CN113030209A - Method for rapidly and controllably preparing flexible graphene electrode and application - Google Patents
Method for rapidly and controllably preparing flexible graphene electrode and application Download PDFInfo
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Abstract
A method for rapidly and controllably preparing a flexible graphene electrode and application thereof relate to a method for preparing a graphene electrode and application thereof. The invention aims to solve the problems of high cost, time-consuming preparation, complex process, use of toxic reagents and poor product stability and repeatability of the graphene electrode prepared by the conventional method. The method comprises the following steps: firstly, preparing a graphene/absolute ethyl alcohol suspension solution; secondly, exposing the viscous conductive adhesive; and thirdly, dropwise adding the graphene/absolute ethyl alcohol suspension solution to the part of the double-sided carbon conductive adhesive tape, which is exposed out of the viscous conductive adhesive, and drying. The flexible graphene electrode is used for preparing metal micro-nano structures, electrochemical biosensors or portable electric analysis and electronic equipment. The method is convenient and quick, simple in process, low in cost, environment-friendly and nontoxic, and can be used for preparing various metal micro-nano structures. The flexible graphene electrode can be obtained.
Description
Technical Field
The invention relates to a method for preparing a graphene electrode and application thereof.
Background
With the updating and iteration of electronic products, wearable, foldable, portable and lightweight flexible electronic devices are greatly concerned by people, higher requirements are also put forward on energy storage devices corresponding to the flexible electronic devices, and the materials not only need to have high flexibility and high elastic modulus, but also need to have excellent electrochemical performance, so that the flexible electrode has great potential in the research field of novel electronic products. Graphene, as a two-dimensional nanomaterial consisting of a single layer of carbon atoms and arranged in a hexagonal honeycomb lattice, shows excellent physical and chemical properties, has excellent comprehensive properties such as high conductivity, adsorptivity, structural flexibility and the like, and is an ideal material for preparing a flexible electrode for developing a flexible electronic device with higher performance.
Chemical Vapor Deposition (CVD) is one of the traditional methods for preparing graphene-based/modified electrodes, and is the growth of single-or multi-layer graphene from a solid surface with a catalyst substrate. The method can produce a large amount of graphene, but the growth conditions of the graphene are harsh, the cost is high, advanced and expensive instruments are needed, and the method is a time-consuming process. Another widely used method is electrochemical stripping, and oxidizing reagents (such as nitric acid and sulfuric acid) and reducing reagents (such as dimethylhydrazine) have extremely high toxicity, and often cause pollution problems of graphene products, thereby causing great harm to the environment and human bodies. In addition to these traditional methods, it is easier to prepare graphene modified electrodes by drop coating, i.e. by dropping a graphene dispersion onto a specific surface. However, physically deposited graphene is easily exfoliated from solid substrates, resulting in poor stability and reproducibility of use.
Disclosure of Invention
The invention aims to solve the problems of high cost, time-consuming preparation, complex process, use of toxic reagents and poor product stability and repeatability in the existing method for preparing the graphene electrode, and provides a method for rapidly and controllably preparing the flexible graphene electrode and application thereof.
A method for rapidly and controllably preparing a flexible graphene electrode is completed according to the following steps:
firstly, preparing a graphene/absolute ethyl alcohol suspension solution:
adding graphene powder into absolute ethyl alcohol, and performing ultrasonic treatment to obtain a uniformly dispersed graphene/absolute ethyl alcohol suspension solution;
secondly, the substrate paper surface of a section of double-sided carbon conductive adhesive tape is downward, the adhesive surface is upward, then the two ends of the double-sided carbon conductive adhesive tape are fixed, and the adhesive conductive adhesive is exposed in the middle;
and thirdly, dropwise adding the graphene/absolute ethyl alcohol suspension solution to the part of the double-sided carbon conductive adhesive tape exposed out of the viscous conductive adhesive, and then evaporating the absolute ethyl alcohol by using a hair drier to obtain the flexible graphene electrode.
The flexible graphene electrode is used for preparing metal micro-nano structures, electrochemical biosensors or portable electric analysis and electronic equipment.
The invention has the advantages that:
firstly, a common double-sided carbon conductive adhesive tape for SEM test is adopted, a flexible graphene electrode is prepared by a rapid and controllable method, and an industrial-grade graphene nanosheet can be fixed on the surface of the double-sided carbon conductive adhesive tape by a simple dripping and coating method, so that the flexible graphene electrode is rapidly obtained; moreover, the graphene powder is added into the absolute ethyl alcohol to prepare uniform suspension, so that the content of the graphene dripped on the exposed adhesive conductive adhesive can be accurately controlled, and the preparation process is quantitative and controllable;
the flexible graphene electrode can be conveniently applied under the condition of not damaging the double-sided adhesive property; for example, it can be easily fixed on various solid supports to develop various portable electric analysis and electronic devices; in addition, in addition to conventional applications as an electroanalytical electrode, such graphene electrodes having viscosity and flexibility can be used as substrates for bench-top fabrication of various metal nanostructures by a template-controlled electrodeposition technique;
the method is convenient and quick, simple in process, low in cost, environment-friendly and nontoxic, and can be used for preparing various metal nano structures;
thirdly, the common double-sided carbon conductive adhesive tape for SEM test is used as a substrate, and a simple dripping and coating method is adopted to quickly obtain the flexible graphene electrode; compared with a chemical vapor deposition method, the preparation of the ultramicro flexible graphene electrode and the metal nano structure by using the double-sided carbon conductive adhesive tape is convenient and quick, saves time and greatly reduces cost; besides expensive equipment, the chemical vapor deposition method has the disadvantages of time consumption, harsh graphene growth conditions and high cost; the double-sided carbon conductive adhesive tape can be used immediately only by cutting off a proper size, dripping a certain volume of graphene solution, and quickly volatilizing ethanol by using a blower;
compared with an electrochemical stripping method, the method has more outstanding advantages; the oxidation reagent (such as nitric acid and sulfuric acid) and the reduction reagent (such as dimethylhydrazine) used in the electrochemical stripping method have extremely high toxicity, and can cause great harm to the environment and human bodies in both the preparation process and the use process. Similarly, compared with other dropping coating methods, the method has obvious advantages that other dropping coating methods are used for dropping on the solid surface, graphene is easy to fall off from the solid surface only by virtue of physical adsorption, and the double sides of the carbon conductive adhesive tape used by the method are sticky, so that graphene powder dropped on the surface is firmly adhered and is not easy to fall off, and the obtained graphene electrode has stability and reproducibility;
performing electrochemical characterization on the flexible graphene electrode prepared by the invention by using an electroactive substance, taking a 1.0mmol/L potassium ferricyanide solution and a 0.1mol/L potassium chloride solution as electrolytes, and adopting cyclic voltammetry for testing, wherein multiple scanning results show reversible redox response and little CV curve change, which proves that the graphene electrode prepared by the invention has good stability and reproducibility;
sixthly, the flexible graphene electrode prepared by the invention is used for detecting ascorbic acid and dopamine with different concentrations, a cyclic voltammetry curve shows that the oxidation peak current of the flexible graphene electrode has obvious correlation with the concentration, the peak current shows a wide response range along with the change of the ascorbic acid and dopamine concentration, the detection limit of the ascorbic acid can be up to (0.061 +/-0.002) mM and the detection limit of the dopamine can be up to (0.0016 +/-0.0001) mM according to a linear fitting equation, and the results strongly prove the great potential of the flexible graphene electrode prepared by the invention in the aspect of electrochemical biosensing;
the prepared graphene flexible electrode can be conveniently applied under the condition that the double-sided adhesive performance is not damaged; for example, flexible graphene electrodes, or metal nanostructures deposited thereon, can be easily affixed to a variety of solid supports for the development of portable electroanalytical and electronic devices by peeling the electrodes away from the substrate.
The graphene flexible electrode can be obtained.
Drawings
Fig. 1 is an optical digital photograph of a flexible graphene electrode prepared in the first example;
fig. 2 is a cyclic voltammetry graph of a flexible graphene electrode prepared in example one in an electrolyte;
fig. 3 is CV curves measured at different scanning rates of the flexible graphene electrode prepared in the first example;
FIG. 4 shows the square root v of the peak current Ip and the potential sweep rate in FIG. 31/2A linear relationship therebetween;
FIG. 5 shows K at different concentrations for the flexible graphene electrode prepared in the first embodiment3Fe(CN)6CV curve in electrolyte;
FIG. 6 is a correlation between peak current and concentration for different concentrations in FIG. 5;
fig. 7 is a cyclic voltammetry curve of a flexible graphene electrode prepared according to the first example for detecting ascorbic acid with different concentrations;
FIG. 8 is a linear fit plot of FIG. 7;
fig. 9 is a cyclic voltammetry curve of a flexible graphene electrode prepared according to the first embodiment for detecting different concentrations of dopamine;
FIG. 10 is a linear fit plot of FIG. 9;
FIG. 11 is a scanning electron micrograph of gold nanostructures prepared in example two;
FIG. 12 is a high power scanning electron micrograph of gold nanostructures made according to example two;
FIG. 13 is a scanning electron microscope image of a platinum micro-nanostructure prepared in example III;
fig. 14 is a high-power scanning electron microscope image of the platinum micro-nano structure prepared in the third embodiment.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the method for rapidly and controllably preparing the flexible graphene electrode is completed according to the following steps:
firstly, preparing a graphene/absolute ethyl alcohol suspension solution:
adding graphene powder into absolute ethyl alcohol, and performing ultrasonic treatment to obtain a uniformly dispersed graphene/absolute ethyl alcohol suspension solution;
secondly, the substrate paper surface of a section of double-sided carbon conductive adhesive tape is downward, the adhesive surface is upward, then the two ends of the double-sided carbon conductive adhesive tape are fixed, and the adhesive conductive adhesive is exposed in the middle;
and thirdly, dropwise adding the graphene/absolute ethyl alcohol suspension solution to the part of the double-sided carbon conductive adhesive tape exposed out of the viscous conductive adhesive, and then evaporating the absolute ethyl alcohol by using a hair drier to obtain the flexible graphene electrode.
The graphene powder described in step one of the present embodiment was purchased from nanoxpore, model graphene black 3X.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the volume ratio of the mass of the graphene powder to the absolute ethyl alcohol in the first step is (50 mg-500 mg):10 mL; the power of ultrasonic treatment in the step one is 900W-1200W, and the time of ultrasonic treatment is 5 min-10 min. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the thickness of the double-sided carbon conductive adhesive tape in the second step is 150-170 μm, the width is 23-28 mm, and the length is 35-40 mm. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the double-sided carbon conductive adhesive tape in the second step is made of non-woven fabric as a base material, both sides of the adhesive tape contain acrylic pressure-sensitive adhesive with carbon powder as conductive filler, and the specific resistance is (1.8 +/-0.2) multiplied by 104Omega cm. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the ratio of the volume of the graphene/absolute ethyl alcohol suspension solution to the area of the part of the double-sided carbon conductive adhesive tape exposed out of the viscous conductive adhesive is 100 mu L (600 mm)2～800mm2). The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the flexible graphene electrode is used for preparing a metal micro-nano structure, an electrochemical biosensor or portable electric analysis and electronic equipment.
The seventh embodiment: the present embodiment differs from the sixth embodiment in that: the flexible graphene electrode is used for preparing a metal micro-nano structure and is completed according to the following steps:
firstly, tearing off base paper on a flexible graphene electrode, and then flatly adhering the base paper to a glass sheet plated with metal;
secondly, placing a template with a nano-aperture on the flexible graphene electrode, enabling the graphene to be in contact with the template with the nano-aperture, then evacuating air between the template and the double-sided carbon conductive adhesive tape, and finally compacting to obtain an assembled graphene electrode metal sheet;
thirdly, forming a round hole in the bottom of the electrolytic cell, then placing the assembled graphene electrode metal sheet at the bottom of the electrolytic cell, aligning a template with a nano-aperture with the round hole, sealing by using an O-shaped ring, connecting the electrolytic cell base, the assembled graphene electrode metal sheet and the electrolytic cell together by using screws, and tightening;
adding electrolyte into an electrolytic cell, taking the assembled graphene electrode metal sheet as a working electrode, Ag/AgCl as a reference electrode and a platinum wire as a counter electrode, and depositing at constant voltage under the conditions of room temperature and nitrogen atmosphere to obtain a metal micro-nano structure on the assembled graphene electrode metal sheet;
the electrolyte in the fourth step is mixed liquid of chloroauric acid, boric acid and water, mixed liquid of chloroplatinic acid, sulfuric acid and water or mixed liquid of copper sulfate, sulfuric acid and water. The other steps are the same as in the sixth embodiment.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the metal-plated glass sheet in the first step is a metal layer with the thickness of 100nm deposited on the glass sheet by a physical vapor deposition method, the size of the glass sheet is 76mm multiplied by 26mm multiplied by 2mm, and the metal is gold, platinum or copper; the template with the nano-aperture in the second step is made of an alumina porous membrane or a polycarbonate porous membrane; the thickness of the alumina porous membrane is 58-62 μm; the thickness of the polycarbonate porous membrane is 6-8 μm; the diameter of the template with the nano-aperture in the step two is 13 mm-25 mm, and the aperture density is 6 multiplied by 108/cm2～2×109/cm2(ii) a The material of the electrolytic cell in the third step is polytetrafluoroethylene, and the diameter of the round hole at the bottom of the electrolytic cell is 8 mm. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the concentration of the chloroauric acid in the mixed solution of the chloroauric acid, the boric acid and the water in the fourth step is 25mmol/L, and the concentration of the boric acid is 0.3 mol/L; the concentration of the chloroplatinic acid in the mixed solution of the chloroplatinic acid, the sulfuric acid and the water in the fourth step is 10mmol/L, and the concentration of the sulfuric acid is 0.2 mol/L; the concentration of copper sulfate in the mixed solution of copper sulfate, sulfuric acid and water in the step four is 0.4mol/L, and the concentration of sulfuric acid is 10 mmol/L. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: the constant voltage deposition in the fourth step adopts a CHI 1040A electrochemical analyzer, selects an Amperometric i-t curve mode, the deposition voltage is-0.2V to-0.4V, and the deposition time is 50s to 1200 s. The other steps are the same as those in the first to ninth embodiments.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
The first embodiment is as follows: the method for rapidly and controllably preparing the flexible graphene electrode is completed according to the following steps:
firstly, preparing a graphene/absolute ethyl alcohol suspension solution:
adding 300mg of graphene powder into 10mL of absolute ethyl alcohol, and performing ultrasonic treatment for 5min at the ultrasonic power of 1200W to obtain a uniformly dispersed graphene/absolute ethyl alcohol suspension solution;
the graphene powder in the first step is purchased from Nanoxplore company and has the model of graphene Black 3X;
secondly, the substrate paper surface of a section of double-sided carbon conductive adhesive tape is downward, the adhesive surface is upward, then the two ends of the double-sided carbon conductive adhesive tape are fixed, and the adhesive conductive adhesive is exposed in the middle;
the thickness of the double-sided carbon conductive adhesive tape in the second step is 160 micrometers, the width of the double-sided carbon conductive adhesive tape is 25mm, the length of the double-sided carbon conductive adhesive tape is 35mm, the covering sizes of the two ends are respectively 25mm multiplied by 5mm, wherein 25mm is the width of the double-sided carbon conductive adhesive tape, and 5mm is the length of the covered double-sided carbon conductive adhesive tape;
the double-sided carbon conductive adhesive tape in the second step is made of non-woven fabric as a substrate material, both sides of the double-sided carbon conductive adhesive tape contain acrylic pressure-sensitive adhesive with carbon powder as conductive filler, and the specific resistance is 1.8 multiplied by 104Ωcm；
And thirdly, dropwise adding 100 mu L of graphene/absolute ethyl alcohol suspension solution to the part of the double-sided carbon conductive adhesive tape, where the viscous conductive adhesive is exposed, and then evaporating the absolute ethyl alcohol by using a hair drier for 10min to obtain the flexible graphene electrode.
Cutting the flexible graphene electrode prepared in the first embodiment into a circle with a diameter of 19mm +/-0.5 mm, as shown in fig. 1;
fig. 1 is an optical digital photograph of the flexible graphene electrode prepared in the first embodiment.
Tearing off the substrate paper on the flexible graphene electrode, and thenFlatly adhering the graphene film to a gold-plated glass sheet to obtain an assembled graphene electrode; the gold-plated glass sheet is formed by depositing a gold layer with the thickness of 100nm on a glass sheet by a physical vapor deposition method; the size of the glass sheet is 76mm multiplied by 26mm multiplied by 2 mm; opening a round hole at the bottom of the electrolytic cell, placing the assembled graphene electrode at the bottom of the electrolytic cell, aligning the assembled graphene electrode with the round hole, enabling the flexible graphene electrode to face the inside of the electrolytic cell, sealing by using an O-shaped ring, connecting the electrolytic cell base, the assembled graphene electrode and the electrolytic cell together by using screws, and tightening; the electrolytic cell is made of polytetrafluoroethylene, and the diameter of a round hole at the bottom of the electrolytic cell is 8 mm; electrolyte is filled in the electrolytic cell, and the electrolyte is K3Fe(CN)6KCl and water, wherein K3Fe(CN)6The concentration of (3) is 1mmol/L, and the concentration of KCl is 0.1 mol/L; the assembled graphene electrode is a working electrode, Ag/AgCl (3M NaCl) is a reference electrode, a platinum wire is a counter electrode, and cyclic voltammetry scanning is performed by using a CHI 1040A electrochemical analyzer; performing 50 times of cyclic voltammetry scans in the electrolyte, and changing K in the electrolyte3Fe(CN)6The cyclic voltammogram is shown in fig. 5 and 6;
fig. 2 is a cyclic voltammetry graph of a flexible graphene electrode prepared in example one in an electrolyte;
as can be seen from fig. 2, these CVs all show reversible redox reactions, with negligible changes, i.e. no signs of degradation upon repeated scans, and changes in peak current within (2%), indicating satisfactory stability and reproducibility of the flexible graphene electrode.
Fig. 3 is CV curves measured at different scanning rates of the flexible graphene electrode prepared in the first example;
FIG. 4 shows the square root v of the peak current Ip and the potential sweep rate in FIG. 31/2A linear relationship therebetween;
FIG. 5 shows K at different concentrations for the flexible graphene electrode prepared in the first embodiment3Fe(CN)6CV curve in electrolyte;
FIG. 6 is a correlation between peak current and concentration for different concentrations in FIG. 5;
the flexible graphene electrode prepared in the first embodiment is used for detecting ascorbic acid and dopamine solutions with different concentrations; dissolving ascorbic acid and dopamine solutions with different concentrations in 0.1M PBS buffer solution respectively, and adjusting the pH value to 7.2; cyclic voltammetric scans were performed using a CHI 1040A electrochemical analyzer. As shown in FIGS. 7 to 8 and FIGS. 9 to 10;
fig. 7 is a cyclic voltammetry curve of a flexible graphene electrode prepared according to the first example for detecting ascorbic acid with different concentrations;
FIG. 8 is a linear fit plot of FIG. 7;
fig. 9 is a cyclic voltammetry curve of a flexible graphene electrode prepared according to the first embodiment for detecting different concentrations of dopamine;
FIG. 10 is a linear fit plot of FIG. 9;
fig. 7 to 9 show the results of the flexible graphene electrode prepared according to the first embodiment for quantitative analysis and medical-related experimental analysis. The ascorbic acid CV graphs measured on the flexible graphene electrode in fig. 7 and 8 show that there is a clear correlation between the oxidation peak current and the concentration, and a linear calibration curve (R) can be established in the concentration range of 0.02mM to 5.0mM20.9991). FIGS. 9 and 10 are CV graphs and linear correlation curves of measured dopamine, and the results obtained are similar to ascorbic acid, and R is obtained in the concentration range of 0.001mM to 0.031mM20.9951 linear calibration curve. The detection Limits (LOD) for ascorbic acid and dopamine were determined to be (0.061. + -. 0.002) mM and (0.0016. + -. 0.0001) mM, respectively, based on the parameters fitted to the calibration curve. The linear response range of these LODs obtained on graphene electrodes, as well as ascorbic acid (0.02mM to 5.0mM) and dopamine (0.001 to 0.031mM), is comparable to the currently known LODs and linear response ranges of electrodes. The above results confirm that the flexible graphene electrode prepared by the present invention has good reproducibility, stability and quantitative capability in conventional electrochemical analysis as a typical low-cost carbon electrode.
Example two: the method for preparing the flexible graphene electrode again according to the embodiment I comprises the following steps of:
firstly, tearing off base paper on a flexible graphene electrode, and then flatly adhering the base paper to a gold-plated glass sheet;
the gold-plated glass sheet in the first step is a gold layer with the thickness of 100nm deposited on the glass sheet by a physical vapor deposition method, and the size of the glass sheet is 76mm multiplied by 26mm multiplied by 2 mm;
secondly, placing a template with a nano-aperture on the flexible graphene electrode, enabling the graphene to be in contact with the template with the nano-aperture, then evacuating air between the template and the double-sided carbon conductive adhesive tape, and finally compacting to obtain an assembled graphene electrode metal sheet;
the template with the nano-aperture in the step two is made of a polycarbonate porous membrane; the thickness of the polycarbonate porous membrane is 6 mu m; the diameter of the template with the nano-aperture in the second step is 25mm, and the aperture density is 6 multiplied by 108/cm2；
Thirdly, forming a round hole in the bottom of the electrolytic cell, then placing the assembled graphene electrode metal sheet at the bottom of the electrolytic cell, aligning a template with a nano-aperture with the round hole, sealing by using an O-shaped ring, connecting the electrolytic cell base, the assembled graphene electrode metal sheet and the electrolytic cell together by using screws, and tightening;
the material of the electrolytic cell in the third step is polytetrafluoroethylene, and the diameter of the round hole at the bottom of the electrolytic cell is 8 mm;
adding electrolyte into an electrolytic cell, taking the assembled graphene electrode metal sheet as a working electrode, Ag/AgCl as a reference electrode and a platinum wire as a counter electrode, and depositing at constant voltage under the conditions of room temperature and nitrogen atmosphere to obtain a gold micro-nanostructure on the assembled graphene electrode metal sheet;
the electrolyte in the fourth step is a mixed solution of chloroauric acid, boric acid and water, wherein the concentration of the chloroauric acid is 25mmol/L, and the concentration of the boric acid is 0.3 mol/L; the constant voltage deposition in the fourth step adopts a CHI 1040A electrochemical analyzer, selects an 'Amperometric i-t curve' mode, the deposition voltage is-0.2V, and the deposition time is 200 s.
FIG. 11 is a scanning electron microscope image of the gold micro-nano structure prepared in example two;
FIG. 12 is a high-power scanning electron microscope image of the gold micro-nano structure prepared in example two;
as can be seen from FIGS. 11 to 12, the gold micro-nano structures prepared in the second embodiment are uniformly distributed, have different shapes, and have sizes ranging from 0.5 μm to 5 μm.
Example three: the method for preparing the flexible graphene electrode rapidly and controllably comprises the following steps of:
firstly, tearing off base paper on a flexible graphene electrode, and then flatly adhering the base paper to a gold-plated glass sheet;
the metal-plated glass sheet in the first step is a gold layer with the thickness of 100nm deposited on the glass sheet by a physical vapor deposition method, and the size of the glass sheet is 76mm multiplied by 26mm multiplied by 2 mm;
secondly, placing a template with a nano-aperture on the flexible graphene electrode, enabling the graphene to be in contact with the template with the nano-aperture, then evacuating air between the template and the double-sided carbon conductive adhesive tape, and finally compacting to obtain an assembled graphene electrode metal sheet;
the template with the nano-aperture in the step two is made of a polycarbonate porous membrane; the thickness of the polycarbonate porous membrane is 6 mu m; the diameter of the template with the nano-aperture in the second step is 25mm, and the aperture density is 6 multiplied by 108/cm2；
Thirdly, forming a round hole in the bottom of the electrolytic cell, then placing the assembled graphene electrode metal sheet at the bottom of the electrolytic cell, aligning a template with a nano-aperture with the round hole, sealing by using an O-shaped ring, connecting the electrolytic cell base, the assembled graphene electrode metal sheet and the electrolytic cell together by using screws, and tightening;
the material of the electrolytic cell in the third step is polytetrafluoroethylene, and the diameter of the round hole at the bottom of the electrolytic cell is 8 mm;
adding electrolyte into an electrolytic cell, taking the assembled graphene electrode metal sheet as a working electrode, Ag/AgCl as a reference electrode and a platinum wire as a counter electrode, and depositing at constant voltage under the conditions of room temperature and nitrogen atmosphere to obtain a platinum micro-nanostructure on the assembled graphene electrode metal sheet;
the electrolyte in the fourth step is a mixed solution of chloroplatinic acid, sulfuric acid and water, wherein the concentration of the chloroplatinic acid in the mixed solution of the chloroplatinic acid, the sulfuric acid and the water is 10mmol/L, and the concentration of the sulfuric acid is 0.2 mol/L; the constant voltage deposition in the fourth step adopts a CHI 1040A electrochemical analyzer, selects an 'Amperometric i-t curve' mode, the deposition voltage is-0.3V, and the deposition time is 1200 s.
FIG. 13 is a scanning electron microscope image of a platinum micro-nanostructure prepared in example III;
fig. 14 is a high-power scanning electron microscope image of the platinum micro-nano structure prepared in the third embodiment.
As can be seen from fig. 13 to 14, the platinum micro-nano structures prepared in the third embodiment are relatively uniformly distributed, uniform in morphology, mostly hemispherical, and uniform in size, and the size distribution is between 0.5 μm and 8 μm.
Claims (10)
1. A method for preparing a flexible graphene electrode in a rapid and controllable manner is characterized in that the method for preparing the flexible graphene electrode in a rapid and controllable manner is completed according to the following steps:
firstly, preparing a graphene/absolute ethyl alcohol suspension solution:
adding graphene powder into absolute ethyl alcohol, and performing ultrasonic treatment to obtain a uniformly dispersed graphene/absolute ethyl alcohol suspension solution;
secondly, the substrate paper surface of a section of double-sided carbon conductive adhesive tape is downward, the adhesive surface is upward, then the two ends of the double-sided carbon conductive adhesive tape are fixed, and the adhesive conductive adhesive is exposed in the middle;
and thirdly, dropwise adding the graphene/absolute ethyl alcohol suspension solution to the part of the double-sided carbon conductive adhesive tape exposed out of the viscous conductive adhesive, and then evaporating the absolute ethyl alcohol by using a hair drier to obtain the flexible graphene electrode.
2. The method for rapidly and controllably preparing the flexible graphene electrode according to claim 1, wherein the volume ratio of the mass of the graphene powder to the absolute ethyl alcohol in the step one is (50 mg-500 mg):10 mL; the power of ultrasonic treatment in the step one is 900W-1200W, and the time of ultrasonic treatment is 5 min-10 min.
3. The method for rapidly and controllably preparing the flexible graphene electrode according to claim 1, wherein the double-sided carbon conductive adhesive tape in the second step has a thickness of 150 μm to 170 μm, a width of 23mm to 28mm, and a length of 35mm to 40 mm.
4. The method as claimed in claim 1 or 3, wherein the double-sided carbon conductive adhesive tape in step two is made of non-woven fabric as a base material, and has acrylic pressure sensitive adhesive with carbon powder as conductive filler on both sides, and has a resistivity of (1.8 ± 0.2) × 104Ωcm。
5. The method for rapidly and controllably preparing the flexible graphene electrode according to claim 1, wherein the ratio of the volume of the graphene/absolute ethyl alcohol suspension solution to the area of the part of the double-sided carbon conductive adhesive tape exposed out of the adhesive conductive adhesive in the step three is 100 μ L (600 mm)2～800mm2)。
6. The application of the flexible graphene electrode prepared by the preparation method according to claim 1, wherein the flexible graphene electrode is used for preparing metal micro-nano structures, electrochemical biosensors or portable electric analysis and electronic equipment.
7. The application of the flexible graphene electrode prepared by the preparation method according to claim 6, wherein the flexible graphene electrode is used for preparing a metal micro-nano structure, and the preparation method comprises the following steps:
firstly, tearing off base paper on a flexible graphene electrode, and then flatly adhering the base paper to a glass sheet plated with metal;
secondly, placing a template with a nano-aperture on the flexible graphene electrode, enabling the graphene to be in contact with the template with the nano-aperture, then evacuating air between the template and the double-sided carbon conductive adhesive tape, and finally compacting to obtain an assembled graphene electrode metal sheet;
thirdly, forming a round hole in the bottom of the electrolytic cell, then placing the assembled graphene electrode metal sheet at the bottom of the electrolytic cell, aligning a template with a nano-aperture with the round hole, sealing by using an O-shaped ring, connecting the electrolytic cell base, the assembled graphene electrode metal sheet and the electrolytic cell together by using screws, and tightening;
adding electrolyte into an electrolytic cell, taking the assembled graphene electrode metal sheet as a working electrode, Ag/AgCl as a reference electrode and a platinum wire as a counter electrode, and depositing at constant voltage under the conditions of room temperature and nitrogen atmosphere to obtain a metal micro-nano structure on the assembled graphene electrode metal sheet;
the electrolyte in the fourth step is mixed liquid of chloroauric acid, boric acid and water, mixed liquid of chloroplatinic acid, sulfuric acid and water or mixed liquid of copper sulfate, sulfuric acid and water.
8. The use of the flexible graphene electrode according to the preparation method of claim 7, wherein the metal-coated glass sheet in the first step is prepared by depositing a metal layer with a thickness of 100nm on a glass sheet by physical vapor deposition, the glass sheet has a size of 76mm x 26mm x 2mm, and the metal is gold, platinum or copper; the template with the nano-aperture in the second step is made of an alumina porous membrane or a polycarbonate porous membrane; the thickness of the alumina porous membrane is 58-62 μm; the thickness of the polycarbonate porous membrane is 6-8 μm; the diameter of the template with the nano-aperture in the step two is 13 mm-25 mm, and the aperture density is 6 multiplied by 108/cm2～2×109/cm2(ii) a Step threeThe material of the electrolytic cell is polytetrafluoroethylene, and the diameter of the round hole at the bottom of the electrolytic cell is 8 mm.
9. The application of the flexible graphene electrode prepared by the preparation method according to claim 7 or 8, wherein the concentration of the chloroauric acid in the mixed solution of the chloroauric acid, the boric acid and the water in the step four is 25mmol/L, and the concentration of the boric acid is 0.3 mol/L; the concentration of the chloroplatinic acid in the mixed solution of the chloroplatinic acid, the sulfuric acid and the water in the fourth step is 10mmol/L, and the concentration of the sulfuric acid is 0.2 mol/L; the concentration of copper sulfate in the mixed solution of copper sulfate, sulfuric acid and water in the step four is 0.4mol/L, and the concentration of sulfuric acid is 10 mmol/L.
10. The application of the flexible graphene electrode prepared by the preparation method according to claim 9, wherein the constant voltage deposition in the fourth step is performed by using a CHI 1040A electrochemical analyzer, an 'Amperotic i-t curve' mode is selected, the deposition voltage is-0.2V-0.4V, and the deposition time is 50 s-1200 s.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114146055A (en) * | 2021-12-10 | 2022-03-08 | 广东石油化工学院 | Preparation method of controllable phospholipid micelle |
| CN116399924A (en) * | 2023-04-12 | 2023-07-07 | 澳门科技大学 | Photoelectrochemical working electrode, preparation method thereof and photoelectrochemical device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103806040A (en) * | 2013-11-08 | 2014-05-21 | 西安交通大学 | Electrochemical synthesis method of nickel-phosphorus alloy nanotube array |
| CN108493001A (en) * | 2018-03-17 | 2018-09-04 | 东华理工大学 | A method of simply preparing graphite high flexibility electrode and flexible super capacitor |
| CN109709178A (en) * | 2019-02-28 | 2019-05-03 | 杭州电子科技大学 | A kind of preparation method and application of nanometer of platinum/graphen flexible electrode |
| CN110441367A (en) * | 2019-07-22 | 2019-11-12 | 大连理工大学 | It is a kind of to detect Cu using nanogold-graphene combination electrode2+Electrochemical method |
| CN111999357A (en) * | 2020-07-31 | 2020-11-27 | 惠州市钰芯电子材料有限公司 | Preparation method of nano silver wire array sensor and application of nano silver wire array sensor in ascorbic acid biomolecule determination |
-
2021
- 2021-03-16 CN CN202110278709.8A patent/CN113030209B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103806040A (en) * | 2013-11-08 | 2014-05-21 | 西安交通大学 | Electrochemical synthesis method of nickel-phosphorus alloy nanotube array |
| CN108493001A (en) * | 2018-03-17 | 2018-09-04 | 东华理工大学 | A method of simply preparing graphite high flexibility electrode and flexible super capacitor |
| CN109709178A (en) * | 2019-02-28 | 2019-05-03 | 杭州电子科技大学 | A kind of preparation method and application of nanometer of platinum/graphen flexible electrode |
| CN110441367A (en) * | 2019-07-22 | 2019-11-12 | 大连理工大学 | It is a kind of to detect Cu using nanogold-graphene combination electrode2+Electrochemical method |
| CN111999357A (en) * | 2020-07-31 | 2020-11-27 | 惠州市钰芯电子材料有限公司 | Preparation method of nano silver wire array sensor and application of nano silver wire array sensor in ascorbic acid biomolecule determination |
Non-Patent Citations (2)
| Title |
|---|
| WANG LI等: "Simple and Large-Scale Strategy to Prepare Flexible Graphene Tape Electrode" * |
| 辜孔良: "天然原料合成Al4SiC4的机理与性能研究" * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114146055A (en) * | 2021-12-10 | 2022-03-08 | 广东石油化工学院 | Preparation method of controllable phospholipid micelle |
| US11697101B2 (en) | 2021-12-10 | 2023-07-11 | Guangdong University Of Petrochemical Technology | Method for preparing phospholipid micelles |
| CN116399924A (en) * | 2023-04-12 | 2023-07-07 | 澳门科技大学 | Photoelectrochemical working electrode, preparation method thereof and photoelectrochemical device |
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