CN114093682A - Laser preparation method and application of graphene/Co-CoO composite electrode material - Google Patents
Laser preparation method and application of graphene/Co-CoO composite electrode material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 122
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 239000007772 electrode material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 30
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000003990 capacitor Substances 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011889 copper foil Substances 0.000 claims abstract description 7
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000004945 silicone rubber Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 10
- 239000010409 thin film Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 18
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 231100000481 chemical toxicant Toxicity 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
A laser preparation method and application of a graphene/Co-CoO composite electrode material are disclosed, firstly preparing a graphene oxide/cobalt acetate dispersion liquid, dripping the graphene oxide/cobalt acetate dispersion liquid on a PET or PI substrate, and airing at room temperature to obtain a graphene oxide/cobalt acetate film; then setting a pattern to be processed, a corresponding scanning speed and a corresponding scanning interval in control software matched with the scanning galvanometer, and setting laser parameters through a computer connected with a laser; finally, performing laser direct writing on the graphene oxide/cobalt acetate film by using a laser and a scanning galvanometer in the air to obtain a patterned graphene/Co-CoO composite electrode material film; preparing a micro super capacitor by using the prepared interdigital graphene/Co-CoO composite electrode material film, conductive silver paste, copper foil, RTV (room temperature vulcanized) silicone rubber and polyvinyl alcohol/phosphoric acid gel electrolyte; the method has the advantages of simplicity, high efficiency, low preparation cost and environmental friendliness, and the prepared micro super capacitor has excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of nano composite materials and micro super capacitors, and particularly relates to a laser preparation method and application of a graphene/Co-CoO composite electrode material.
Background
The micro super capacitor is a device for storing energy by utilizing double electric layers and redox reaction, has the advantages of long cycle life, good stability, quick charge and discharge, high power, energy density, portability and the like, can be used as an energy storage device of wearable and portable electronic products, and the electrochemical performance of the micro super capacitor is determined to a great extent by electrode materials. Graphene has excellent mechanical/electrochemical stability, high conductivity and large specific surface area, is widely used as an electrode material of a micro supercapacitor, but has low specific capacitance. CoO as an electrode material of a micro super capacitor has the advantages of high specific capacitance, low cost, rich content and the like, but the power density, rate capability and cycle life of the CoO are poor. The advantages of the graphene and the CoO can be simultaneously exerted by combining the graphene and the CoO, and the prepared graphene/CoO composite electrode material has the advantages of high specific capacitance, high energy and power density and long cycle life.
The existing method for preparing the graphene/CoO composite electrode material mainly comprises a chemical synthesis method, a hydrothermal method, a high-temperature calcination method and an electrodeposition method; the methods are long in preparation period, harsh in synthesis conditions, and require toxic chemical reagents, and the like, and the processing of a patterned structure cannot be realized while preparing materials, so that the large-scale preparation of the graphene/CoO composite electrode material and the application of the graphene/CoO composite electrode material in a micro supercapacitor are seriously influenced. Therefore, the method has important significance for promoting the application of the graphene/CoO composite electrode material in the micro supercapacitor by simply preparing the graphene/CoO composite electrode material in an environment-friendly, efficient and patterned structure.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a laser preparation method and application of a graphene/Co-CoO composite electrode material, which can be used for preparing a patterned graphene/Co-CoO composite electrode material film and preparing a micro supercapacitor with excellent electrochemical performance based on the processed interdigital graphene/Co-CoO composite electrode material film.
In order to achieve the purpose, the invention adopts the technical scheme that:
a laser preparation method of a graphene/Co-CoO composite electrode material comprises the following steps:
(a) ultrasonically mixing graphene oxide and cobalt acetate tetrahydrate to obtain a graphene oxide/cobalt acetate dispersion liquid;
(b) dripping the graphene oxide/cobalt acetate dispersion liquid on a PET or PI substrate, and airing at room temperature to obtain a graphene oxide/cobalt acetate film;
(c) setting a pattern to be processed, a corresponding scanning speed and a corresponding scanning interval in control software matched with a scanning galvanometer, and setting laser parameters through a computer connected with a laser;
(d) and performing laser direct writing on the graphene oxide/cobalt acetate film by using a laser and a scanning galvanometer in the air to obtain the patterned graphene/Co-CoO composite electrode material film, wherein the direct-written pattern comprises a rectangular shape and an interdigital shape.
The application of the graphene/Co-CoO composite electrode material comprises the following steps: and preparing the micro super capacitor by using the prepared interdigital graphene/Co-CoO composite electrode material film, conductive silver paste, copper foil, RTV (room temperature vulcanized) silicone rubber and polyvinyl alcohol/phosphoric acid gel electrolyte.
The preparation process of the miniature super capacitor is as follows: firstly, adhering a cut copper foil to two sides of an interdigital graphene/Co-CoO composite electrode material film by using conductive silver paste to serve as a current collector and drying, then packaging and drying a copper strip and the conductive silver paste by using RTV (room temperature vulcanized) silicon rubber, and then dripping polyvinyl alcohol/phosphoric acid gel electrolyte on the surface of the interdigital graphene/Co-CoO composite electrode material film and naturally drying at room temperature for not less than 24 hours.
The polyvinyl alcohol/phosphoric acid gel electrolyte is prepared by continuously stirring a mixture of 3g of polyvinyl alcohol and 6g of phosphoric acid in 30mL of deionized water at 85 ℃ for 1 h.
The interdigital graphene/Co-CoO composite electrode material film has the following structure: the current collector consists of 12 fingers, each polarity is 6, the length of each finger is 5mm, the width of each finger is 1mm, the distance between every two adjacent fingers is 200 mu m, and the width of a current collector area connected to the two sides is 3 mm.
The preparation process of the graphene oxide/cobalt acetate dispersion liquid in the step (a) is as follows: adding a mixture of 0.6g of graphene oxide and 0.3-1.2 g of cobalt acetate tetrahydrate into 60ml of deionized water, and ultrasonically dispersing for 4 hours by using an ultrasonic cell crusher.
The preparation process of the graphene oxide/cobalt acetate film in the step (b) is as follows: and (3) dropwise coating the graphene oxide/cobalt acetate dispersion liquid on the surface of a PET or PI substrate, and naturally drying at room temperature for not less than 24 h.
When the laser direct writing is carried out in the step (d), firstly, the graphene oxide/cobalt acetate film is fixed in a processing area of a scanning galvanometer, then, the direct writing is carried out according to the graph set in the step (c) and laser parameters to obtain a patterned graphene/Co-CoO composite electrode material film, and then, the laser parameters are adjusted to remove redundant graphene oxide/cobalt acetate.
The parameters of the graphene/Co-CoO composite electrode material film prepared by laser direct writing in the step (d) are as follows: the laser has the advantages that the diameter of a light spot is 86 micrometers, the laser power is 0.8W, the laser wavelength is 532nm or 1064nm, the scanning speed is 150-550 mm/s, the linear filling interval is 12-24 micrometers, and the laser is a picosecond laser and a nanosecond laser.
The invention has the beneficial effects that:
according to the method, picosecond laser or nanosecond laser and a scanning galvanometer are used for carrying out laser direct writing on the graphene oxide/cobalt acetate film in the air to obtain the patterned graphene/Co-CoO composite electrode material film, so that the defects that a large amount of toxic chemical reagents are required, the process is complex, an additional binder is required and the like in the traditional preparation process of the graphene/CoO composite electrode material are overcome, and the graphene/CoO composite electrode material is efficiently prepared by the laser; has the advantages of simplicity, high efficiency, low preparation cost and environmental protection.
The micro supercapacitor prepared by using the interdigital graphene/Co-CoO composite electrode material film and the polyvinyl alcohol/phosphoric acid gel electrolyte shows excellent electrochemical performance and mechanical flexibility, and can be used as an energy storage device of portable and wearable electronic equipment.
Drawings
FIG. 1 is a schematic diagram of the preparation method and application of the present invention.
FIG. 2(a) is a graph showing the results of Raman spectroscopy on the graphene/Co-CoO composite electrode material obtained in example 1; fig. 2(b) is a graph showing the results of X-ray diffraction tests (2 θ is 5 to 80 °) of the graphene/Co-CoO composite electrode material obtained in example 1.
Fig. 3(a) is a graph showing the results of X-ray diffraction tests (2 θ 27 to 80 °) on the graphene/Co-CoO composite electrode material obtained in example 1 (scan speeds of 150mm/s, 250mm/s, and 350 mm/s); fig. 3(b) is a graph showing the results of X-ray diffraction tests (2 θ is 27 to 80 °) of the graphene/Co-CoO composite electrode material obtained in example 1 (scan speeds are 450mm/s and 550 mm/s).
FIG. 4 is a graph of the X-ray photoelectron spectroscopy test result of the graphene oxide/cobalt acetate and graphene/Co-CoO composite electrode material (scanning speed 150mm/s) obtained in example 1; wherein FIG. 4(a) is a high resolution spectrum of C1s, and FIG. 4(b) is a high resolution spectrum of Co 2 p.
FIG. 5 is a scanning electron microscope test result chart of the graphene/Co-CoO composite electrode material (scanning speed of 150mm/s) obtained in example 1.
FIG. 6 is a transmission electron microscope test result chart of the graphene/Co-CoO composite electrode material (scanning speed of 150mm/s) obtained in example 1.
FIG. 7 is a graph showing the results of the specific surface area test of the graphene/Co-CoO composite electrode material obtained in example 1 (scan speed of 150 mm/s); wherein fig. 7(a) is a nitrogen adsorption-desorption isotherm of the graphene/Co-CoO composite electrode material, and fig. 7(b) is a pore size distribution of the graphene/Co-CoO composite electrode material.
FIG. 8 is a graph of the results of electrochemical testing of a micro-supercapacitor made in example 2 using graphene/Co-CoO interdigitated electrodes and a polyvinyl alcohol/phosphoric acid gel electrolyte; wherein fig. 8(a) is a cyclic voltammetry test result graph of the micro supercapacitor, fig. 8(b) is a constant current charging and discharging test result graph of the micro supercapacitor, fig. 8(c) is an area specific capacitance of the micro supercapacitor, and fig. 8(d) is a cyclic stability test result graph of the micro supercapacitor.
Figure 9 is a nyquist plot for a miniature supercapacitor made in example 2 using graphene/Co-CoO interdigitated electrodes and a polyvinyl alcohol/phosphate gel electrolyte.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1, as shown in fig. 1, a laser preparation method of a graphene/Co-CoO composite electrode material includes the following steps:
(a) adding a mixture of 0.6g of graphene oxide and 0.9g of cobalt acetate tetrahydrate into 60ml of deionized water, and ultrasonically dispersing for 4 hours by using an ultrasonic cell crusher to obtain a graphene oxide/cobalt acetate dispersion liquid;
(b) 7ml of graphene oxide/cobalt acetate dispersion liquid is dripped on the surface of a PET (0.1 multiplied by 35 multiplied by 65mm) substrate and naturally dried for 48h at room temperature;
(c) setting a pattern to be processed and corresponding scanning speed and scanning distance in control software matched with a scanning galvanometer, and setting laser parameters through a computer connected with a picosecond laser (the pulse width is 10ps, and the laser wavelength is 532 nm);
(d) performing laser direct writing on the graphene oxide/cobalt acetate film by using a picosecond laser and a scanning galvanometer to obtain a patterned graphene/Co-CoO composite electrode material film;
when laser direct writing is carried out, firstly fixing the graphene oxide/cobalt acetate film in a processing area of a scanning galvanometer, then carrying out direct writing according to the graph set in the step (c) and laser parameters to obtain a patterned graphene/Co-CoO composite electrode material film, and then adjusting the laser parameters to remove redundant graphene oxide/cobalt acetate;
the pattern of the direct writing of the embodiment is rectangular, and the distance of the linear filling is 18 μm; the scanning speed during laser direct writing is 150-550 mm/s, the spot diameter is 86 μm, and the laser power is 0.8W.
The graphene/Co-CoO composite electrode material film obtained in the embodiment is detected:
the raman spectrum test result is shown in fig. 2(a), and it can be seen that the prepared graphene/Co-CoO composite electrode material has a CoO peak, a D peak, a G peak and a 2D peak in the raman spectrum; the appearance of a CoO peak indicates that the prepared composite material contains CoO, and the appearance of a 2D peak indicates that the graphene oxide is reduced into graphene by laser. The Raman spectrum of the graphene/Co-CoO composite electrode material prepared at the scanning speed of 150mm/s has the weakest D peak and the strongest 2D peak, which shows that the defect density is the lowest. The X-ray powder diffraction (XRD) test results of the prepared graphene/Co-CoO composite electrode material are shown in fig. 2(b) and fig. 3, and the sharp diffraction peak related to the graphite (002) crystal face and the weak diffraction peak related to the oxygen-containing functional group (100) crystal face also indicate that the graphene oxide is reduced into graphene by laser; and diffraction peaks corresponding to cobalt and compounds thereof indicate that cobalt and compounds thereof in the composite material are Co and CoO. The X-ray photoelectron spectroscopy (XPS) test result of the prepared graphene/Co-CoO composite electrode material is shown in fig. 4, the weakening of the characteristic peak corresponding to the C-O bond also indicates that the graphene oxide is reduced into graphene by laser, and the result of the Co 2p high-resolution XPS spectrum also indicates that the composite material contains Co and CoO. The Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) test results of the graphene/Co-CoO composite electrode material prepared at the scanning speed of 150mm/s are shown in fig. 5 and 6, and Co-CoO particles with the particle size of 10-500 nm are uniformly distributed on the surface of the porous graphene. The specific surface area test result of the graphene/Co-CoO composite electrode material prepared at the scanning speed of 150mm/s is shown in FIG. 7, and it can be seen that the prepared composite electrode material has a hierarchical pore structure; wherein the micropores (<2nm) can realize effective charge storage, and the mesopores (2-50 nm) and the macropores (>50nm) can promote the transmission of electrolyte ions.
Example 2, under the condition that other laser direct writing process parameters in example 1 are not changed, the scanning speed is changed to 150mm/s, and the direct writing pattern is changed to an interdigital shape; and preparing the micro super capacitor by using the obtained interdigital graphene/Co-CoO composite electrode material film, conductive silver paste, copper foil, RTV silicon rubber and polyvinyl alcohol/phosphoric acid gel electrolyte.
The interdigital graphene/Co-CoO composite electrode material film prepared by the embodiment is composed of 12 interdigital parts, each interdigital part is 5mm in length and 1mm in width, the distance between every two adjacent interdigital parts is 200 micrometers, and the width of a current collector area connected to the two sides is 3 mm.
Firstly, adhering a cut copper foil to two sides of an interdigital graphene/Co-CoO composite electrode material film by using conductive silver paste to serve as a current collector, drying for 2 hours at 55 ℃, then packaging the copper strip and the silver paste by using RTV (room temperature vulcanized) silicon rubber, drying for 4 hours at 55 ℃, and then dripping polyvinyl alcohol/phosphoric acid gel electrolyte on the surface of the interdigital graphene/Co-CoO composite electrode material film and naturally drying for 24 hours at room temperature. To prepare a polyvinyl alcohol/phosphoric acid gel electrolyte, a mixture of 3g of polyvinyl alcohol and 6g of phosphoric acid was continuously stirred in 30mL of deionized water at 85 ℃ for 1 hour. As shown in fig. 8 and 9, the electrochemical performance test of the prepared micro-supercapacitor includes cyclic voltammetry test, constant current charge/discharge test and electrochemical impedance test. The area specific capacitance, the power density and the energy density of the prepared micro super capacitor respectively reach 466.26mF cm-2、1.91mW cm-2And 93.25. mu. Wh cm-2. After 5000 cycles, the specific capacitance of the prepared micro-supercapacitor kept 87% of the initial specific capacitance.
Example 3, in the case of example 1, the scanning speed was changed to 150mm/s and the pitch of the linear filling was changed to 12 μm, 14 μm, 16 μm, 20 μm, 22 μm, 24 μm, without changing other laser direct writing process parameters. The effect of the graphene/Co-CoO composite electrode material film obtained in the example is similar to that of the graphene/Co-CoO composite electrode material film obtained in the example 1.
Example 4, the preparation process of the graphene oxide/cobalt acetate dispersion of example 1 was changed to: adding a mixture of 0.6g of graphene oxide and 0.3g, 0.6g, 0.75g and 1.2g of cobalt acetate tetrahydrate into 60ml of deionized water, and ultrasonically dispersing for 4 hours by using an ultrasonic cell crusher; in the case of example 1, in which the other laser direct writing process parameters were not changed, the scanning speed was changed to 150 mm/s. The effect of the graphene/Co-CoO composite electrode material film obtained in the example is similar to that of the graphene/Co-CoO composite electrode material film obtained in the example 1.
Example 5, in the case of the laser direct writing process parameters of example 1 being unchanged, the laser used was changed to a nanosecond laser (pulse width 1ns, wavelength 1064 nm). The effect of the graphene/Co-CoO composite electrode material film obtained in the example is similar to that of the graphene/Co-CoO composite electrode material film obtained in the example 1.
Claims (9)
1. A laser preparation method of a graphene/Co-CoO composite electrode material is characterized by comprising the following steps:
(a) ultrasonically mixing graphene oxide and cobalt acetate tetrahydrate to obtain a graphene oxide/cobalt acetate dispersion liquid;
(b) dripping the graphene oxide/cobalt acetate dispersion liquid on a PET or PI substrate, and airing at room temperature to obtain a graphene oxide/cobalt acetate film;
(c) setting a pattern to be processed, a corresponding scanning speed and a corresponding scanning interval in control software matched with a scanning galvanometer, and setting laser parameters through a computer connected with a laser;
(d) and performing laser direct writing on the graphene oxide/cobalt acetate film by using a laser and a scanning galvanometer in the air to obtain the patterned graphene/Co-CoO composite electrode material film, wherein the direct-written pattern comprises a rectangular shape and an interdigital shape.
2. The use of the graphene/Co-CoO composite electrode material according to claim 1, wherein: and preparing the micro super capacitor by using the prepared interdigital graphene/Co-CoO composite electrode material film, conductive silver paste, copper foil, RTV (room temperature vulcanized) silicone rubber and polyvinyl alcohol/phosphoric acid gel electrolyte.
3. The application of the graphene/Co-CoO composite electrode material according to claim 2, wherein the preparation process of the miniature supercapacitor is as follows: firstly, adhering a cut copper foil to two sides of an interdigital graphene/Co-CoO composite electrode material film by using conductive silver paste to serve as a current collector and drying, then packaging and drying a copper strip and the conductive silver paste by using RTV (room temperature vulcanized) silicon rubber, and then dripping polyvinyl alcohol/phosphoric acid gel electrolyte on the surface of the interdigital graphene/Co-CoO composite electrode material film and naturally drying at room temperature for not less than 24 hours.
4. The use of the graphene/Co-CoO composite electrode material according to claim 2, wherein: the polyvinyl alcohol/phosphoric acid gel electrolyte is prepared by continuously stirring a mixture of 3g of polyvinyl alcohol and 6g of phosphoric acid in 30mL of deionized water at 85 ℃ for 1 h.
5. The application of the graphene/Co-CoO composite electrode material according to claim 2, wherein the structure of the interdigital graphene/Co-CoO composite electrode material film is as follows: the electrode is composed of 12 fingers, each polarity is 6, the length of each finger is 5mm, the width of each finger is 1mm, the distance between every two adjacent fingers is 200 micrometers, and the width of a current collector connecting area on two sides of the electrode is 3 mm.
6. The laser preparation method of the graphene/Co-CoO composite electrode material according to claim 1, wherein the graphene oxide/cobalt acetate dispersion liquid in the step (a) is prepared by the following steps: adding a mixture of 0.6g of graphene oxide and 0.3-1.2 g of cobalt acetate tetrahydrate into 60ml of deionized water, and ultrasonically dispersing for 4 hours by using an ultrasonic cell crusher.
7. The laser preparation method of the graphene/Co-CoO composite electrode material according to claim 1, wherein the graphene oxide/cobalt acetate thin film in the step (b) is prepared by the following steps: and (3) dropwise coating the graphene oxide/cobalt acetate dispersion liquid on the surface of a PET or PI substrate, and naturally drying at room temperature for not less than 24 h.
8. The laser preparation method of the graphene/Co-CoO composite electrode material according to claim 1, wherein in the step (d) of laser direct writing, firstly, the graphene oxide/cobalt acetate film is fixed in a processing area of a scanning galvanometer, then, the direct writing is performed according to the pattern and the laser parameters set in the step (c) to obtain a patterned graphene/Co-CoO composite electrode material film, and then, the laser parameters are adjusted to remove the redundant graphene oxide/cobalt acetate.
9. The laser preparation method of the graphene/Co-CoO composite electrode material according to claim 1, wherein the parameters for preparing the graphene/Co-CoO composite electrode material film by laser direct writing in the step (d) are as follows: the laser has the advantages that the diameter of a light spot is 86 micrometers, the laser power is 0.8W, the laser wavelength is 532nm or 1064nm, the scanning speed is 150-550 mm/s, the linear filling interval is 12-24 micrometers, and the laser is a picosecond laser and a nanosecond laser.
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