute of a traditional Ag/AgCl electrode, the problems of light degradation and degradation, high cost, difficult storage and transportation and the like of the Ag/AgCl electrode can be solved, but the unmodified carbon fiber has almost no polar group and active substance on the surface, an underwater double electric layer has poor stability, and is difficult to respond to low-frequency weak signals in the sea.
Disclosure of Invention
The invention aims to provide a modified carbon material, a preparation method and application thereof, an ocean electric field sensor electrode and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a modified carbon material, which comprises the following steps:
carrying out heat treatment on the carbon material to obtain a high-temperature treated carbon material;
electrolyzing the high-temperature treated carbon material serving as an anode, a platinum sheet serving as a cathode and a saturated calomel electrode serving as a reference electrode in an electrolyte to obtain the modified carbon material;
the electrolyte includes dicyandiamide.
Preferably, the carbon material includes carbon fiber, carbon felt, carbon cloth, carbon rod or carbon foam.
Preferably, the heat treatment temperature is 300-600 ℃, the heat preservation time is 20-60 min, and the heating rate of heating to the heat treatment temperature is 3-10 ℃/min.
Preferably, the electrolyte further comprises potassium chloride;
the mass concentration of dicyandiamide and potassium chloride in the electrolyte is 2%.
Preferably, the voltage of the electrolysis is 3-7V, and the time is 5-20 min.
Preferably, the carbon material is sequentially washed and dried before the heat treatment;
the cleaning solution adopted by the cleaning is a mixed solution of ethanol and acetone in a volume ratio of 1: 1.
The invention also provides a modified carbon material prepared by the preparation method in the technical scheme, which comprises a carbon material and the polydicyanamide grafted on the surface of the carbon material.
The invention also provides application of the modified carbon material in the technical scheme in preparation of the ocean electric field sensor electrode.
The invention provides an ocean electric field sensor electrode which comprises an electrode, a lead and a packaging structure, wherein the electrode is arranged on the lead;
the electrode is connected with a lead; the packaging structure packages the contact area of the electrode and the lead;
the electrode is made of the modified carbon material in the technical scheme.
The invention also provides the application of the ocean electric field sensor electrode in the technical scheme in detecting the electric field signals in the ocean.
The invention provides a preparation method of a modified carbon material, which comprises the following steps: carrying out heat treatment on the carbon material to obtain a high-temperature treated carbon material; electrolyzing the high-temperature treated carbon material serving as an anode, a platinum sheet serving as a cathode and a saturated calomel electrode serving as a reference electrode in an electrolyte to obtain the modified carbon material; the electrolyte includes dicyandiamide. Firstly, carrying out heat treatment on a carbon material to introduce oxygen-containing groups on the surface of the carbon material so as to provide more active sites for the subsequent modification; secondly, in the process of carrying out the electrolytic treatment (comprising three stages, namely electrochemical oxidation, electrochemical grafting and electrochemical polymerization), oxidizing oxygen-containing groups such as carbonyl, hydroxyl and the like on the surface of the carbon material into carboxyl; then dicyandiamide in the electrolyte is adsorbed on the surface of the carbon fiber through electrostatic or hydrogen bond interaction and is grafted to the surface of the carbon material through a chemical bond; finally, with the prolonging of the electro-grafting time, the polymerization reaction is carried out between dicyandiamide molecules which are grafted to the surface of the carbon material, and a layer of dicyandiamide film is formed on the surface of the carbon material. On the basis, the polarity of the surface of the carbon material can be remarkably improved, the capability of adsorbing ions in a solution is improved, and an electrode/seawater interface double electric layer stable structure (shown in figure 15) is more favorably formed, so that the poly-dicyandiamide film has excellent response performance to an electric field. According to the description of the embodiment, the specific capacitance of the modified carbon material prepared by the preparation method disclosed by the invention reaches 9.368F/g; the charge transfer resistance and the low-frequency capacitive reactance are obviously reduced; self-noise is
Figure BDA0003489199690000031
The potential drift amount is 0.24mV/d, and the low-frequency weak electric field signals of 1mHz and 0.01V/m can be normally responded, so that the response sensitivity and the accuracy of the electrode are obviously improved.
Compared with the traditional Ag/AgCl electrode, the modified carbon material prepared by the preparation method has the following beneficial effects:
1. the selectable carbon material has wide source and low cost;
2. the process is simple and rapid, the chemical stability of the modified sample is high, and the dry transportation and storage are convenient;
3. the impedance of the modified carbon material is significantly reduced. Under the frequency of 10mHz, the impedance is only 8.89 omega, and the characteristic of low frequency and low impedance is favorable for reducing the self noise of the electrode and improving the sensitivity of ocean electric field signal detection;
4. the modified carbon material prepared by the invention has low potential drift amount which is only 0.24mV/d and is equivalent to an Ag/AgCl electrode, thus being beneficial to improving the electrode detection capability, avoiding data overflow and reducing the electrode self-noise;
5. the counter electrode prepared from the modified carbon material can normally respond to electric field signals of 1mHz and 0.01V/m, and widens the range of low-frequency response signals (the normal frequency response range is 0.01Hz or more, and the normal response field intensity is 0.1V/m or more);
6. the linear error of the paired electrode prepared from the modified carbon material is only 0.082%, which is equivalent to that of an Ag/AgCl electrode, and the accuracy of the electric field signal of the carbon material electrode is obviously improved.
7. The electric field sensor formed by the counter electrode prepared from the modified carbon material has higher response sensitivity than that formed by the Ag/AgCl electrode, and can detect electric field signals at a longer distance.
Drawings
FIG. 1 is an SEM image of a carbon fiber of example 1;
FIG. 2 is an SEM image of the high temperature treated carbon fiber of example 1;
FIG. 3 is an SEM image of a modified carbon fiber of example 1;
FIG. 4 is a TEM image of the modified carbon fiber of example 1;
FIG. 5 is an XPS survey scan of the carbon fibers, high temperature treated carbon fibers and modified carbon fibers of example 1;
FIG. 6 is an XPS peak spectra of the carbon fiber of example 1;
FIG. 7 is an XPS peak spectra of the high temperature treated carbon fiber of example 1;
FIG. 8 is an XPS peak spectra of the modified carbon fiber of example 1;
FIG. 9 is a cyclic voltammogram of the carbon fiber, the high temperature treated carbon fiber, and the modified carbon fiber described in example 1;
FIG. 10 is a complex plane view of the AC impedance of the electrodes of the carbon fiber, the high temperature processed carbon fiber and the modified carbon fiber according to example 1 (the inset is an equivalent circuit diagram);
FIG. 11 is a graph of the potential stability of carbon fibers, high temperature treated carbon fibers, modified carbon fibers, and Ag/AgCl as described in example 1;
FIG. 12 is a graph of the frequency response of the high temperature processed carbon fibers, modified carbon fibers, and Ag/AgCl of example 1;
FIG. 13 is a schematic structural diagram of a potential stability testing apparatus;
FIG. 14 is a schematic structural diagram of a frequency response testing apparatus;
FIG. 15 is a schematic diagram of the mechanism of the modified carbon material of the present invention applied to an electrode of an ocean electric field sensor for detecting electric field signals in the ocean.
Detailed Description
The invention provides a preparation method of a modified carbon material, which comprises the following steps:
carrying out heat treatment on the carbon material to obtain a high-temperature treated carbon material;
electrolyzing the high-temperature treated carbon material serving as an anode, a platinum sheet serving as a cathode and a saturated calomel electrode serving as a reference electrode in an electrolyte to obtain the modified carbon material;
the electrolyte includes dicyandiamide.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
The carbon material is subjected to heat treatment to obtain the high-temperature treated carbon material.
In the present invention, it is preferable that the carbon material is washed and dried in this order before the heat treatment. In the present invention, the cleaning liquid used for cleaning is preferably a mixed liquid of ethanol and acetone in a volume ratio of 1: 1. In the present invention, the washing is preferably performed under the condition of ultrasound; the process of the ultrasound is not limited in any way, and can be performed by a process known to those skilled in the art. The number and time of the washing are not particularly limited in the present invention, and those known to those skilled in the art may be used. In a specific embodiment of the present invention, the number of times of cleaning is specifically 3, and the time of each cleaning is specifically 15 min. The drying process is not particularly limited, and may be performed by a method known to those skilled in the art. In a specific embodiment of the present invention, the drying is specifically performed in an oven.
In the present invention, the carbon material preferably includes carbon fiber, carbon felt, carbon cloth, carbon rod, or carbon foam.
In the invention, the temperature of the heat treatment is preferably 300-600 ℃, more preferably 500-600 ℃, and most preferably 600 ℃; the heat preservation time is preferably 20-60 min, more preferably 20-40 min, and most preferably 30 min; the heating rate of the heating to the heat treatment temperature is preferably 3-10 ℃, more preferably 3-8 ℃, and most preferably 5 ℃/min. In the present invention, the heat treatment is preferably performed in a muffle furnace.
After the carbon material is treated at high temperature, the carbon material treated at high temperature is used as an anode, a platinum sheet is used as a cathode, a saturated calomel electrode is used as a reference electrode, and electrolysis is carried out in electrolyte to obtain the modified carbon material.
The platinum sheet and the saturated calomel electrode are not limited in any way in the invention, and the platinum sheet and the saturated calomel electrode can be adopted by the method well known by the technical personnel in the field.
In the present invention, the electrolyte includes dicyandiamide, and further preferably includes potassium chloride; in the present invention, the mass concentration of both dicyandiamide and potassium chloride in the electrolyte is preferably 2%. In the present invention, the solvent of the electrolyte is preferably water, and the water is preferably distilled water.
In the invention, the voltage of the electrolysis is preferably 3-7V, more preferably 5-7V, and most preferably 7V; the time is preferably 5 to 20min, more preferably 5 to 10min, and most preferably 10 min.
The invention also provides a modified carbon material prepared by the preparation method in the technical scheme, which comprises a carbon material and the polydicyanamide grafted on the surface of the carbon material.
The grafting amount of the dicyandiamide is not limited at all, and a microscopic dicyandiamide film can be formed on the surface of the carbon material (the microscopic form can be understood as that the dicyandiamide film can be seen under SEM).
The invention also provides application of the modified carbon material in the technical scheme in preparation of the ocean electric field sensor electrode.
The invention provides an ocean electric field sensor electrode which comprises an electrode, a lead and a packaging structure, wherein the electrode is arranged on the lead;
the electrode is connected with a lead; the packaging structure packages the contact area of the electrode and the lead;
the electrode is made of the modified carbon material in the technical scheme.
The size of the electrode is not limited in any way, and can be adjusted according to actual needs. In a particular embodiment of the invention, the electrode has a length of in particular 9cm and a weight of in particular 0.3 g.
In the present invention, the encapsulation structure preferably encapsulates the contact area of the electrode and the lead with epoxy resin.
In the invention, the marine electric field sensor electrode also preferably comprises a sealed cavity and a microporous protection sleeve; the sealing cavity and the micropore protective sleeve are sequentially sleeved on the outer side of the electrode.
The invention also provides the application of the ocean electric field sensor electrode in the technical scheme in detecting the electric field signals in the ocean. The method of the present invention is not particularly limited, and the method may be performed by a method known to those skilled in the art. In an embodiment of the invention, the marine electric field sensor electrodes are preferably used in pairs according to the potential nearest principle.
The modified carbon material, the preparation method and the application thereof, the marine electric field sensor electrode and the application thereof provided by the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Placing carbon fiber (marked as CF) in a mixed solution of ethanol and acetone with a volume ratio of 1:1, and ultrasonically cleaning for 3 times, wherein each time is 15 min; putting the carbon fiber into an oven for drying, and then putting the carbon fiber into a muffle furnace for heat treatment, wherein the temperature of the heat treatment is 600 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 30min, so as to obtain high-temperature treated carbon fiber (marked as CF 600);
electrolyzing 0.5g of the high-temperature treated carbon fiber serving as an anode, a platinum sheet serving as a cathode and a Saturated Calomel Electrode (SCE) serving as a reference electrode in an electrolyte (the mass concentration of dicyandiamide is 2%, the mass concentration of potassium chloride is 2%, and a solvent is distilled water), wherein the voltage of the electrolysis is 7V, and the time is 10 min; obtaining the modified carbon fiber (marked as CF-7V);
cutting the modified carbon fiber into 9cm long to prepare 0.3g of modified carbon fiber bundle;
connecting the modified carbon fiber bundle with a lead, and packaging a contact area with epoxy resin; placing the modified carbon fiber bundle in a sealed cavity, and installing a micropore protective sleeve outside the modified carbon fiber bundle to obtain an ocean electric field sensor electrode;
performing SEM tests on the carbon fibers, the high-temperature treated carbon fibers and the modified carbon fibers, wherein the test results are shown in figures 1-3, wherein figure 1 is an SEM image of the carbon fibers, figure 2 is an SEM image of the high-temperature treated carbon fibers, and figure 3 is an SEM image of the modified carbon fibers; as can be seen from FIGS. 1 to 3, a small number of spots and scratches exist on the surface of the carbon fiber; the high-temperature treatment of the surface of the carbon fiber generates grooves formed by oxidation; a layer of polymer film is arranged on the surface of the modified carbon fiber;
the modified carbon fiber is subjected to a TEM test, the test result is shown in FIG. 4, and the existence of a polymer film on the surface of the modified carbon fiber can be further verified by the test result shown in FIG. 4;
performing XPS test on the carbon fiber, the high-temperature treated carbon fiber and the modified carbon fiber, wherein the test results are shown in figures 5-8 and table 1, wherein figure 5 is an XPS full scan spectrogram of the carbon fiber, the high-temperature treated carbon fiber and the modified carbon fiber, figure 6 is an XPS peak separation spectrum of the carbon fiber, figure 7 is an XPS peak separation spectrum of the high-temperature treated carbon fiber, figure 8 is an XPS peak separation spectrum of the modified carbon fiber, and table 1 is the types and contents of carbon functional groups on the surfaces of the carbon fiber, the high-temperature treated carbon fiber and the modified carbon fiber; as can be seen from FIGS. 5 to 8 and Table 1, the nitrogen content of the carbon fiber is only 4.38%, while the nitrogen content of the modified carbon fiber is as high as 9.18%. According to the analysis of the position of the fitted peak of C1s, an additional peak of C6 appears in the high-temperature-treated carbon fiber, and the peak of the binding energy belongs to a carboxyl group. The modified carbon fiber surface also exhibited a peak of C5 (-CONH), demonstrating that dicyandiamide was grafted to the carbon fiber surface.
Types and contents of carbon functional groups on surfaces of the carbon fibers, the high-temperature-treated carbon fibers and the modified carbon fibers described in Table 1
Figure BDA0003489199690000071
Figure BDA0003489199690000081
Cyclic voltammetry tests are performed on the carbon fibers, the high-temperature treated carbon fibers and the modified carbon fibers, and the test results are shown in fig. 9 and table 2, and as can be seen from fig. 9, cyclic voltammetry curves of the carbon fibers, the high-temperature treated carbon fibers and the modified carbon fibers all present similar rectangles, have no obvious peak current and present typical double electric layer characteristics; as is clear from Table 2, the specific capacitance of CF-7V was 9.368F/g, which is 31.6 times that of CF. The reason is that dicyandiamide can be continuously polymerized on the surface of carbon fiber along with the proceeding of the grafting process, and the introduction of a nitrogen-containing group can cause the increase of the capacitance of an electric double layer of an electrode;
TABLE 2 specific capacitance and multiplying factor of carbon fibers, high temperature treated carbon fibers and modified carbon fibers
Electrode for electrochemical cell CF CF600 CF-7V
Specific capacitance (F/g) 0.296 12.804 9.368
Multiplying power 1 43.2 31.6
Performing electrochemical impedance test on the carbon fiber, the high-temperature treated carbon fiber and the modified carbon fiber, wherein the test results are shown in fig. 10 and table 3, wherein fig. 10 is an electrode alternating current impedance complex plan view (an inset is an equivalent circuit diagram) of the carbon fiber, the high-temperature treated carbon fiber and the modified carbon fiber, and table 3 is impedance fitting parameters (wherein Rs is contact resistance, including self internal resistance, electrolyte resistance and interface resistance of a carbon fiber electrode, Rct is charge transfer resistance, and CPE-P represents the degree of deviation of a constant phase angle from a pure capacitance-Zim/Ω (at 10mHz) of the electrode impedance value at a frequency of 10mHz) of the carbon fiber, the high-temperature treated carbon fiber and the modified carbon fiber; as can be seen from FIG. 10 and Table 3, the Rs of CF-7V was slightly increased as compared with CF, because the conductivity of the polycyanum film formed on the surface of the electrode was inferior to that of carbon fiber. And R of CF-7VctAt the minimum, because the poly cyanamide on the surface of the carbon fiber has a conjugated chain structure, electrons are easier to transmit between the poly cyanamide and the poly cyanamide. At a frequency of 10mHz, the-Zim/Ω of CF is 452.74 Ω, while the-Zim/Ω of CF-7V is 7.73 Ω, which is about 1/58 of CF. This will broaden the frequency range of the carbon fiber electrode response to the external electric field, especially to the low frequency rangeWill be more efficient;
TABLE 3 impedance fitting parameters for carbon fibers, high temperature treated carbon fibers, and modified carbon fibers
Figure BDA0003489199690000082
Figure BDA0003489199690000091
The potential stability testing device shown in fig. 13 is adopted to perform the potential stability test on the carbon fibers, the high-temperature treated carbon fibers, the modified carbon fibers and the Ag/AgCl, and the testing process is as follows: according to the principle of potential approximation, carbon fibers, high-temperature treated carbon fibers and modified carbon fibers are respectively paired to obtain paired electrodes, the paired electrodes are placed in seawater (sodium chloride solution with the mass concentration of 3.5 wt% is used as seawater simulation liquid), the temperature and the seawater salinity are kept constant, a high-precision multichannel signal recorder is used for carrying out potential acquisition, the sampling interval is set to be 1min, and the testing time is 7 days. The test results are shown in fig. 11 and table 4, where fig. 11 is a potential stability curve of the carbon fiber, the high-temperature-treated carbon fiber, the modified carbon fiber, and the Ag/AgCl, and table 4 is a potential drift amount of the carbon fiber, the high-temperature-treated carbon fiber, the modified carbon fiber, and the Ag/AgCl for 7 days, and it can be seen from fig. 11 and table 4 that the CF potential drift amount is always large and the modified group potential is relatively stable in the whole test process. The potential drift amount of CF-7V is only 1.68mV (1.12mV) in seven days, which is equivalent to that of Ag/AgCl (see inset and Table 4), and the long-term stability of CF-7V is equivalent to that of Ag/AgCl;
table 4 shows the amount of potential shift of carbon fibers, high-temperature-treated carbon fibers, modified carbon fibers, and Ag/AgCl for 7 days
Figure BDA0003489199690000092
By using the frequency response testing device shown in fig. 14, the frequency response test is performed on the high-temperature-treated carbon fiber, the modified carbon fiber and the Ag/AgCl, and the testing process is as follows: an electric field signal transmitting device is connected to two ends of a titanium plate which is placed in parallel, and transmits a sine alternating current signal with certain frequency and amplitude to simulate an underwater electric field environment. According to the principle of potential approximation, carbon fibers, high-temperature treated carbon fibers and modified carbon fibers are respectively paired to obtain paired electrodes, the paired electrodes are placed between titanium plates in parallel along the direction of electric field lines, the electrode spacing is 10cm, the induced electric field change between the paired electrodes is recorded through a signal acquisition instrument, and data analysis is carried out.
The test results are shown in FIG. 12, in which FIG. 12 is the response curve of the counter electrode under the action of 1mHz and 1mV applied electric field, and it can be seen from FIG. 12 that the response curves of CF and CF600 are severely shifted, and CF-7V can respond as normally as the Ag/AgCl electrode.
Example 2
Placing the carbon felt in a mixed solution of ethanol and acetone with a volume ratio of 1:1, and ultrasonically cleaning for 3 times, wherein each time is 15 min; putting the carbon felt into an oven for drying, and then putting the carbon felt into a muffle furnace for heat treatment, wherein the temperature of the heat treatment is 600 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 30min, so as to obtain a high-temperature treatment carbon felt;
electrolyzing 0.5g of the high-temperature treated carbon felt serving as an anode, a platinum sheet serving as a cathode and a Saturated Calomel Electrode (SCE) serving as a reference electrode in an electrolyte (the mass concentration of dicyandiamide is 2%, the mass concentration of potassium chloride is 2%, and a solvent is distilled water), wherein the current of the electrolysis is 0.36A, and the time is 10 min; obtaining the modified carbon felt;
connecting the modified carbon felt with a lead, and packaging a contact area with epoxy resin; and (3) placing the modified material in a sealed cavity, and installing a micropore protective sleeve outside the modified material to obtain the ocean electric field sensor electrode. The performance test of the ocean electric field sensor electrode is similar to that of the embodiment 1.
Example 3
Placing the carbon rod in a mixed solution of ethanol and acetone with a volume ratio of 1:1, and ultrasonically cleaning for 3 times, wherein each time is 15 min; putting the carbon rod into an oven for drying, and then putting the carbon rod into a muffle furnace for heat treatment, wherein the temperature of the heat treatment is 600 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 30min, so as to obtain a high-temperature treatment carbon rod;
electrolyzing 0.5g of the high-temperature treatment carbon rod serving as an anode, a platinum sheet serving as a cathode and a Saturated Calomel Electrode (SCE) serving as a reference electrode in an electrolyte (the mass concentration of dicyandiamide is 2%, the mass concentration of potassium chloride is 2%, and a solvent is distilled water), wherein the voltage of the electrolysis is 7V, and the time is 10 min; obtaining the modified carbon rod;
connecting the modified carbon rod with a lead, and packaging the contact area with epoxy resin; and placing the modified carbon rod in a sealed cavity, and installing a micropore protective sleeve outside the modified carbon rod to obtain the ocean electric field sensor electrode. The performance test of the ocean electric field sensor electrode is similar to that of the embodiment 1.
Example 4
Placing the carbon felt in a mixed solution of ethanol and acetone with a volume ratio of 1:1, and ultrasonically cleaning for 3 times, wherein each time is 15 min; putting the carbon felt into an oven for drying, and then putting the carbon felt into a muffle furnace for heat treatment, wherein the temperature of the heat treatment is 600 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 30min, so as to obtain a high-temperature treatment carbon felt;
electrolyzing 0.5g of the high-temperature treated carbon felt as an anode, a platinum sheet as a cathode and a Saturated Calomel Electrode (SCE) as a reference electrode in an electrolyte (the mass concentration of dicyandiamide is 2%, the mass concentration of potassium chloride is 2%, and a solvent is distilled water), wherein the voltage of the electrolysis is 7V, and the time is 10 min; obtaining the modified carbon felt;
connecting the modified carbon felt with a lead, and packaging a contact area with epoxy resin; and placing the modified carbon felt in a sealed cavity, and installing a micropore protective sleeve outside the modified carbon felt to obtain the ocean electric field sensor electrode. The performance test of the ocean electric field sensor electrode is similar to that of the embodiment 1.
Example 5
Placing the carbon cloth in a mixed solution of ethanol and acetone with a volume ratio of 1:1, and ultrasonically cleaning for 3 times, wherein each time is 15 min; putting the carbon cloth into an oven for drying, and then putting the carbon cloth into a muffle furnace for heat treatment, wherein the temperature of the heat treatment is 600 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 30min, so as to obtain high-temperature treatment carbon cloth;
electrolyzing 0.5g of the high-temperature-treated carbon cloth serving as an anode, a platinum sheet serving as a cathode and a Saturated Calomel Electrode (SCE) serving as a reference electrode in an electrolyte (the mass concentration of dicyandiamide is 2%, the mass concentration of potassium chloride is 2%, and a solvent is distilled water), wherein the voltage of the electrolysis is 7V, and the time is 10 min; obtaining the modified carbon felt;
connecting the modified carbon cloth with a lead, and packaging the contact area with epoxy resin; and arranging the modified carbon in a sealed cavity, and arranging a micropore protective sleeve outside the modified carbon to obtain the ocean electric field sensor electrode. The performance test of the ocean electric field sensor electrode is similar to that of the embodiment 1.
Example 6
Placing the foamy carbon in a mixed solution of ethanol and acetone with a volume ratio of 1:1, and ultrasonically cleaning for 3 times, wherein each time is 15 min; putting the foam carbon into an oven for drying, and then putting the foam carbon into a muffle furnace for heat treatment, wherein the temperature of the heat treatment is 600 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 30min, so as to obtain high-temperature treatment foam carbon;
electrolyzing 0.5g of the high-temperature-treated foamy carbon serving as an anode, a platinum sheet serving as a cathode and a Saturated Calomel Electrode (SCE) serving as a reference electrode in an electrolyte (the mass concentration of dicyandiamide is 2%, the mass concentration of potassium chloride is 2%, and a solvent is distilled water), wherein the electrolysis voltage is 7V, and the time is 10 min; obtaining the modified carbon foam;
connecting the modified carbon foam with a lead, and encapsulating a contact area with epoxy resin; and arranging the modified carbon in a sealed cavity, and arranging a micropore protective sleeve outside the modified carbon to obtain the ocean electric field sensor electrode. The performance test of the ocean electric field sensor electrode is similar to that of the embodiment 1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A method for producing a modified carbon material, characterized by comprising the steps of:
carrying out heat treatment on the carbon material to obtain a high-temperature treated carbon material;
electrolyzing the high-temperature treated carbon material serving as an anode, a platinum sheet serving as a cathode and a saturated calomel electrode serving as a reference electrode in an electrolyte to obtain the modified carbon material;
the electrolyte includes dicyandiamide.
2. The method of claim 1, wherein the carbon material comprises carbon fiber, carbon felt, carbon cloth, carbon rod, or carbon foam.
3. The method according to claim 1, wherein the heat treatment temperature is 300 to 600 ℃, the holding time is 20 to 60min, and the temperature rise rate for raising the temperature to the heat treatment temperature is 3 to 10 ℃/min.
4. The method of claim 1, wherein the electrolyte further comprises potassium chloride;
the mass concentration of dicyandiamide and potassium chloride in the electrolyte is 2%.
5. The method according to claim 1, wherein the electrolysis voltage is 3 to 7V and the time is 5 to 20 min.
6. The production method according to claim 1, wherein the carbon material is washed and dried in this order before the heat treatment;
the cleaning solution adopted by the cleaning is a mixed solution of ethanol and acetone in a volume ratio of 1: 1.
7. The modified carbon material prepared by the preparation method according to any one of claims 1 to 6, which comprises a carbon material and dicyandiamide grafted on the surface of the carbon material.
8. Use of the modified carbon material of claim 7 in the preparation of an electrode for a marine electric field sensor.
9. An ocean electric field sensor electrode is characterized by comprising an electrode, a lead and a packaging structure;
the electrode is connected with a lead; the packaging structure packages the contact area of the electrode and the lead;
the material for the electrode is the modified carbon material according to claim 7.
10. Use of the marine electric field sensor electrode of claim 9 for detecting electric field signals in the sea.
CN202210091046.3A 2022-01-26 2022-01-26 Modified carbon material, preparation method and application thereof, ocean electric field sensor electrode and application thereof Active CN114481249B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210091046.3A CN114481249B (en) 2022-01-26 2022-01-26 Modified carbon material, preparation method and application thereof, ocean electric field sensor electrode and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210091046.3A CN114481249B (en) 2022-01-26 2022-01-26 Modified carbon material, preparation method and application thereof, ocean electric field sensor electrode and application thereof

Publications (2)

Publication Number Publication Date
CN114481249A true CN114481249A (en) 2022-05-13
CN114481249B CN114481249B (en) 2023-06-02

Family

ID=81475027

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210091046.3A Active CN114481249B (en) 2022-01-26 2022-01-26 Modified carbon material, preparation method and application thereof, ocean electric field sensor electrode and application thereof

Country Status (1)

Country Link
CN (1) CN114481249B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107576699A (en) * 2016-07-05 2018-01-12 中国海洋大学 A kind of carbon-based Ag/AgCl electric field electrodes preparation method of high-specific surface area foam
CN111799479A (en) * 2020-07-20 2020-10-20 中国海洋大学 Chitosan-transition metal ion composite modified cathode material and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107576699A (en) * 2016-07-05 2018-01-12 中国海洋大学 A kind of carbon-based Ag/AgCl electric field electrodes preparation method of high-specific surface area foam
CN111799479A (en) * 2020-07-20 2020-10-20 中国海洋大学 Chitosan-transition metal ion composite modified cathode material and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
QIANG FU等: "Synthesis of nitrogenated carbon films by cathodic electrodeposition at the solid–liquid interface" *

Also Published As

Publication number Publication date
CN114481249B (en) 2023-06-02

Similar Documents

Publication Publication Date Title
CN104391030B (en) A kind of heavy metal ion Cd built based on alginic acid functionalization graphene 2+, Pb 2+and Cu 2+the preparation method of sensor and application
CN108318568A (en) A kind of electrochemical sensor and preparation method for Sensitive Detection heavy metal cadmium ion
Lu et al. CuO nanothorn arrays on three-dimensional copper foam as an ultra-highly sensitive and efficient nonenzymatic glucose sensor
CN105118688A (en) Preparation and application of bacterial cellulose/active carbon fiber/graphene film material
CN104198555B (en) A kind of poly-porphyrin/In Glassy Carbon Electrode Modified With Nano-gold, preparation method and applications
Liu et al. Ultrasensitive detection of ferulic acid using poly (diallyldimethylammonium chloride) functionalized graphene‐based electrochemical Sensor
Liu et al. Electrochemical and electric field response properties of highly sensitive electrodes based on carbon fiber with oxygen and nitrogen surface groups
Ismail et al. Cyclic voltammetry and electrochemical impedance spectroscopy of partially reduced graphene oxide-PEDOT: PSS transducer for biochemical sensing
CN109959684B (en) Preparation of double-identification type chlorpyrifos sensor, method for detecting chlorpyrifos residues in vegetables and detection device
CN106932449A (en) The preparation method of electrochemical sensor and its application in plumbum ion concentration is detected
CN114481249B (en) Modified carbon material, preparation method and application thereof, ocean electric field sensor electrode and application thereof
Baranski Alternating current voltammetry with carbon fiber microelectrodes
CN105572188B (en) (PANI/RGO)n/ Hemin modified electrode and its electrochemical detection method to hydrogen peroxide
CN104326468A (en) Three dimensional graphene with functionalized amino, biosensor, preparation method and applications
Han et al. Effect of oxygen-containing groups on electrochemical and marine electric field response properties of carbon fiber electrode
Pang et al. A disposable and sensitive sensor based on a ZIF-8@ graphene modified carbon paper electrode for the quantitative determination of luteolin
CN100386621C (en) Method for manufacturing nano carbon disk electrode with radius less than 500nm
CN113109400B (en) Preparation method of ammonia gas sensor based on graphene/polypyrrole
CN112326753B (en) Preparation method and application of triclosan molecular imprinting membrane electrochemical sensor
CN104817694B (en) A kind of quick method for preparing polyaniline nano sensing material
CN109799278A (en) The preparation and test method of 4,4 '-ODL-MIP/PANI
CN109517167B (en) Preparation method and test method of polyaniline/activated carbon composite material
CN109799274B (en) Preparation and test method of conductive polymer film material
Gao et al. Some electrochemical features of supported bilayer lipid membranes
CN112820848A (en) Preparation method of flexible self-supporting melanin electrode

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant