CN113030209B - Method for preparing flexible graphene electrode in rapid and controllable manner and application - Google Patents
Method for preparing flexible graphene electrode in rapid and controllable manner and application Download PDFInfo
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Abstract
A method for preparing a flexible graphene electrode in a rapid and controllable manner 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, toxic reagent use and poor product stability and repeatability of the graphene electrode prepared by the existing method. The method comprises the following steps: 1. preparing graphene/absolute ethyl alcohol suspension solution; 2. exposing the adhesive conductive adhesive; 3. and (3) dripping the graphene/absolute ethyl alcohol suspension solution into the part of the double-sided carbon conductive adhesive tape, which exposes the adhesive conductive adhesive, and drying. The flexible graphene electrode is used for preparing a metal micro-nano structure, for preparing an electrochemical biosensor or for preparing portable electroanalysis and electronic equipment. The method is convenient and quick, has simple process, low cost, is environment-friendly and nontoxic, and can prepare various metal micro-nano structures. The invention can obtain the flexible graphene electrode.
Description
Technical Field
The invention relates to a method for preparing a graphene electrode and application thereof.
Background
Along with the updating iteration of electronic products, wearable, foldable, portable and lightweight flexible electronic devices are greatly focused by people, and higher requirements are also put 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 flexible electrodes have great potential in the research field of novel electronic products. The graphene, which is a two-dimensional nanomaterial consisting of single-layer carbon atoms and arranged in a hexagonal honeycomb lattice, has excellent physical and chemical properties, has excellent comprehensive properties such as high conductivity, adsorptivity, structural flexibility and the like, is an ideal material for preparing flexible electrodes and is used for developing flexible electronic devices with higher performance.
Chemical Vapor Deposition (CVD) is one of the traditional methods of preparing graphene-based/modified electrodes, which is to grow 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 condition of the graphene is 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, where oxidizing agents (e.g., nitric acid, sulfuric acid) and reducing agents (e.g., dimethylhydrazine) have extremely high toxicity, and often cause pollution problems for graphene products, which can cause significant harm to the environment and human body. In addition to these conventional methods, a more convenient method for preparing graphene-modified electrodes is a drop coating method, i.e., a method of dropping graphene dispersion onto a specific surface. However, physically deposited graphene is easily detached from the solid substrate, resulting in poor stability and reproducibility of use.
Disclosure of Invention
The invention aims to solve the problems of high cost, time consumption, complex process, toxic reagent use and poor product stability and repeatability of the graphene electrode prepared by the existing method, and provides a method for preparing a flexible graphene electrode in a rapid and controllable way and application of the flexible graphene electrode.
A method for preparing a flexible graphene electrode in a rapid and controllable manner is completed according to the following steps:
1. preparing graphene/absolute ethanol suspension solution:
adding graphene powder into absolute ethyl alcohol, and performing ultrasonic treatment to obtain a graphene/absolute ethyl alcohol suspension solution with uniform dispersion;
2. the base material paper surface of a section of double-sided carbon conductive adhesive tape is downward, the adhesive surface is upward, two ends of the double-sided carbon conductive adhesive tape are fixed, and the adhesive conductive adhesive is exposed in the middle;
3. and (3) dripping the graphene/absolute ethyl alcohol suspension solution into the part of the double-sided carbon conductive adhesive tape, which exposes the adhesive conductive adhesive, and evaporating absolute ethyl alcohol by using an electric hair drier to obtain the flexible graphene electrode.
The flexible graphene electrode is used for preparing a metal micro-nano structure, for preparing an electrochemical biosensor or for preparing portable electroanalysis and electronic equipment.
The invention has the advantages that:
1. according to the invention, a common double-sided carbon conductive adhesive tape for SEM test is adopted, a flexible graphene electrode is prepared by a rapid controllable method, and an industrial grade graphene nano sheet can be fixed on the surface of the double-sided carbon conductive adhesive tape by a simple dripping method, namely, the flexible graphene electrode is rapidly obtained; in addition, the graphene powder is added into absolute ethyl alcohol to prepare uniform suspension containing liquid, so that the content of graphene dropwise added on exposed adhesive conductive adhesive can be accurately controlled, and the quantitative and controllable preparation process is realized;
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 mounted on a variety of solid supports to develop a variety of portable electrical analysis and electronics; in addition, such a graphene electrode having adhesiveness and flexibility can be used as a substrate for bench-type fabrication of various metal nanostructures by a template-controlled electrodeposition technique, in addition to the conventional application as an electroanalytical electrode;
2. the method is convenient and quick, has simple process, low cost, environmental protection and no toxicity, and can prepare various metal nano structures;
3. according to the invention, a common double-sided carbon conductive adhesive tape for SEM test is adopted as a substrate, and a simple dripping method is adopted to rapidly obtain a flexible graphene electrode; compared with a chemical vapor deposition method, the preparation of the ultra-micro flexible graphene electrode and the metal nanostructure by using the double-sided carbon conductive tape is convenient and quick, saves time and greatly reduces cost; the chemical vapor deposition method has the defects of time consumption besides expensive equipment, harsh growth conditions of graphene and high cost; the double-sided carbon conductive adhesive tape is utilized, a certain volume of graphene solution is dripped only by cutting off the proper size, and the ethanol is volatilized quickly by using a blower, so that the double-sided carbon conductive adhesive tape can be used immediately;
4. compared with an electrochemical stripping method, the method has more outstanding advantages; the oxidizing reagent (such as nitric acid and sulfuric acid) and the reducing reagent (such as dimethylhydrazine) used in the electrochemical stripping method have extremely high toxicity, and can cause extremely great harm to the environment and human body both in the preparation process and the use process. Similarly, compared with other dripping methods, the invention has obvious advantages that other dripping methods are used for dripping on the solid surface, and graphene is easy to fall off from the solid surface only by physical adsorption, and the carbon conductive adhesive tape used by the invention has adhesiveness on both sides, so that graphene powder dripped on the surface is firmly adhered and is not easy to fall off, and the obtained graphene electrode has stability and reproducibility;
5. electrochemical characterization is carried out on the flexible graphene electrode prepared by the invention by using electroactive substances, 1.0mmol/L potassium ferricyanide solution and 0.1mol/L potassium chloride solution are used as electrolyte, cyclic voltammetry is adopted for testing, and a plurality of scanning results show reversible redox response and small CV curve change, so that the graphene electrode prepared by the invention has good stability and reproducibility;
6. the flexible graphene electrode prepared by the invention is used for detecting ascorbic acid and dopamine with different concentrations, a cyclic voltammogram shows obvious correlation between oxidation peak current and concentration, peak current changes along with the concentration of the ascorbic acid and the concentration of the dopamine show a wide response range, 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 electrochemical biosensing;
7. the graphene flexible electrode prepared by the method can be conveniently applied under the condition of not damaging the double-sided adhesive property; for example, flexible graphene electrodes or together with metal nanostructures electrodeposited thereon can be easily affixed to a variety of solid supports to develop portable electroanalysis and electronic devices.
The invention can obtain the graphene flexible electrode.
Drawings
FIG. 1 is an optical digital photograph of a flexible graphene electrode prepared in accordance with example one;
FIG. 2 is a cyclic voltammogram of a flexible graphene electrode prepared in example one in an electrolyte;
FIG. 3 is a CV curve measured at different scan rates for a flexible graphene electrode prepared in accordance with example one;
FIG. 4 shows the square root v of the peak current Ip and the potential sweep rate in FIG. 3 1/2 Linear relationship between;
FIG. 5 shows K at different concentrations for a flexible graphene electrode prepared in accordance with example one 3 Fe(CN) 6 CV curve in electrolyte;
FIG. 6 is a correlation between peak current and concentration for different concentrations in FIG. 5;
FIG. 7 is a cyclic voltammogram of a flexible graphene electrode prepared in example one for detecting different concentrations of ascorbic acid;
FIG. 8 is a linear fit of FIG. 7;
FIG. 9 is a cyclic voltammogram of a flexible graphene electrode prepared in example one for detecting different concentrations of dopamine;
FIG. 10 is a linear fit of FIG. 9;
FIG. 11 is a low-power scanning electron microscope image of the gold nanostructure prepared in example two;
FIG. 12 is a high-power scanning electron microscope image of the gold nanostructure prepared in example two;
FIG. 13 is a low power scanning electron microscope image of the platinum micro-nano structure prepared in example three;
FIG. 14 is a high power scanning electron microscope image of the platinum micro-nano structure prepared in example three.
Detailed Description
The following examples further illustrate the invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit of the invention are intended to be within the scope of the present invention.
The first embodiment is as follows: the method for preparing the flexible graphene electrode in a rapid and controllable manner is completed according to the following steps:
1. preparing graphene/absolute ethanol suspension solution:
adding graphene powder into absolute ethyl alcohol, and performing ultrasonic treatment to obtain a graphene/absolute ethyl alcohol suspension solution with uniform dispersion;
2. the base material paper surface of a section of double-sided carbon conductive adhesive tape is downward, the adhesive surface is upward, two ends of the double-sided carbon conductive adhesive tape are fixed, and the adhesive conductive adhesive is exposed in the middle;
3. and (3) dripping the graphene/absolute ethyl alcohol suspension solution into the part of the double-sided carbon conductive adhesive tape, which exposes the adhesive conductive adhesive, and evaporating absolute ethyl alcohol by using an electric hair drier to obtain the flexible graphene electrode.
The graphene powder described in step one of this embodiment is purchased from Nanoxplore corporation under the model GrapheBlack 3X.
The second embodiment is as follows: the present embodiment differs from the specific 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) 10mL; the power of the ultrasonic treatment in the first step is 900-1200W, and the ultrasonic treatment time is 5-10 min. The other steps are the same as in the first embodiment.
And a third specific embodiment: this 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 mu m, the width is 23-28 mm, and the length is 35-40 mm. The other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: the double-sided carbon conductive adhesive tape in the second step is made of non-woven fabric as a base material, and comprises acrylic pressure-sensitive adhesive with carbon powder added as conductive filler on both sides, wherein the resistivity is (1.8+/-0.2) multiplied by 10 4 Omega cm. The other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: the volume of the graphene/absolute ethyl alcohol suspension solution and the double-sided carbon conductive adhesive tape in the third step expose the adhesive conductive adhesiveThe area ratio of the portions was 100. Mu.L (600 mm) 2 ～800mm 2 ). Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiments are flexible graphene electrodes for use in the preparation of metal micro-nanostructures, for use in the preparation of electrochemical biosensors, or for use in the preparation of portable electroanalysis and electronic devices.
Seventh embodiment: the present embodiment differs from the sixth embodiment in that: the flexible graphene electrode is used for preparing the metal micro-nano structure and is completed according to the following steps:
1. tearing off the base paper on the flexible graphene electrode, and then flatly adhering the base paper to a metal-plated glass sheet;
2. placing a template with a nano aperture on a flexible graphene electrode, enabling graphene to be in contact with the template with the nano aperture, evacuating air between the template and the double-sided carbon conductive adhesive tape, and finally compacting to obtain an assembled graphene electrode metal sheet;
3. a round hole is formed in the bottom of the electrolytic cell, the assembled graphene electrode metal sheet is placed at the bottom of the electrolytic cell, a template with a nano aperture is aligned with the round hole, an O-shaped ring is used for sealing, and a screw is used for connecting the electrolytic cell base, the assembled graphene electrode metal sheet and the electrolytic cell together and tightening;
4. adding electrolyte into an electrolytic cell, taking an assembled graphene electrode metal sheet as a working electrode, taking Ag/AgCl as a reference electrode, taking a platinum wire as a counter electrode, adopting constant voltage deposition under the conditions of room temperature and nitrogen atmosphere, and obtaining a metal micro-nano structure on the assembled graphene electrode metal sheet;
and step four, the electrolyte is a mixed solution of chloroauric acid, boric acid and water, a mixed solution of chloroplatinic acid, sulfuric acid and water or a mixed solution of copper sulfate, sulfuric acid and water. The other steps are the same as in the sixth embodiment.
Eighth embodiment: one difference between the present embodiment and the first to seventh embodiments is that: the metal-plated glass sheet in step one is formed on glass by physical vapor depositionDepositing a metal layer with the thickness of 100nm on a glass sheet, wherein 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 nanometer 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 mu m; the thickness of the polycarbonate porous membrane is 6-8 mu m; the diameter of the template with the nanometer aperture in the second step is 13 mm-25 mm, and the pore density is 6 multiplied by 10 8 /cm 2 ～2×10 9 /cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And step three, the electrolytic cell is made of polytetrafluoroethylene, and the diameter of a round hole at the bottom of the electrolytic cell is 8mm. The other steps are the same as those of embodiments one to seven.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: the concentration of chloroauric acid in the mixed solution of chloroauric acid, boric acid and water in the step four is 25mmol/L, and the concentration of boric acid is 0.3mol/L; the concentration of the chloroplatinic acid in the mixed solution of chloroplatinic acid, sulfuric acid and water in the step four is 10mmol/L, and the concentration of the sulfuric acid is 0.2mol/L; the concentration of the copper sulfate in the mixed solution of the copper sulfate, the sulfuric acid and the water in the step four is 0.4mol/L, and the concentration of the sulfuric acid is 10mmol/L. Other steps are the same as those of embodiments one to eight.
Detailed description ten: the present embodiment differs from the first to ninth embodiments in that: and step four, adopting a CHI 1040A electrochemical analyzer for constant voltage deposition, and selecting an 'Amperetic i-t cut' mode, wherein the deposition voltage is-0.2V to-0.4V, and the deposition time is 50s to 1200s. The other steps are the same as those of embodiments one to nine.
The present invention will be described in detail with reference to the accompanying drawings and examples.
Embodiment one: the method for preparing the flexible graphene electrode in a rapid and controllable manner is completed according to the following steps:
1. preparing graphene/absolute ethanol suspension solution:
adding 300mg of graphene powder into 10mL of absolute ethyl alcohol, and performing ultrasonic treatment for 5min under the ultrasonic power of 1200W to obtain a graphene/absolute ethyl alcohol suspension solution with uniform dispersion;
the graphene powder in the first step is purchased from Nanoxplore corporation and is of the model GrapheBlack 3X;
2. the base material paper surface of a section of double-sided carbon conductive adhesive tape is downward, the adhesive surface is upward, 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 mu m, the width is 25mm, the length is 35mm, the covered sizes at the two ends are 25mm multiplied by 5mm respectively, 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 base material, and contains acrylic pressure-sensitive adhesive with carbon powder added as conductive filler on both sides, wherein the resistivity is 1.8x10 4 Ωcm；
3. And (3) dripping 100 mu L of graphene/absolute ethyl alcohol suspension solution into the part of the double-sided carbon conductive adhesive tape, which exposes the adhesive conductive adhesive, and evaporating absolute ethyl alcohol by using an electric hair drier for 10min to obtain the flexible graphene electrode.
Cutting the flexible graphene electrode prepared in the first embodiment into a round shape with the diameter of 19mm plus or minus 0.5mm, wherein the round shape is shown in figure 1;
fig. 1 is an optical digital photograph of a flexible graphene electrode prepared in example one.
Tearing off base material paper on the flexible graphene electrode, and flatly adhering the base material paper to a glass sheet plated with gold to obtain an assembled graphene electrode; the glass sheet plated with gold is formed by depositing a gold layer with the thickness of 100nm on the glass sheet by a physical vapor deposition method; the size of the glass sheet is 76mm multiplied by 26mm multiplied by 2mm; a round hole is formed in the bottom of the electrolytic cell, the assembled graphene electrode is placed at the bottom of the electrolytic cell, the assembled graphene electrode is aligned with the round hole, the flexible graphene electrode faces the inside of the electrolytic cell and is sealed by an O-shaped ring, and the electrolytic cell base, the assembled graphene electrode and the electrolytic cell are connected together by screws and are tightened; the electrolytic cell is made of polytetrafluoroethylene, and the diameter of a round hole at the bottom of the electrolytic cell is 8mm; electrolyte is filled in the electrolytic cell,the electrolyte is composed of K 3 Fe(CN) 6 Mixing KCl and water to obtain a mixture, wherein K 3 Fe(CN) 6 The concentration of (2) is 1mmol/L, and the concentration of KCl is 0.1mol/L; the assembled graphene electrode is used as a working electrode, ag/AgCl (3M NaCl) is used as a reference electrode, a platinum wire is used as a counter electrode, and cyclic voltammetry scanning is carried out by adopting a CHI 1040A electrochemical analyzer; performing continuous 50 times of cyclic voltammetry scanning in electrolyte, wherein the cyclic voltammetry scanning curve is shown in figure 2, and changing K in electrolyte 3 Fe(CN) 6 The cyclic voltammograms are shown in figures 5 and 6;
FIG. 2 is a cyclic voltammogram of a flexible graphene electrode prepared in example one in an electrolyte;
as can be seen from fig. 2, these CVs all showed reversible redox reactions with negligible small changes, i.e. no sign of degradation at repeated scans, peak current changes within (2%), indicating satisfactory stability and reproducibility of the flexible graphene electrode.
FIG. 3 is a CV curve measured at different scan rates for a flexible graphene electrode prepared in accordance with example one;
FIG. 4 shows the square root v of the peak current Ip and the potential sweep rate in FIG. 3 1/2 Linear relationship between;
FIG. 5 shows K at different concentrations for a flexible graphene electrode prepared in accordance with example one 3 Fe(CN) 6 CV 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; respectively dissolving ascorbic acid and dopamine solutions with different concentrations in 0.1M PBS buffer solution, and adjusting the pH value to 7.2; cyclic voltammetry was performed using a CHI 1040A electrochemical analyzer. See fig. 7-8, fig. 9-10;
FIG. 7 is a cyclic voltammogram of a flexible graphene electrode prepared in example one for detecting different concentrations of ascorbic acid;
FIG. 8 is a linear fit of FIG. 7;
FIG. 9 is a cyclic voltammogram of a flexible graphene electrode prepared in example one for detecting different concentrations of dopamine;
FIG. 10 is a linear fit of FIG. 9;
fig. 7 to 9 show the results of the flexible graphene electrode prepared in example one for quantitative analysis and medical-related experimental analysis. FIGS. 7 and 8 ascorbic acid CV plots measured on flexible graphene electrodes show that there is a clear correlation between peak oxidation current and concentration, and a linear calibration curve can be established over a concentration range of 0.02mM-5.0mM (R 2 = 0.9991). FIGS. 9 and 10 are CV diagrams and linear correlation curves of measured dopamine, and the obtained results are similar to ascorbic acid in a concentration range of 0.001mM to 0.031mM, yielding R 2 Linear calibration curve= 0.9951. The detection Limits (LOD) of ascorbic acid and dopamine were determined to be (0.061.+ -. 0.002) mM and (0.0016.+ -. 0.0001) mM, respectively, based on the fitting parameters of the calibration curve. These LOD and linear response ranges of ascorbic acid (0.02 mM to 5.0 mM) and dopamine (0.001 to 0.031 mM) obtained on graphene electrodes are comparable to the currently known electrode LOD and linear response ranges. The above results demonstrate that the flexible graphene electrode prepared by the invention has good reproducibility, stability and quantification capability in conventional electrochemical analysis as a typical low-cost carbon electrode.
Embodiment two: according to the method for preparing the flexible graphene electrode in the first embodiment, the flexible graphene electrode is prepared again, and the preparation of the gold micro-nano structure by taking the prepared flexible graphene electrode as a raw material is completed according to the following steps:
1. tearing off the base paper on the flexible graphene electrode, and then flatly adhering the base paper to a glass sheet plated with gold;
the gold-plated glass sheet in the first step is formed by depositing a gold layer with a thickness of 100nm on the glass sheet by a physical vapor deposition method, wherein the dimensions of the glass sheet are 76mm multiplied by 26mm multiplied by 2mm;
2. placing a template with a nano aperture on a flexible graphene electrode, enabling graphene to be in contact with the template with the nano aperture, 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 nanometer aperture in the second step is made of a polycarbonate porous membrane; the thickness of the polycarbonate porous membrane is 6 mu m; the template with the nano pore diameter in the second step has the diameter of 25mm and the pore density of 6 multiplied by 10 8 /cm 2 ；
3. A round hole is formed in the bottom of the electrolytic cell, the assembled graphene electrode metal sheet is placed at the bottom of the electrolytic cell, a template with a nano aperture is aligned with the round hole, an O-shaped ring is used for sealing, and a screw is used for connecting the electrolytic cell base, the assembled graphene electrode metal sheet and the electrolytic cell together and tightening;
the material of the electrolytic cell in the third step is polytetrafluoroethylene, and the diameter of a round hole at the bottom of the electrolytic cell is 8mm;
4. adding electrolyte into an electrolytic cell, taking an assembled graphene electrode metal sheet as a working electrode, taking Ag/AgCl as a reference electrode, taking a platinum wire as a counter electrode, adopting constant voltage deposition under the conditions of room temperature and nitrogen atmosphere, and obtaining a gold micro-nano structure 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 0.3mol/L; and step four, adopting a CHI 1040A electrochemical analyzer for constant voltage deposition, and selecting an 'Amperetic i-t cut' mode, wherein the deposition voltage is-0.2V, and the deposition time is 200s.
FIG. 11 is a low power scanning electron microscope image of the gold micro-nano structure prepared in the second embodiment;
FIG. 12 is a high power scanning electron microscope image of the gold micro-nano structure prepared in the second embodiment;
as can be seen from FIGS. 11 to 12, the gold micro-nano structures prepared in the second embodiment are uniformly distributed, have different morphologies, and have a size distribution of 0.5 to 5 μm.
Embodiment III: according to the method for preparing the flexible graphene electrode in the first embodiment, the flexible graphene electrode is prepared again, and the preparation of the platinum micro-nano structure by taking the prepared flexible graphene electrode as a raw material is completed according to the following steps:
1. tearing off the base paper on the flexible graphene electrode, and then flatly adhering the base paper to a glass sheet plated with gold;
the metal-plated glass sheet in the first step is formed by depositing a gold layer with the thickness of 100nm on the glass sheet by a physical vapor deposition method, wherein the dimensions of the glass sheet are 76mm multiplied by 26mm multiplied by 2mm;
2. placing a template with a nano aperture on a flexible graphene electrode, enabling graphene to be in contact with the template with the nano aperture, 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 nanometer aperture in the second step is made of a polycarbonate porous membrane; the thickness of the polycarbonate porous membrane is 6 mu m; the template with the nano pore diameter in the second step has the diameter of 25mm and the pore density of 6 multiplied by 10 8 /cm 2 ；
3. A round hole is formed in the bottom of the electrolytic cell, the assembled graphene electrode metal sheet is placed at the bottom of the electrolytic cell, a template with a nano aperture is aligned with the round hole, an O-shaped ring is used for sealing, and a screw is used for connecting the electrolytic cell base, the assembled graphene electrode metal sheet and the electrolytic cell together and tightening;
the material of the electrolytic cell in the third step is polytetrafluoroethylene, and the diameter of a round hole at the bottom of the electrolytic cell is 8mm;
4. adding electrolyte into an electrolytic cell, taking an assembled graphene electrode metal sheet as a working electrode, taking Ag/AgCl as a reference electrode, taking a platinum wire as a counter electrode, adopting constant voltage deposition under the conditions of room temperature and nitrogen atmosphere, and obtaining a platinum micro-nano structure 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 0.2mol/L; and step four, adopting a CHI 1040A electrochemical analyzer for constant voltage deposition, and selecting an 'Amperetic i-t cut' mode, wherein the deposition voltage is-0.3V, and the deposition time is 1200s.
FIG. 13 is a low power scanning electron microscope image of the platinum micro-nano structure prepared in example three;
FIG. 14 is a high power scanning electron microscope image of the platinum micro-nano structure prepared in example three.
From fig. 13 to 14, it can be seen that the platinum micro-nano structures prepared in the third embodiment are relatively uniformly distributed, have uniform morphology, are mostly hemispherical, have uniform size, and have a size distribution of 0.5 μm to 8 μm.
Claims (8)
1. The application of the flexible graphene electrode is characterized in that the flexible graphene electrode is used for preparing a metal micro-nano structure, and the application is completed according to the following steps:
1. tearing off the base paper on the flexible graphene electrode, and then flatly adhering the base paper to a metal-plated glass sheet;
the preparation method of the flexible graphene electrode in the first step is completed according to the following steps:
(1) preparing graphene/absolute ethanol suspension solution:
adding graphene powder into absolute ethyl alcohol, and performing ultrasonic treatment to obtain a graphene/absolute ethyl alcohol suspension solution with uniform dispersion;
(2) the base material paper surface of a section of double-sided carbon conductive adhesive tape is downward, the adhesive surface is upward, two ends of the double-sided carbon conductive adhesive tape are fixed, and the adhesive conductive adhesive is exposed in the middle;
(3) dropwise adding the graphene/absolute ethyl alcohol suspension solution to a part of the double-sided carbon conductive adhesive tape, which exposes the adhesive conductive adhesive, and evaporating absolute ethyl alcohol by using an electric hair drier to obtain a flexible graphene electrode;
2. placing a template with a nano aperture on a flexible graphene electrode, enabling graphene to be in contact with the template with the nano aperture, 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 nanometer aperture in the second step is made of an alumina porous membrane or a polycarbonate porous membrane;
3. a round hole is formed in the bottom of the electrolytic cell, the assembled graphene electrode metal sheet is placed at the bottom of the electrolytic cell, a template with a nano aperture is aligned with the round hole, an O-shaped ring is used for sealing, and a screw is used for connecting the electrolytic cell base, the assembled graphene electrode metal sheet and the electrolytic cell together and tightening;
4. adding electrolyte into an electrolytic cell, taking an assembled graphene electrode metal sheet as a working electrode, taking Ag/AgCl as a reference electrode, taking a platinum wire as a counter electrode, adopting constant voltage deposition under the conditions of room temperature and nitrogen atmosphere, and obtaining a metal micro-nano structure on the assembled graphene electrode metal sheet;
and step four, the electrolyte is a mixed solution of chloroauric acid, boric acid and water, a mixed solution of chloroplatinic acid, sulfuric acid and water or a mixed solution of copper sulfate, sulfuric acid and water.
2. The use of the flexible graphene electrode according to claim 1, wherein the volume ratio of the graphene powder to the absolute ethanol in the step (1) is (50 mg-500 mg) 10mL; the power of the ultrasonic treatment in the first step is 900-1200W, and the ultrasonic treatment time is 5-10 min.
3. The use of the flexible graphene electrode according to claim 1, wherein the double-sided carbon conductive tape in the step (2) has a thickness of 150 μm to 170 μm, a width of 23mm to 28mm, and a length of 35mm to 40mm.
4. The flexible graphene electrode according to claim 1 or 3, wherein the double-sided carbon conductive tape in step (2) is a pressure-sensitive adhesive comprising a nonwoven fabric as a base material, and an acrylic pressure-sensitive adhesive comprising carbon powder as a conductive filler on both sides thereof, and has a specific resistance of (1.8.+ -. 0.2). Times.10 4 Ωcm。
5. The use of a flexible graphene electrode according to claim 1, characterized in that the graphite of step (3)The ratio of the volume of the alkene/absolute ethyl alcohol suspension solution to the area of the part of the double-sided carbon conductive tape where the adhesive conductive adhesive is exposed is 100 mu L (600 mm) 2 ～800mm 2 )。
6. The use of a flexible graphene electrode according to claim 1, wherein the metal-coated glass sheet in step one is a metal layer with a thickness of 100nm deposited on the glass sheet by physical vapor deposition, the dimensions of the glass sheet being 76mm x 26mm x 2mm, the metal being gold, platinum or copper; the thickness of the alumina porous membrane is 58-62 mu m; the thickness of the polycarbonate porous membrane is 6-8 mu m; the diameter of the template with the nanometer aperture in the second step is 13 mm-25 mm, and the pore density is 6 multiplied by 10 8 /cm 2 ～2×10 9 /cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And step three, the electrolytic cell is made of polytetrafluoroethylene, and the diameter of a round hole at the bottom of the electrolytic cell is 8mm.
7. The application of the flexible graphene electrode according to claim 1 or 6, wherein the concentration of chloroauric acid in the mixed solution of chloroauric acid, boric acid and water in the fourth step is 25mmol/L, and the concentration of boric acid is 0.3mol/L; the concentration of the chloroplatinic acid in the mixed solution of chloroplatinic acid, sulfuric acid and water in the step four is 10mmol/L, and the concentration of the sulfuric acid is 0.2mol/L; the concentration of the copper sulfate in the mixed solution of the copper sulfate, the sulfuric acid and the water in the step four is 0.4mol/L, and the concentration of the sulfuric acid is 10mmol/L.
8. The application of the flexible graphene electrode according to claim 7, wherein the constant voltage deposition in the fourth step adopts a CHI 1040A electrochemical analyzer, and an 'amberotic i-t curve' mode is selected, wherein the deposition voltage is-0.2V to-0.4V, and the deposition time is 50s to 1200s.
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