CN112687474A - Miniature super capacitor - Google Patents
Miniature super capacitor Download PDFInfo
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- CN112687474A CN112687474A CN201910987662.5A CN201910987662A CN112687474A CN 112687474 A CN112687474 A CN 112687474A CN 201910987662 A CN201910987662 A CN 201910987662A CN 112687474 A CN112687474 A CN 112687474A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides a miniature super capacitor, which comprises a substrate, a current collector layer, an electrode layer and an electrolyte layer, wherein the current collector layer is arranged on the substrate; wherein the current collector layer is disposed on the substrate, the electrode layer is disposed on the current collector layer, and the electrolyte layer is disposed on the electrode layer; the electrode layer is internally provided with a pattern area, electrolyte is filled in the pattern area, and the pattern area is in a fractal geometric pattern type, a planar interdigital type or a concentric circle type. According to the micro super capacitor provided by the embodiment of the invention, the energy density of the micro super capacitor is improved.
Description
Technical Field
The invention relates to a super capacitor, in particular to a micro super capacitor with higher energy density.
Background
Energy storage devices are indispensable and important components in the development of modern electronic technology, and the development of electrochemical energy storage devices has huge potential and broad market prospect. The development of small electronic devices (such as micro-electromechanical systems, radio frequency identification electronic tags and micro sensors), especially wearable electronic devices, puts new demands on electrochemical energy storage devices, and it is the development direction of micro energy storage technology to improve the capacity, power and other properties of the devices while realizing miniaturization and flexibility.
At present, micro primary and secondary batteries are applied to commercial devices, but are still limited by problems such as low power density and high manufacturing cost. The super capacitor stores energy through charge adsorption or oxidation reduction reaction on the surface of the electrode, and has the advantages of high power density, good cycle stability and the like. The micro super capacitor is used as a high-power-density energy storage device, can be used independently or jointly with a micro battery, and realizes high-energy and high-power electric energy output.
In recent years, researchers have fabricated miniature supercapacitors by photolithography, electrochemical deposition, plasma reduction, chemical vapor deposition, and the like. However, the technologies have the problems of complex preparation process, expensive production equipment, long process time consumption and the like, so that the product cost is high and the technologies are difficult to be used for batch production. The printing technology has the advantages of low cost, high efficiency, simple process, flexible material selection and the like, and has important advantages in the direction of manufacturing the micro super capacitor on a large scale. In the existing research of printing the miniature super capacitor, the energy density of the device is low due to the limitation of materials, structures, processes and the like, and the requirement of practical application cannot be met temporarily. In addition, the existing research mostly focuses on the research of new materials, and lacks the attention on the electrode structure and the device design. Therefore, a printed micro supercapacitor with high energy density is needed to solve the problem of low device performance, and to promote the industrial and large-scale application of the micro supercapacitor.
Disclosure of Invention
One of the primary objects of the present invention is to provide a micro supercapacitor comprising a substrate, a current collector layer, an electrode layer and an electrolyte layer; wherein the current collector layer is disposed on the substrate, the electrode layer is disposed on the current collector layer, and the electrolyte layer is disposed on the electrode layer; the electrode layer is internally provided with a pattern area, electrolyte is filled in the pattern area, and the pattern area is in a fractal geometric pattern type, a planar interdigital type or a concentric circle type.
According to the micro super capacitor provided by the embodiment of the invention, the energy density of the micro super capacitor is improved.
Drawings
FIG. 1 is a schematic structural diagram of a micro supercapacitor according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of an electrode layer according to an embodiment of the present invention;
FIG. 2a is a schematic view of a pattern region according to an embodiment of the present invention;
FIG. 3 is a schematic view of an electrode layer according to another embodiment of the present invention;
FIG. 3a is a schematic diagram of a first repeating unit of a pattern region according to an embodiment of the present invention;
FIG. 4 is a schematic view of an electrode layer according to another embodiment of the present invention;
FIG. 5 is a schematic view of an electrode layer according to another embodiment of the present invention;
FIG. 6 is a schematic structural diagram of a micro supercapacitor according to another embodiment of the present invention;
FIG. 7a is a cyclic voltammogram of a printed micro supercapacitor made according to example 1 of the present invention at different scan speeds;
FIG. 7b is a constant current charge and discharge curve for printed micro-supercapacitors made according to example 1 of the present invention at different current densities;
fig. 7c is an energy density curve of the printed micro-supercapacitor made in examples 1, 2 and 3 of the present invention at different scanning speeds.
Detailed Description
Exemplary embodiments that embody features and advantages of the invention are described in detail below in the specification. It is to be understood that the invention is capable of other embodiments and that various changes in form and details may be made therein without departing from the scope of the invention and the description and drawings are to be regarded as illustrative in nature and not as restrictive. In the present invention, the terms "first", "second", "third", "fourth", and the like are used for distinguishing between them in terms of nomenclature, and are not intended to limit components, structures, and the like.
As shown in fig. 1, an embodiment of the present invention provides a micro supercapacitor, including a substrate 10, a current collector layer 20 disposed on the substrate 10, an electrode layer 30 disposed on the current collector layer 20, and an electrolyte layer 40 covering the electrode layer 30; a pattern region is provided in the electrode layer 30, and an electrolyte is filled in the pattern region.
In one embodiment, the pattern region includes a fractal geometric pattern.
In the present invention, in the electrode layer 30 shown in fig. 2, 3, 4, and 5, the black portion represents an electrode, and the white portion represents a pattern region.
In one embodiment, referring to fig. 2 and 2a, the pattern region shown in fig. 2 includes a right-angled U-shape connected to the region outside the electrode layer 30 through the bar- shaped portions 30a and 30 b.
In one embodiment, the right-angled U-shape includes a first bar 31, a second bar 32 and a third bar 33, the first bar 31 and the third bar 33 are connected to two ends of the second bar 32 in parallel and are perpendicular to the second bar 32, the first bar 31 and the third bar 33 are located on the same side of the second bar 32, an opening is formed between the first bar 31 and the third bar 33, and the first bar 31 and the second bar 32 are connected to two ends of the third bar 33 through one end respectively.
In one embodiment, the first strip 31 and the third strip 33 are the same, i.e., the same length and width.
In one embodiment, the right angle U-shape has two ends formed at the ends of the first strip 31 and the third strip 33, respectively.
In one embodiment, the first bar 31 of the right-angled U-shape is connected to the region outside the electrode layer 30 through the bar 30a, and the bar 30a is disposed in the same direction as the first bar 31, i.e., the bar 30a and the first bar 31 have the same axis.
In one embodiment, the width of the bar 30a is the same as the width of the first bar 31.
In one embodiment, the third bars 33 of the right-angled U-shape are connected to the region outside the electrode layer 30 by bars 30b, the bars 30b being perpendicular to the third bars 33.
In one embodiment, the structure shown in fig. 2a after the right-angled U-shape with the opening facing upward is rotated 90 ° counterclockwise is defined as a second right-angled U-shape 302, and in conjunction with fig. 3a, the opening of the second right-angled U-shape 302 is to the left; the configuration shown in fig. 2a after rotating the upward-opening right-angled U-shape clockwise by 90 ° is defined as a third right-angled U-shape 303, the opening of which third right-angled U-shape 303 is to the right in connection with fig. 3 a.
In one embodiment, referring to fig. 3 and 3a, the pattern region shown in fig. 3 includes a first basic unit, a second basic unit, a third basic unit and a fourth basic unit which are connected, wherein the first basic unit is a second right-angle U-shape 302, the second basic unit is a right-angle U-shape 301, the third basic unit is a right-angle U-shape 301, and the fourth basic unit is a third right-angle U-shape 303.
In one embodiment, the first basic unit, the second basic unit, the third basic unit and the fourth basic unit are connected through a bar.
In one embodiment, one end of the second rectangular U-shape 302 of the first base unit is connected to one end of the rectangular U-shape 301 as the second base unit by a strip shape, the other end of the rectangular U-shape 301 of the second base unit is connected to one end of the rectangular U-shape 301 of the third base unit by a strip shape, and the other end of the rectangular U-shape 301 of the third base unit is connected to one end of the third rectangular U-shape 303 of the fourth base unit by a strip shape.
In one embodiment, the three bars connecting the first basic unit, the second basic unit, the third basic unit and the fourth basic unit are the same, i.e., the length and the width are the same.
In one embodiment, the other end of the second rectangular U-shape 302 of the first basic unit is connected to the region outside the electrode layer 30 by a strip shape, and the strip shape is disposed parallel to the opening direction of the second rectangular U-shape 302; the other end portion of the third right-angle U-shape 303 of the fourth basic unit is connected to the region other than the electrode layer 30 by a strip shape, and the strip shape is arranged perpendicular to the opening direction of the third right-angle U-shape 303.
In one embodiment, the second rectangular U-shape 302 of the first base unit is positioned opposite the opening of the rectangular U-shape 301 of the second base unit, and the third rectangular U-shape 303 of the fourth base unit is positioned opposite the opening of the rectangular U-shape 301 of the third base unit.
In one embodiment, the second rectangular U-shape 302 of the first base unit is disposed opposite the third rectangular U-shape 303 of the fourth base unit.
In one embodiment, the pattern shown in fig. 3a is defined as a first repeating unit, a structure of the first repeating unit rotated 90 ° counterclockwise is defined as a second repeating unit, a structure of the first repeating unit rotated 90 ° clockwise is defined as a third repeating unit, and a structure of the first repeating unit rotated 180 ° is defined as a fourth repeating unit.
In one embodiment, the pattern region includes at least one of the first repeating unit, the second repeating unit, the third repeating unit and the fourth repeating unit, preferably a multiple of four, such as four, eight, twelve, sixteen, and the like.
In one embodiment, the pattern region as shown in FIG. 4 includes a second repeating unit, a first repeating unit, and a third repeating unit, which are sequentially connected.
In one embodiment, the pattern region as shown in fig. 5 includes a first repeating unit, a second repeating unit, a fourth repeating unit, a second repeating unit, a first repeating unit, a third repeating unit, a fourth repeating unit, a third repeating unit, and a first repeating unit, which are sequentially connected.
In one embodiment, the stripes connecting the repeating units are the same, i.e., the length and width are the same.
In the present invention, "first stripe", "second stripe", "third stripe", "stripe", and the like all refer to a long stripe-shaped region.
In one embodiment, the electrode layer 30 may be planar interdigitated, concentric circular, or the like.
In one embodiment, the super capacitor may be a double-layer type, a pseudo-capacitor type or a hybrid type super capacitor; the double-layer electrode is mainly based on physical adsorption and desorption of ions, and the pseudo-capacitive electrode is mainly based on surface rapid Faraday redox reaction; one electrode of the hybrid super capacitor is a double-layer electrode, and the other electrode of the hybrid super capacitor is a pseudocapacitive electrode.
In one embodiment, as shown in fig. 1, the current collector layer 20, the electrode layer 30, the electrolyte layer 40, etc. may be formed on one surface of the substrate 10; as shown in fig. 6, it may be formed on both surfaces of the substrate 10.
In one embodiment, in the device shown in fig. 6, in which the electrode layers 30 are disposed on both sides of the substrate 10, the substrate 10 includes a blank region, only the current collector layer 20 is disposed on the blank region, and the electrode layer 30 and the electrolyte layer 40 are not present, and at least one through hole 11 penetrating through the substrate 10 and the two current collector layers 20 can be opened on the blank region, and the through hole 11 can be electrically connected, so that the upper and lower current collector layers 20 form a series or parallel circuit, and voltage and current can be adjusted as needed.
In one embodiment, the number of the through holes 11 may be one or more, such as two, three, four, etc.
In one embodiment, the conductive connection can be performed by disposing a conductive wire or silver paste in the through hole 11.
In one embodiment, the electrodes may be formed on the substrate by printing.
In one embodiment, the printing method of the electrode may be screen printing, gravure printing, inkjet printing, flexo printing, or a combination of these printing methods.
The material of the substrate in the present invention is not particularly limited, and may be any non-conductive material, such as polyethylene terephthalate, paper, textile cloth, and the like.
In one embodiment, the material of the current collector may be one or more of carbon, silver, gold, platinum, aluminum, copper, and nickel; for example, the current collector may be made of carbon nanoparticles, metal nanowires, or a combination thereof.
In one embodiment, the electrolyte may be a polyvinyl alcohol-aqueous acidic alkaline neutral electrolyte, a polyoxyethylene organic electrolyte, or an ionic liquid electrolyte.
In one embodiment, the electrolyte includes, but is not limited to, a polyvinyl alcohol-sulfuric acid electrolyte, a polyvinyl alcohol-phosphoric acid electrolyte, a polyvinyl alcohol-potassium hydroxide electrolyte, a polyvinyl alcohol sodium sulfate electrolyte, a 1-butyl-3-methylimidazolium hexafosfate ionic liquid electrolyte.
In one embodiment, the electrode material may be selected from one or more of activated carbon, graphene, carbon nanomaterial, metal oxide, and conductive polymer.
In one embodiment, the packaging material of the supercapacitor can be one or more of polyethylene terephthalate, ethylene-vinyl acetate copolymer, polydimethylsiloxane, polytetrafluoroethylene and polymethyl methacrylate.
According to the micro super capacitor provided by the embodiment of the invention, the energy density of the micro super capacitor is improved through the optimization of the electrode structure.
According to the micro super capacitor provided by the embodiment of the invention, the structure of the device is optimized through the design of the through holes, so that the quality of the active substance in unit area is improved, the capacity in unit area is improved, and the energy density of the micro super capacitor is further improved.
The micro super capacitor provided by the embodiment of the invention adopts a printing technology in the preparation process, and has the characteristics of low cost, high efficiency and flexible design, so that the micro super capacitor with higher energy density can be rapidly prepared in a large batch, and can be widely applied to the fields of micro electro mechanical systems, wearable equipment and the like.
The following describes a micro supercapacitor according to an embodiment of the present invention with reference to the accompanying drawings and specific examples. Wherein, unless otherwise stated, all are conventional methods; the materials and reagents used, unless otherwise specified, are commercially available.
Example 1
The method for preparing the planar interdigital type double-sided flexible micro supercapacitor comprises the following steps:
(1) uniformly mixing activated carbon, graphene, a conductive additive and a high-molecular binder in an organic solvent to prepare electrode slurry;
(2) screen-printing silver paste on the front and back surfaces of a polyethylene terephthalate substrate through a planar interdigital screen printing plate, and then curing and drying in an oven to serve as a current collector; two through holes are formed in the current collector and are connected through conductive silver adhesive to form a parallel circuit;
(3) screen printing the electrode slurry prepared in the step (1) on the current collector layer prepared in the step (2) through a planar interdigital screen, and then drying in a vacuum oven to be used as an electrode layer;
(4) printing a polyvinyl alcohol-phosphoric acid electrolyte on the electrode layer prepared in the step (3), covering the interdigital electrodes, and drying in an oven;
(5) the polyethylene terephthalate with the adhesive layer is used as a packaging material, the device packaging is completed through heating and curing, one surface of the structure of the flexible micro super capacitor is as shown in figure 1, the structure of the reverse surface is the same, the parallel connection is formed through the through holes, and the planar interdigital double-sided flexible micro super capacitor is prepared, the thickness of the planar interdigital double-sided flexible micro super capacitor is less than 200 microns, and the planar interdigital double-sided flexible micro super capacitor has good flexibility.
Fig. 7a is a performance graph of the double-sided via-parallel supercapacitor made in example 1 tested by cyclic voltammetry at different scanning speeds, and the result shows that a better rectangle is still maintained at a higher scanning speed, which illustrates the advantage of maintaining high power density of the supercapacitor. Fig. 7b is a graph of the capacity of the supercapacitor of example 1 tested using constant current charge and discharge, illustrating its high energy density.
Example 2
The method for preparing the fractal geometric pattern type double-sided miniature supercapacitor comprises the following steps:
(1) uniformly mixing activated carbon, graphene, a conductive additive and a high-molecular binder in an organic solvent to prepare electrode slurry;
(2) the silver paste is printed on the front and the back of the polyethylene terephthalate substrate through a fractal geometric pattern type screen printing plate by silk screen, and then is cured and dried in an oven to be used as a current collector; two through holes are formed in the current collector and are connected through conductive silver adhesive to form a parallel circuit;
(3) screen printing the electrode slurry prepared in the step (1) on the current collector layer prepared in the step (2) through a fractal geometric pattern type screen printing plate, and then drying in a vacuum oven to be used as an electrode layer;
(4) printing a polyvinyl alcohol-phosphoric acid electrolyte on the electrode layer prepared in the step (3), covering the interdigital electrodes, and drying in an oven;
(5) the structure of the electrode layer of the flexible micro super capacitor is shown in figure 4, the thickness of the electrode layer is less than 200 microns, and the electrode layer has good flexibility.
Example 3
The flexible micro-supercapacitor is prepared according to the same raw materials and steps as those of example 1, and the difference from example 1 is mainly that the electrode structure of the prepared micro-supercapacitor is formed on only one side (interdigital-single side) of the substrate.
Fig. 7c is a graph of energy density at different scan speeds for the supercapacitors produced in example 1 (interdigital-double sided), example 2 (fractal geometry-double sided) and example 3 (interdigital-single sided). Fig. 7c shows that compared to the single-sided printing of example 3, the energy density of the double-sided parallel-connected supercapacitor of example 1 is significantly improved at different scanning speeds.
In fig. 7c, the energy density of example 2 (fractal geometry-two-sided) was calculated using cyclic voltammetry testing for performance at different scan speeds. Comparing the curve of example 2 in fig. 7c with the curve of example 1, it can be seen that the capacity per unit area can be further improved using the fractal geometric pattern type electrode, thereby improving the energy density.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.
Claims (10)
1. A miniature ultracapacitor, comprising:
a substrate;
a current collector layer disposed on the substrate;
an electrode layer disposed on the current collector layer; and
an electrolyte layer disposed on the electrode layer;
the electrode layer is internally provided with a pattern area, electrolyte is filled in the pattern area, and the pattern area is in a fractal geometric pattern type, a planar interdigital type or a concentric circle type.
2. The micro-supercapacitor of claim 1, wherein the pattern region comprises a right-angled U-shape.
3. The micro-supercapacitor of claim 2, wherein the right-angle U-shape is comprised of a first bar, a second bar, and a third bar, the first bar and the third bar are connected in parallel at both ends of the second bar and are perpendicular to the second bar, the first bar and the third bar are located at the same side of the second bar, and an opening is formed between the first bar and the third bar.
4. The micro-supercapacitor of claim 2, wherein the structure after the right-angle U-shape is rotated 90 ° counterclockwise is defined as a second right-angle U-shape, and the structure after the right-angle U-shape is rotated 90 ° clockwise is defined as a third right-angle U-shape; the pattern region includes a first repeating unit including a first basic unit, a second basic unit, a third basic unit and a fourth basic unit connected, the first basic unit is the second right-angle U-shape, the second basic unit is the right-angle U-shape, the third basic unit is the right-angle U-shape, and the fourth basic unit is the third right-angle U-shape.
5. The micro-supercapacitor of claim 4, wherein the first, second, third, and fourth base cells are connected by a bar shape, respectively.
6. The micro-supercapacitor of claim 4, wherein a structure after the first repeating unit is rotated 90 ° counterclockwise is defined as a second repeating unit, a structure after the first repeating unit is rotated 90 ° clockwise is defined as a third repeating unit, and a structure after the first repeating unit is rotated 180 ° is defined as a fourth repeating unit; the pattern region includes at least one of a first repeating unit, a second repeating unit, a third repeating unit, and a fourth repeating unit.
7. The micro-supercapacitor of claim 6, wherein the pattern region comprises at least one first repeating unit, at least one second repeating unit, at least one third repeating unit, and at least one fourth repeating unit.
8. The micro-supercapacitor of claim 6, wherein the pattern region comprises a second repeating unit, a first repeating unit, and a third repeating unit, which are connected in sequence.
9. The micro-supercapacitor of claim 6, wherein the pattern region comprises a first repeating unit, a second repeating unit, a fourth repeating unit, a second repeating unit, a first repeating unit, a third repeating unit, a fourth repeating unit, a third repeating unit, a first repeating unit, which are connected in sequence.
10. The micro-supercapacitor of any one of claims 1 to 9, wherein the substrate comprises blank areas and electrode areas in which the current collector layer, the electrode layer and the electrolyte layer are respectively disposed on opposite surfaces of the substrate; in the blank area, the two opposite surfaces of the substrate are respectively provided with the current collector layers, and the blank area is provided with at least one through hole which penetrates through the substrate and the current collector layers.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113793757A (en) * | 2021-09-26 | 2021-12-14 | 北京服装学院 | Flexible planar capacitor and preparation method and application thereof |
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| EP2413347A1 (en) * | 2010-07-28 | 2012-02-01 | Nxp B.V. | Fringe capacitor based on fractal patterns |
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| CN113793757A (en) * | 2021-09-26 | 2021-12-14 | 北京服装学院 | Flexible planar capacitor and preparation method and application thereof |
| CN113793757B (en) * | 2021-09-26 | 2024-03-22 | 北京服装学院 | Flexible planar capacitor and preparation method and application thereof |
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