CN113205965B - Planar asymmetric miniature super capacitor and preparation method thereof - Google Patents
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
The invention discloses a planar asymmetric miniature super capacitor and a preparation method thereof, wherein the method comprises the following steps: (1) forming a layer of a second electrode precursor on the first electrode precursor; (2) presetting a first laser parameter and a second laser parameter; (3) executing a laser integrated processing program, and processing a second electrode precursor into a second electrode with a preset pattern under first laser parameters; processing the first electrode precursor into a first electrode with a preset pattern under a second laser parameter; (4) enclosing the first electrode and the second electrode in a middle hollow area by using a prepreg with the periphery closed and the middle hollow; (5) coating an electrolyte on the middle hollow area to cover the first electrode and the second electrode; (6) and packaging to form the planar asymmetric miniature super capacitor. The invention has the advantages of rapidness, high efficiency, high processing precision and the like, and the prepared device has wider voltage window, energy density and high rate performance and is beneficial to realizing large-scale production.
Description
Technical Field
The invention belongs to the technical field of miniature super capacitor preparation, and particularly relates to a preparation method of a planar asymmetric super capacitor based on laser direct writing.
Background
In order to promote the miniaturization, portability and function integration development of high-performance electronic equipment, the development of a micro energy storage device which is highly compatible with the high-performance electronic equipment and has low cost, high electrochemical performance and function integration is urgently needed so as to meet the great increase of the requirements in the fields of high-end communication, portable intelligent equipment, aerospace, biomedical treatment and the like. In the information age, Micro Supercapacitors (MSCs) have attracted considerable attention in applications of advanced electronic products due to their ultra-high power density and ultra-long cycle life, and may even replace micro batteries in some fields.
At present, the preparation process of the planar asymmetric MSCs has the defects of time and energy consumption, complicated steps and the like. Therefore, it is desirable to develop a simple, efficient, highly accurate and low-cost method for rapidly manufacturing planar asymmetric MSCs.
Disclosure of Invention
The invention aims to provide a planar asymmetric miniature supercapacitor and a preparation method thereof, and the planar asymmetric miniature supercapacitor has the advantages of simplicity in operation, low cost, high processing efficiency, high processing precision and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a planar asymmetric miniature supercapacitor comprises the following steps:
(1) forming a layer of a second electrode precursor on the first electrode precursor;
(2) presetting a first laser parameter and a second laser parameter, wherein the repetition frequency of the first laser parameter is lower than that of the second laser parameter, and the scanning speed of the first laser parameter is higher than that of the second laser parameter;
(3) executing a laser integrated processing program, processing the second electrode precursor into a first preset pattern under the first laser parameter so as to form a second electrode on the first electrode precursor, wherein the surface of the first electrode precursor except the second electrode is exposed; processing the surface exposed area of the first electrode precursor into a second preset pattern matched with the first preset pattern under the second laser parameter so as to form a first electrode on the first electrode precursor, wherein the first electrode and the second electrode are positioned on the same plane due to volume expansion in the processing process, and the first electrode and the second electrode form an asymmetric structure;
(4) positioning a prepreg with the periphery closed and the middle hollowed out in an aligned mode on the first electrode precursor so as to enclose the first electrode and the second electrode in the middle hollowed-out area of the prepreg;
(5) coating an electrolyte on the middle hollow area of the prepreg to cover the first electrode and the second electrode;
(6) and packaging to form the planar asymmetric miniature super capacitor.
Preferably, the step (2) further includes presetting a third laser parameter, wherein the repetition frequency of the third laser parameter is higher than that of the first laser parameter, and the scanning speed of the third laser parameter is higher than that of the second laser parameter; after forming the second electrode in step (3) and before forming the first electrode, machining a surface of the second electrode into a porous structure under the third laser parameters to form a porous second electrode.
Preferably, the repetition frequency of the first laser parameter is 5-50 kHz, and the scanning speed is 1000-5000 mm/s; the repetition frequency of the second laser parameter is 200 kHz-80 MHz, and the scanning speed is 1-200 mm/s.
Preferably, the repetition frequency of the third laser parameter is 200 kHz-80 MHz, and the scanning speed is 1000-5000 mm/s.
Preferably, the thickness of the first electrode precursor is 50 to 500 μm, and the thickness of the second electrode precursor is 1 to 100 μm.
Preferably, the first predetermined pattern of the first electrode is one of an interdigital shape, a circular shape, an arc shape and a linear shape, and correspondingly, the second electrode is one of an interdigital shape, a circular shape, an arc shape and a linear shape matched with the first electrode; the distance between the first electrode and the second electrode is 10-1000 mu m.
Preferably, the first electrode precursor is a carbon precursor, correspondingly, the first electrode is laser-induced graphene; the second electrode precursor is MXenes and correspondingly the second electrode is an MXenes electrode.
Preferably, the thickness of the prepreg is 5-50 μm greater than that of the first electrode; and (5) coating the electrolyte to the thickness so that the electrolyte and the peripheral closed area of the prepreg are positioned on the same plane.
A planar asymmetric micro supercapacitor prepared by the preparation method of any one of the above.
The beneficial effects of the invention include: according to the invention, based on different interaction mechanisms of laser and substances, different laser parameters are preset in the same laser processing equipment, and an integrated processing program is executed, so that the integrated processing of the planar asymmetric miniature supercapacitor is realized, and the method has the advantages of rapidness, high efficiency, high processing precision and the like.
Drawings
FIG. 1 is a schematic flow chart of the preparation of planar asymmetric MSCs according to example 1 of the present invention.
FIG. 2 is an SEM photograph of porous MXenes obtained in step S3 of example 1.
FIG. 3 is an SEM photograph of LIG obtained in step S4 of example 1.
Fig. 4 is a schematic diagram of the asymmetric MSCs obtained in step S5 according to the embodiment of the present invention.
FIG. 5 is a CV plot of 50mV/s sweep rate for asymmetric MSCs obtained in example 1 of the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings and preferred embodiments. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
It should be noted that the terms of orientation such as left, right, up, down, top and bottom in the present embodiment are only relative concepts to each other or are referred to the normal use state of the product, and should not be considered as limiting.
In an embodiment of the present invention, a method for manufacturing a planar asymmetric micro supercapacitor is provided, which includes the following steps:
(1) forming a layer of a second electrode precursor on the first electrode precursor;
(2) presetting a first laser parameter and a second laser parameter, wherein the repetition frequency of the first laser parameter is lower than that of the second laser parameter, and the scanning speed of the first laser parameter is higher than that of the second laser parameter;
(3) executing a laser integrated processing program, firstly processing the second electrode precursor into a first preset pattern under the first laser parameter so as to form a second electrode on the first electrode precursor, wherein the surface of the first electrode precursor except the second electrode is exposed, and then processing the exposed area of the surface of the first electrode precursor into a second preset pattern matched with the first preset pattern under the second laser parameter so as to form a first electrode on the first electrode precursor, wherein the first electrode and the second electrode are positioned on the same plane due to volume expansion in the processing process, and the first electrode and the second electrode form an asymmetric structure;
(4) positioning a prepreg with the periphery closed and the middle hollowed out in an aligned mode on the first electrode precursor so as to enclose the first electrode and the second electrode in the middle hollowed-out area of the prepreg;
(5) coating an electrolyte on the middle hollow area of the prepreg to cover the first electrode and the second electrode;
(6) and packaging to form the planar asymmetric miniature super capacitor.
In a preferred embodiment, the step (2) further includes presetting a third laser parameter, wherein the repetition frequency of the third laser parameter is higher than that of the first laser parameter, and the scanning speed of the third laser parameter is higher than that of the second laser parameter; after forming the second electrode in step (3) and before forming the first electrode, machining a surface of the second electrode into a porous structure under the third laser parameters to form a porous second electrode.
In a preferred embodiment, the repetition frequency of the first laser parameter is 5-50 kHz, and the scanning speed is 1000-5000 mm/s; the repetition frequency of the second laser parameter is 200 kHz-80 MHz, and the scanning speed is 1-200 mm/s. The first laser parameter is set to be low repetition frequency (repetition frequency) and high scanning speed (scanning speed), under the optimized first laser parameter, the photothermal effect can be reduced as much as possible, the cold machining effect is generated, the edge burrs are avoided, the appearance of the machined first preset pattern is enabled to be finer, and meanwhile, the set first laser parameter can enable the second electrode precursor except the preset pattern to be removed to expose the first electrode precursor without damaging the first electrode precursor except the first preset pattern. The second laser parameter is set to be high repetition frequency and low scanning speed, and under the optimized second laser parameter, higher thermal effect can be generated, so that the surface of the first electrode precursor is converted into the first electrode.
In a preferred embodiment, the repetition frequency of the third laser parameter is 200 kHz-80 MHz, and the scanning speed is 1000-5000 mm/s. And setting the third laser parameter as a high repetition frequency and a high scanning speed, and generating a lower thermal effect under the optimized third laser parameter to further form a pore network structure on the second electrode so as to form a porous second electrode. That is, in a preferred embodiment, the thermal effect generated at the first laser parameter < the thermal effect generated at the third laser parameter < the thermal effect generated at the second laser parameter.
In a preferred embodiment, the thickness of the first electrode precursor is 50 to 500 μm, and the thickness of the second electrode precursor is 1 to 100 μm.
In a preferred embodiment, the first predetermined pattern of the first electrode is one of an interdigital shape, a circular shape, an arc shape and a linear shape, and correspondingly, the second electrode is one of an interdigital shape, a circular shape, an arc shape and a linear shape matched with the first electrode; the distance between the first electrode and the second electrode is 10-1000 mu m.
When the first preset pattern and the second preset pattern are both interdigital (or called comb-shaped), the two electrode pairs are arranged in a staggered manner (as shown in fig. 1); when the first preset pattern and the second preset pattern are both circular, the two electrodes form the shape of a concentric circle; when the first preset pattern and the second preset pattern are both arc-shaped, the arc-shaped openings of the two electrodes are arranged towards the same direction; when the first preset pattern and the second preset pattern are both linear, the two electrodes are arranged oppositely and in parallel to form a shape. Preferably, the first electrode and the second electrode are interdigital, and the two electrodes are arranged in a staggered manner, but the preset pattern is not limited to the interdigital, and the first electrode and the second electrode with any designable shapes besides the listed patterns can be processed by the laser direct writing technology.
In a preferred embodiment, the first electrode precursor is a carbon precursor, and correspondingly, the first electrode is laser-induced graphene; the second electrode precursor is MXenes and correspondingly the second electrode is an MXenes electrode, more preferably the second electrode is a porous MXenes electrode.
The two-dimensional transition metal carbide and nitride (MXenes) have the advantages of high metal conductivity, high capacitance performance, quick current response, ultra-long cycle life and the like, and because the MXenes material generally has larger surface energy, the accumulation and stacking among the sheets are easy to occur, so that the potential energy storage space among the sheets cannot be completely utilized, the transmission of ions is seriously hindered, and the electrochemical utilization rate of the sheets is reduced. For this reason, researchers have proposed a strategy of three-dimensionally structuring (i.e., forming a porous network structure) MXenes to inhibit stacking between MXenes sheets, which not only increases the specific surface area thereof to provide a large number of active attachment sites for ions, but also facilitates rapid penetration of the electrolyte. However, the current MXenes three-dimensional structuring process still involves hazardous chemical reagents and high temperature specialized equipment. In the embodiment of the invention, the porous reticular MXenes can be prepared in a simple, efficient, low-cost and environment-friendly manner through the predetermined third laser parameter.
In a preferred embodiment, the thickness of the prepreg is 5 to 50 μm greater than the thickness of the first electrode; and (5) coating the electrolyte to the thickness so that the electrolyte and the peripheral closed area of the prepreg are positioned on the same plane.
The invention further provides a planar asymmetric micro supercapacitor prepared by the preparation method.
Example 1
As shown in fig. 1, a method for manufacturing a planar asymmetric micro supercapacitor according to an embodiment of the present invention includes the following steps:
s1, coating an MXenes film 2 on the carbon precursor film 1 to form an upper and lower layer composite structure.
The carbon precursor in the step can be selected from PI (such as a commercially available PI adhesive tape or film, or a material formed by heating and polycondensation of a performed polymer PAA), PEI, polyether ether ketone and the like, and the thickness range of the sheet is 50-500 mu m. The carbon precursor film (length: 1-100cm, width: 10-50cm, thickness: 50-500 μm) is cleaned by deionized water, ethanol, acetone and the like respectively, and then dried in an oven at 60 ℃ for 2-3 h. In this example, the carbon precursor was selected as a commercially available PI film having a thickness of 125 μm,
in this step S1, the MXenes film may be coated only on the area where the second electrode needs to be formed, not on the entire PI film.
MXenes in step S1 can be obtained commercially or prepared by chemical methods. The general chemical formula of MXenes can be Mn+1XnTxWherein M denotes a transition metal (e.g., Ti, Zr, Hf, V, Nb, Ta, Cr, Sc, etc.), X denotes C or/and N, N is generally 1 to 3, and T isxRefers to a surface group (e.g. O)2-、OH-、F-、NH3、NH4+Etc.). In this example, Ti was etched by hydrochloric acid and lithium fluoride3AlC2Preparation of MAX phase to obtain Ti3C2TxPowder material is evenly dispersed in deionized water, and then Ti is sprayed by a spray gun3C2TxThe solution is sprayed on a PI film to form an MXenes uniform film with the thickness of about 50 μm, and the MXenes uniform film is placed in an oven to be dried for 2-5 h at the temperature of 60 ℃.
S2, establishing a 1 st layer in laser processing software, and correspondingly setting laser parameters with low repetition frequency and high scanning speed for pre-patterning MXenes on the upper layer to form a pure MXenes microelectrode.
In the step, a low-repetition-frequency laser is used for directly writing an MXenes film on the upper layer of the carbon precursor at a high scanning speed to remove materials, and the movement of a laser beam is controlled by a computer software design pattern to ablate part of the MXenes layer, so that the MXenes microelectrode structure is obtained, wherein the MXenes microelectrode is interdigital in the example.
The laser parameters in this step were set as follows: the wavelength is 190-10600 nm, the repetition frequency is 5-50 kHz, the power is 1-5W, the scanning speed is 1000-5000 mm/s, and the scanning frequency is 2-10 times. Specifically, in this example, the laser parameters are set as follows: the wavelength was 355nm, the repetition frequency was 30kHz, the power was 2.7W, the scanning speed was 1000mm/s, and the number of scans was 5.
S3, establishing a 2 nd layer in laser processing software, and correspondingly setting laser parameters with high repetition frequency and high scanning speed for reprocessing the patterned MXenes thin film in the step S2 to form a porous MXenes microelectrode.
In step S3, a high repetition frequency laser is used to perform three-dimensional structuring processing on the patterned MXenes film at a high scanning speed, and a pattern is designed by computer software to control the removal of internal functional groups of the MXenes film in the laser beam motion-induced patterned region, so as to form a three-dimensional porous network structure, thereby obtaining a microelectrode structure of porous MXenes.
The laser parameters in this step S3 are set as follows: the wavelength is 190-10600 nm, the repetition frequency is 200 kHz-80 MHz, the power is 1-5W, the scanning speed is 1000-5000 mm/s, and the scanning frequency is 1-10 times. Specifically, in this example, the laser parameters are set as follows: the wavelength was 355nm, the repetition frequency was 200kHz, the power was 2.7W, the scanning speed was 1000mm/s, and the number of scans was 1. The SEM image of the porous MXenes film prepared in this example is shown in fig. 2 (the left and right images are structural morphology images under different multiples), from which it can be known that the MXenes after laser treatment exhibit a porous structure, and the nanosheets have mesoscale pores, which are beneficial to ion transmission and enhance electrochemical performance.
S4, establishing a 3 rd image layer in laser processing software, correspondingly setting laser parameters with high repetition frequency and low scanning speed for inducing a carbon precursor material to form a porous LIG (laser induced graphene) microelectrode in an exposed area on the surface of the carbon precursor, and forming an asymmetric structure with the MXenes microelectrode obtained in the step S3.
In the step, a three-dimensional porous LIG material is induced to the exposed area of the surface of the carbon precursor substrate by using high repetition frequency laser at a low scanning speed, and the porous LIG microelectrode structure is obtained by controlling laser beam motion direct writing through a computer software design pattern. In this example, the LIG microelectrode is an interdigital electrode, which is arranged opposite to the MXenes microelectrode in a staggered manner, and the spacing distance between the LIG microelectrode and the MXenes microelectrode is 10-1000 μm.
The laser parameters in this step S4 are set as follows: the wavelength is 190-10600 nm, the repetition frequency is 200 kHz-80 MHz, the power is 1-5W, the scanning speed is 1-200 mm/s, and the scanning frequency is 1-10 times. Specifically, in this example, the laser parameters are set as follows: the wavelength was 355nm, the repetition frequency was 200kHz, the power was 2.7W, the scanning speed was 20mm/s, and the number of scans was 1. The SEM image of the LIG prepared in this example is shown in fig. 3 (the left and right images are the structural morphology images under different multiples), from which it can be seen that the LIG obtained by laser treatment has a porous structure, which is beneficial for ion transport and enhances electrochemical performance.
S5, selecting the 3 layers to execute the laser integrated processing program, and realizing the integrated preparation of pre-patterning the PI/MXenes composite film obtained in the step S1, firstly forming MXenes electrodes 3, then forming porous MXenes microelectrodes 4 and finally forming LIG microelectrodes 5.
During laser processing, volume expansion is generated during the process that laser irradiation induces graphene on the carbon precursor, and due to the volume expansion, the LIG positive electrode and the MXenes negative electrode can be basically positioned on one plane. The structure has the advantages of no need of a diaphragm and reduction of the thickness of the whole device, and not only can effectively shorten the ion diffusion distance, but also can accelerate the rapid migration capability of ions.
After the laser integration processing of step S5, a schematic diagram of the structure of the formed planar asymmetric electrode is shown in fig. 4, in which the MXenes electrode is used as the negative electrode, and the LIG electrode is used as the positive electrode. In the execution of the laser integrated processing program, the used laser is one of a high repetition frequency femtosecond pulse laser, a high repetition frequency picosecond pulse laser and a high repetition frequency nanosecond pulse laser, wherein the wavelength range of the high repetition frequency femtosecond pulse laser is 190 nm-10.6 mu m, the repetition frequency range is 5 kHz-80 MHz, and the pulse width range is 10 fs-1000 fs; the wavelength range of the high repetition frequency picosecond pulse laser is between 190nm and 10.6 microns, the repetition frequency range is between 5kHz and 80MHz, and the pulse width range is between 10ps and 1000 ps; the wavelength range of the high repetition frequency nanosecond pulse laser is 190 nm-10.6 mu m, the repetition frequency range is 5 kHz-80 MHz, and the pulse width range is 10 ns-1000 ns.
And S6, contrapositioning the prepreg 6 with the periphery closed and the middle hollowed on the carbon precursor film, so as to enclose the LIG positive electrode and the MXenes negative electrode in the middle hollowed area of the prepreg.
In step S6, the prepreg may be made of a hot melt adhesive resin such as Polyurethane (PU), epoxy resin, or silicone resin. The thickness of the selected prepreg is 5-50 mu m larger than that of the MXenes layer, then the prepreg is cut for multiple times at a high scanning speed by using low-repetition-frequency laser until the prepreg is hollowed out, the size of the prepreg is matched with the microelectrode structure of the asymmetric MSCs, and the laser parameters can be set as follows: the wavelength is 190-1064 nm, the repetition frequency is 5-50 kHz, the power is 5-30W, the scanning speed is 200-5000 mm/s, and the scanning frequency is 5-20 times. Specifically, the laser parameters for processing the prepreg in this example are set as follows: the wavelength was 355nm, the repetition frequency was 30kHz, the power was 2.7W, the scanning speed was 500mm/s, and the number of scans was 10.
In this step S6, the prepreg may be fixed to the carbon precursor by hot pressing, the arrangement of the hot press being as follows: the pressure is 0.2-0.5 MPa, the temperature is 180-200 ℃, and the hot pressing time is 2-10 min. Specifically, in this example, the parameters of the press are: the pressure is 0.2MPa, the temperature is 185 ℃, and the hot pressing time is 3 min.
In practical application, step S5 may be repeated, that is, processing is performed on the carbon precursor for multiple times, so as to directly and rapidly obtain an LIG/MXenes asymmetric microelectrode array, and each pair of electrodes in the array is subjected to step S6, so that each pair of electrodes is provided with a prepreg, thereby constructing a grid-shaped prepreg cofferdam array on the carbon precursor.
S7, coating the electrolyte 7 on the middle hollow area of the prepreg to cover the two electrodes.
In step S7, the electrolyte is one of an aqueous electrolyte, an ionic liquid and a gel electrolyte, wherein the aqueous electrolyte includes Na2SO4Electrolyte, Li2SO4LiCl and KCl electrolytes, and the gel electrolyte comprises PVA/H3PO4、PVA/H2SO4And LiCl/PVA, etc., and the ionic liquid includes EMIMNTF2, EMIMBF4, BMIMBF4, BMIMBF6, PYR13TFSI, PYR14TFSI, TEATFB and other acetonitrile electrolyte. In the present example, the number of the first and second,using PVA/H3PO4An electrolyte.
The coating thickness of electrolyte makes the electrolyte and the sealed area all around of prepreg be located the coplanar, and electrolyte and two electrodes all restrict in the fretwork area of prepreg, can effectively restrict the flow of electrolyte, not only can prevent that electrolyte from revealing, also can make the asymmetric ultracapacitor system in plane have higher reliability.
And S8, packaging with a packaging film 8 to form the planar asymmetric miniature super capacitor.
In the step S8, a packaging film with a thickness of 10 to 30 μm is used for packaging (i.e. the product obtained in the previous step is packaged in the packaging film as a whole), so as to obtain the planar asymmetric micro-supercapacitor.
The packaging film mainly includes a PI film, a polyethylene terephthalate (PET) film, and the like. In this example, a 30 μm PI film was used for encapsulation.
After the steps are carried out, the packaged device is cooled to room temperature, and then the planar miniature super capacitor which is good in flexibility, high in integration level and capable of being cut and is expected to be applied in a large scale can be obtained.
The CV curve of the planar LIG/MXenes asymmetric MSCs prepared in the above example at 50mV/s sweep rate is shown in FIG. 5, and the specific capacitance at 50mV/s sweep rate is 5.3mF/cm2The voltage window is 1.2V. According to E ═ 0.5C × U2(E is energy density, C is capacitance, U is voltage window) shows that the energy density can be improved to 4 times of the original energy density. Therefore, the method of the embodiment of the application effectively improves the voltage window of the planar asymmetric MSCs.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several equivalent substitutions or obvious modifications can be made without departing from the spirit of the invention, and all the properties or uses are considered to be within the scope of the invention.
Claims (5)
1. A preparation method of a planar asymmetric miniature supercapacitor is characterized by comprising the following steps:
(1) forming a layer of a second electrode precursor on the first electrode precursor;
(2) presetting a first laser parameter, a second laser parameter and a third laser parameter, wherein the repetition frequency of the first laser parameter is lower than that of the second laser parameter, the scanning speed of the first laser parameter is higher than that of the second laser parameter, the repetition frequency of the third laser parameter is higher than that of the first laser parameter, and the scanning speed of the third laser parameter is higher than that of the second laser parameter; wherein the repetition frequency of the first laser parameter is 5-50 kHz, and the scanning speed is 1000-5000 mm/s; the repetition frequency of the second laser parameter is 200 kHz-80 MHz, and the scanning speed is 1-200 mm/s; the repetition frequency of the third laser parameter is 200 kHz-80 MHz, and the scanning speed is 1000-5000 mm/s;
(3) executing a laser integrated processing program, processing the second electrode precursor into a first preset pattern under the first laser parameter so as to form a second electrode on the first electrode precursor, wherein the surface of the first electrode precursor except the second electrode is exposed; then processing the surface of the second electrode into a porous structure under the third laser parameter to form a porous second electrode; processing the surface exposed area of the first electrode precursor into a second preset pattern matched with the first preset pattern under the second laser parameter so as to form a first electrode on the first electrode precursor, wherein the first electrode and the second electrode are positioned on the same plane due to volume expansion in the processing process, and the first electrode and the second electrode form an asymmetric structure; wherein the first electrode precursor is a carbon precursor and correspondingly the first electrode is laser induced graphene; the second electrode precursor is MXenes, correspondingly, the second electrode is an MXenes electrode;
(4) positioning a prepreg with the periphery closed and the middle hollowed out in an aligned mode on the first electrode precursor so as to enclose the first electrode and the second electrode in the middle hollowed-out area of the prepreg;
(5) coating an electrolyte on the middle hollow area of the prepreg to cover the first electrode and the second electrode;
(6) and packaging to form the planar asymmetric miniature super capacitor.
2. The method according to claim 1, wherein the first electrode precursor has a thickness of 50 to 500 μm and the second electrode precursor has a thickness of 1 to 100 μm.
3. The method of claim 1, wherein the first predetermined pattern of the first electrode is one of an interdigital shape, a circular shape, an arc shape, and a linear shape, and correspondingly, the second electrode is one of an interdigital shape, a circular shape, an arc shape, and a linear shape matched to the first electrode; the distance between the first electrode and the second electrode is 10-1000 mu m.
4. The method according to claim 1, wherein a thickness of the prepreg is 5 to 50 μm greater than a thickness of the first electrode; and (5) coating the electrolyte to the thickness so that the electrolyte and the peripheral closed area of the prepreg are positioned on the same plane.
5. A planar asymmetric micro supercapacitor, which is produced by the production method according to any one of claims 1 to 4.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106449134A (en) * | 2016-11-03 | 2017-02-22 | 北京大学 | A freestyle miniature supercapacitor based on laser graphics and a manufacturing method thereof |
| WO2017223217A1 (en) * | 2016-06-21 | 2017-12-28 | William Marsh Rice University | Laser-induced graphene scrolls (ligs) materials |
| CN109686593A (en) * | 2019-01-17 | 2019-04-26 | 西安交通大学 | One kind is based on secondary laser irradiation preparation MnO2The method of/graphene combination electrode |
| CN110634686A (en) * | 2019-08-14 | 2019-12-31 | 温州大学激光与光电智能制造研究院 | Method for rapidly preparing planar super capacitor |
| CN111968860A (en) * | 2020-07-16 | 2020-11-20 | 北京理工大学 | Integrated self-charging miniature supercapacitor device and preparation thereof |
| CN112466678A (en) * | 2020-10-27 | 2021-03-09 | 西安电子科技大学 | Laser induced MnO2Graphene micro supercapacitor and manufacturing method thereof |
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| WO2016133571A2 (en) * | 2014-11-26 | 2016-08-25 | William Marsh Rice University | Laser induced graphene hybrid materials for electronic devices |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017223217A1 (en) * | 2016-06-21 | 2017-12-28 | William Marsh Rice University | Laser-induced graphene scrolls (ligs) materials |
| CN106449134A (en) * | 2016-11-03 | 2017-02-22 | 北京大学 | A freestyle miniature supercapacitor based on laser graphics and a manufacturing method thereof |
| CN109686593A (en) * | 2019-01-17 | 2019-04-26 | 西安交通大学 | One kind is based on secondary laser irradiation preparation MnO2The method of/graphene combination electrode |
| CN110634686A (en) * | 2019-08-14 | 2019-12-31 | 温州大学激光与光电智能制造研究院 | Method for rapidly preparing planar super capacitor |
| CN111968860A (en) * | 2020-07-16 | 2020-11-20 | 北京理工大学 | Integrated self-charging miniature supercapacitor device and preparation thereof |
| CN112466678A (en) * | 2020-10-27 | 2021-03-09 | 西安电子科技大学 | Laser induced MnO2Graphene micro supercapacitor and manufacturing method thereof |
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