CN111211002A - Method for preparing integrated planar super capacitor on polymer substrate - Google Patents
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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
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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
- H01G11/10—Multiple hybrid or EDL capacitors, e.g. arrays or modules
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
- H01G11/74—Terminals, e.g. extensions of current collectors
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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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- 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
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- 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 discloses a method for preparing an integrated planar supercapacitor on a polymer substrate, in particular to a method for writing patterns by laser, which prepares components such as an electrode material, a current collector, a conductive connector and the like on the polymer substrate in one step by high-temperature carbonization of the laser to form the integrated supercapacitor. The obtained modularized super capacitor has high integration degree, can be used as a power source of flexible and wearable electronic devices, non-contact chips and the like, and has wide market application prospect.
Description
Technical Field
The invention belongs to the field of energy storage, and particularly relates to an integrated planar supercapacitor and a preparation method thereof.
Background
Conventional supercapacitors typically employ a stacked structure of current collector/positive electrode/separator/negative electrode/current collector stacked in sequence. The preparation process of the supercapacitor is complex, and the concentrated existence of a plurality of interfaces makes the supercapacitor easy to generate interface separation in the bending process, so that the supercapacitor is not beneficial to being used as a power source of a wearable and flexible electronic device in the future, and the practical application of the supercapacitor is limited. In response to this problem, in recent years, a novel planar supercapacitor with electrodes, electrolyte, current collector and separator on the same substrate has attracted much attention. The current collector, the electrode, the electrolyte and the diaphragm of the super capacitor are integrated on the same substrate, so that the problem of multi-interface separation of the super capacitor in the bending process is greatly relieved, and the combination of all parts of the super capacitor and the preparation of the bendable super capacitor are facilitated.
At present, a plurality of preparation methods of the planar super capacitor are available, such as printing, suction filtration, photoetching and the like, but the single planar super capacitor prepared by the method has the problems of limited voltage and current. In order to meet the requirements of different application scenarios, people usually need to integrate a plurality of super capacitors in series or in parallel by means of wire connection to adjust output voltage or current in actual production life, the preparation process is complex, the cost is high, the integrity of the integrated super capacitor is reduced, and the integration with other electronic elements is not facilitated. Therefore, a method for simply and efficiently realizing the preparation of the electrode material of the integrated planar super capacitor, the construction of a single capacitor and the series-parallel connection among a plurality of capacitors in one step is designed and developed, so that the efficiency is improved, the cost is reduced, and the large-scale industrial application of the super capacitor is promoted.
Based on the structure, the invention discloses an integrated planar super capacitor and a preparation method thereof. The preparation of the electrode material of the super capacitor, the construction of a single super capacitor and the series-parallel connection integration of a plurality of super capacitors are realized in one step by adopting a laser writing method to carry out high-temperature carbonization on a polymer substrate and directly using the carbonized product as the current collector, the electrode material and the conductive connector of the integrated super capacitor. The obtained device has high integration and excellent flexibility, can realize large-scale production, can be effectively integrated with a flexible wearable electronic product, and has wide market application prospect.
Disclosure of Invention
The invention aims to realize the preparation of a super capacitor electrode material, the construction of a single super capacitor and the series-parallel connection integration of a plurality of super capacitors by adopting a one-step method, and obtain a highly integrated planar flexible super capacitor so as to meet the requirement of wearable electronic equipment on a power source.
In order to achieve the above object, the present invention provides a method for preparing an integrated planar supercapacitor on a polymer substrate, comprising the steps of:
(1) the method comprises the following steps of (1) writing a polymer substrate by using laser according to a pre-designed pattern, obtaining a carbonized product by the high-temperature carbonization of the polymer by using the laser, and realizing the patterned preparation of an electrode, a current collector and a connector in one step;
(2) coating electrolyte on the electrode material part, and reserving a space on the connector part to prepare the integrated planar super capacitor;
(3) the integrated planar super capacitor structure prepared on the polymer substrate is in series connection or parallel connection or combination of series connection and parallel connection, and the output voltage and current of the integrated planar super capacitor can be adjusted according to different design structures.
The laser in the step (1) is one or more of ultraviolet laser, visible laser and infrared laser.
The wavelength range of the laser is 100-300000 nm, and the preferable range is 300-100000 nm;
the power range of the laser is 0.01-100W, and the preferred range is 0.1-10W;
the writing speed of the laser is 0.1-100 mm/s, and the preferable range is 1-20 mm/s;
the writing precision of the laser is 1-10000 μm, and the preferable range is 10-500 μm.
The laser in the step (1) is one or more of ultraviolet laser, visible laser and infrared laser, the wavelength range of the laser is 100-300000 nm, the power range of the laser is 0.01-100W, the writing speed of the laser is 0.1-100 mm/s, and the writing precision of the laser is 1-10000 microns.
The carbonized product obtained by the laser high-temperature carbonization is one or the combination of two of graphene and amorphous carbon, wherein the transverse size of the graphene is 100 nm-100 mu m, the number of layers is 1-10, and the specific surface area of the graphene and the amorphous carbon is 20-3000 m2/g。
The output voltage of the integrated super capacitor is adjustable between 1V and 100V, and the current is adjustable between 1 muA and 100 mA.
The pre-designed patterns in the step (1) comprise electrode patterns of a single super capacitor and patterns of conductive connectors among the super capacitors, wherein the electrode patterns of the single super capacitor are in one or more of a line segment shape, a strip shape, an interdigital shape, a concentric circle shape and a folding shape, and the patterns of the conductive connectors are in one or more of a line segment shape, a zigzag shape and a curve shape.
The shape and the plane size of the pattern obtained by writing are the same as those of the pre-designed pattern, and each electrode or connector respectively has a certain area and thickness, wherein the thickness is between 100nm and 200 mu m, and the preferred range is between 1 mu m and 100 mu m; the area of each electrode is 10 μm2～20cm2Preferably in the range of 1mm2～1cm2(ii) a The area of one section of the conductive connector is 10 mu m2～10cm2Preferably in the range of 1mm2～1cm2。
In the step (1), the polymer substrate is one or more of polyimide, polyetherimide, polyethylene terephthalate, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, polytetrafluoroethylene and polyvinylidene fluoride. Preferred substrates are polyimides, polyetherimides.
The electrolyte in the step (2) is one or more than two of sulfuric acid solution, phosphoric acid solution, potassium hydroxide solution, sodium sulfate solution, lithium chloride solution, sulfuric acid/polyvinyl alcohol, phosphoric acid/polyvinyl alcohol, potassium hydroxide/polyvinyl alcohol, lithium chloride/polyvinyl alcohol, sodium sulfate/polyvinyl alcohol, 1-ethyl-3-methylimidazolium tetrafluoroborate/polyvinylidene fluoride, lithium bistrifluoromethanesulfonylimide/polyvinylidene fluoride and the like. Preferred electrolytes are sulfuric acid/polyvinyl alcohol, phosphoric acid/polyvinyl alcohol, potassium hydroxide/polyvinyl alcohol, lithium chloride/polyvinyl alcohol, sodium sulfate/polyvinyl alcohol, 1-ethyl-3-methylimidazolium tetrafluoroborate/polyvinylidene fluoride.
An integrated planar supercapacitor is obtained by connecting a plurality of individual planar supercapacitors in series, in parallel or in combination of series and parallel, wherein a connector is arranged between the individual planar supercapacitors; the single planar supercapacitor comprises discontinuously patterned positive and negative electrodes; when the n super capacitors are connected in series, the 1 st positive electrode and the 2 nd negative electrode, the 2 nd positive electrode and the 3 rd negative electrode, …, the n-1 st positive electrode and the nth negative electrode are connected through the conductive connecting body respectively; when the n super capacitors are connected in parallel, the positive electrodes of the 1 st to the nth super capacitors are connected through the conductive connector, and the negative electrodes are also connected through the conductive connector. Defining an integrated super capacitor obtained by connecting n super capacitors in series and then connecting m groups of n super capacitors in series in parallel as nS multiplied by mP; defining an integrated super capacitor obtained by connecting n super capacitors in parallel and then connecting m groups of n super capacitors in parallel in series as nP multiplied by mS; for a plurality of supercapacitors A which are not identical1,A2,…,AnDevices integrated in series, using S (A)1～A2～…～An) Represents; for a plurality of supercapacitors A which are not identical1,A2,…,AnParallel integrated devices, using P (A)1～A2～…～An) Is shown in the specification, wherein Ai(i ═ 1,2, …, n) can be a single supercapacitor or an integrated supercapacitor, such as S (1 sx 2P to 2 sx 2P), P (3 sx 2P to 1 sx 1P);
wherein n refers to the number of the super capacitors in series connection; m refers to the number of supercapacitors in parallel: s means serial connection; p refers to parallel connection: an refers to a single or integrated supercapacitor.
The invention has the advantages that:
1. the invention adopts the laser inscription method, and the integrated planar super capacitor is manufactured on the polymer insulating substrate by one step, and the preparation method is simple, has low cost and is suitable for large-scale production.
2. Compared with other methods for preparing electrode materials step by step, constructing a single super capacitor and integrating a plurality of super capacitors, the laser writing method provided by the invention realizes the three steps in one step, simplifies the process, improves the efficiency and obviously improves the integrity of the integrated device electrode and the connector.
3. The integrated planar super capacitor manufactured by the invention has high integration, customizable and adjustable capacity, voltage and good flexibility, and can be further developed into a power source of a flexible wearable electronic product.
Drawings
The invention is described in further detail below with reference to the following figures and embodiments:
FIG. 1.3S device schematic of a concentric circular supercapacitor;
FIG. 2. cyclic voltammograms and capacity retention rates of a single interdigitated supercapacitor under different bending conditions;
FIG. 3.10 is a schematic diagram of a device of a S × 1P linear supercapacitor;
FIG. 4.4S is a cyclic voltammetry test chart of a linear supercapacitor.
Detailed Description
The method of the present invention will be described in detail with reference to specific examples, which are carried out under the premise of the technical scheme of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
The polyimide film substrate is etched by using laser with the wavelength of 450nm and the power of 2.0W and the speed of 4mm/s, the etching pattern is a connector between three serially integrated concentric circular supercapacitors and devices, wherein the radius of an inner circle is 0.6cm, the radius of an outer circle is 1.0cm, the interval between the inner circle and the outer circle is 0.2cm, and the width of the connector is 0.2 cm. After the writing is finished, the electrode is coated with phosphoric acid/polyvinyl alcohol gel electrolyte, and after the electrolyte is solidified, 3 devices connected in series with the concentric circular super capacitor are obtained, as shown in fig. 1.
Electrochemical tests show that the 3S concentric circle super capacitor has an output voltage of 2.4V and shows good series behavior.
Example 2
The polyimide film substrate was scribed at a power of 2.0W, 4mm/s using a laser wavelength of 450nm in a pattern of individual interdigitated supercapacitors, wherein the individual fingers were 1.0cm x 0.1cm in size, the spacing between adjacent fingers was 0.1cm, and there were four fingers for each of the positive and negative electrodes. And coating phosphoric acid/polyvinyl alcohol gel electrolyte on the electrode after the writing is finished, and obtaining the single interdigital supercapacitor after the electrolyte is solidified.
The performance of the interdigital supercapacitor is tested under different bending states, and the result is shown in fig. 2, it can be seen that cyclic voltammetry test curves of the supercapacitor under different bending states almost completely coincide, and the capacity retention rate is close to 100%, which indicates that the laser-inscribed supercapacitor has good flexibility.
Example 3
The polyetherimide film substrate was scribed at a power of 1.5W at a rate of 2mm/s using a laser with a wavelength of 10.6 μm in a pattern of ten serially integrated linear supercapacitors and connectors between the devices, wherein the size of a single linear electrode was 1.0cm x 0.1cm, the spacing of two linear electrodes in the same supercapacitor was 0.1cm, and the connector size was 0.5cm x 0.1 cm. And (3) coating phosphoric acid/polyvinyl alcohol gel electrolyte on the electrode after the writing is finished, and curing the electrolyte to obtain ten serially integrated linear supercapacitors as shown in figure 3.
Electrochemical tests show that the 10S linear supercapacitor has an output voltage of 8.0V, shows good series behavior and has the potential of serving as a power source of a high-voltage electronic device.
Example 4
The polyimide film substrate is etched by using laser with the wavelength of 450nm and at the power of 1.0W and the speed of 1mm/S, the etching pattern is that four linear super capacitors are connected in series to form a group, four groups of integrated super capacitor modules are connected in parallel (namely 4S multiplied by 4P integrated super capacitors), wherein the size of a single linear electrode is 1.0cm x 0.1cm, the interval between two linear electrodes in the same super capacitor is 0.1cm, the size of a connector of a single device connected in series is 0.5cm x 0.1cm, and the size of a connector of each device connected in parallel is 1.0cm x 0.2 cm. And after the writing is finished, coating phosphoric acid/polyvinyl alcohol gel electrolyte on the electrode, and curing the electrolyte to obtain the 4S multiplied by 4P integrated linear supercapacitor.
The cyclic voltammetry test is carried out on the obtained 4S multiplied by 4P integrated super capacitor, as shown in fig. 4, the result shows that the voltage of 3.2V can be stably output, and the capacitance is approximately linearly increased along with the increase of the number of parallel groups, which shows that the integrated super capacitor inscribed by the laser has good series-parallel performance.
Example 5
The polyetherimide film substrate was scribed at a power of 1.5W at a rate of 2mm/s using a laser with a wavelength of 10.6 μm in a pattern of 3 serially integrated linear supercapacitors and connectors between the devices, wherein the size of a single linear electrode was 1.0cm x 0.1cm, the spacing of two linear electrodes in the same supercapacitor was 0.1cm, and the connector size was 0.5cm x 0.1 cm. And after the writing is finished, coating 1-ethyl-3-methylimidazolium tetrafluoroborate/polyvinylidene fluoride gel electrolyte at the electrode, and curing the electrolyte to obtain 3 serially-integrated linear supercapacitors.
Electrochemical tests show that the 3S linear supercapacitor has an output voltage of 9V, and the laser writing integrated supercapacitor has good adaptability to different electrolytes.
Claims (9)
1. A method of making an integrated planar supercapacitor on a polymer substrate, comprising: the method specifically comprises the following steps:
(1) the method comprises the following steps of (1) writing a polymer substrate by using laser according to a pre-designed pattern, obtaining a carbonized product by the high-temperature carbonization of the polymer by using the laser, and realizing the patterned preparation of an electrode, a current collector and a connector in one step;
(2) coating electrolyte on the electrode material part, and reserving a space on the connector part to prepare the integrated planar super capacitor;
(3) the integrated planar super capacitor structure prepared on the polymer substrate is in series connection or parallel connection or combination of series connection and parallel connection, and the output voltage and current of the integrated planar super capacitor can be adjusted according to different design structures.
2. A method of making an integrated planar supercapacitor according to claim 1, wherein: the laser in the step (1) is one or more of ultraviolet laser, visible laser and infrared laser, the wavelength range of the laser is 100-300000 nm, the power range of the laser is 0.01-100W, the writing speed of the laser is 0.1-100 mm/s, and the writing precision of the laser is 1-10000 microns.
3. A method of making an integrated planar supercapacitor according to claim 1, wherein: the pre-designed patterns comprise electrode patterns of a single super capacitor and patterns of conductive connectors among the super capacitors, wherein the electrode patterns of the single super capacitor are in one or more of a line segment shape, a strip shape, an interdigital shape, a concentric circle shape and a folding shape, and the patterns of the conductive connectors are in one or more of a line segment shape, a folding line shape and a curve shape.
4. A method of making an integrated planar supercapacitor according to claim 1, wherein: the shape and plane size of the pattern obtained by the writing are the same as those of the pre-designed pattern, each electrode or connector respectively has a certain area and thickness, wherein the thickness is between 100nm and 200 mu m, and the area of a single electrode is 10 mu m2～20cm2Between, the area of a section of conductive connector is 10 μm2～10cm2In the meantime.
5. A method of making an integrated planar supercapacitor according to claim 1, wherein: the polymer substrate is one or more than two of polyimide, polyetherimide, polyethylene terephthalate, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, polytetrafluoroethylene and polyvinylidene fluoride.
6. A method of making an integrated planar supercapacitor according to claim 1, wherein: the carbonized product obtained by the laser high-temperature carbonization is one or the combination of two of graphene and amorphous carbon, wherein the transverse size of the graphene is 100 nm-100 mu m, the number of layers is 1-10, and the specific surface area of the graphene and the amorphous carbon is 20-3000 m2/g。
7. A method of making an integrated planar supercapacitor according to claim 1, wherein: the output voltage of the integrated super capacitor is adjustable between 1V and 100V, and the current is adjustable between 1 muA and 100 mA.
8. A method of making an integrated planar supercapacitor according to claim 1, wherein: the electrolyte in the step (2) is one or more than two of sulfuric acid solution, phosphoric acid solution, potassium hydroxide solution, sodium sulfate solution, lithium chloride solution, sulfuric acid/polyvinyl alcohol, phosphoric acid/polyvinyl alcohol, potassium hydroxide/polyvinyl alcohol, lithium chloride/polyvinyl alcohol, sodium sulfate/polyvinyl alcohol, 1-ethyl-3-methylimidazolium tetrafluoroborate/polyvinylidene fluoride, lithium bistrifluoromethanesulfonylimide/polyvinylidene fluoride and the like.
9. An integrated planar supercapacitor prepared by the method of any one of claims 1 to 8, wherein: the integrated planar super capacitor is obtained by connecting a plurality of single planar super capacitors in series, in parallel or in combination of series connection and parallel connection, and a connector is arranged among the plurality of single planar super capacitors; the single planar supercapacitor comprises discontinuously patterned positive and negative electrodes; when the n super capacitors are connected in series, the 1 st positive electrode and the 2 nd negative electrode, and the 2 nd positive electrode andthe 3 rd negative electrode, …, the n-1 st positive electrode and the nth negative electrode are connected through a conductive connector; when n super capacitors are connected in parallel, the anodes of the 1 st to nth super capacitors are connected through a conductive connector, and the cathodes of the 1 st to nth super capacitors are also connected through a conductive connector; defining an integrated super capacitor obtained by connecting n super capacitors in series and then connecting m groups of n super capacitors in series in parallel as nS multiplied by mP; defining an integrated super capacitor obtained by connecting n super capacitors in parallel and then connecting m groups of n super capacitors in parallel in series as nP multiplied by mS; for a plurality of supercapacitors A which are not identical1,A2,…,AnDevices integrated in series, using S (A)1～A2～…～An) Represents; for a plurality of supercapacitors A which are not identical1,A2,…,AnParallel integrated devices, using P (A)1～A2～…～An) Is shown in the specification, wherein Ai(i ═ 1,2, …, n) can be a single supercapacitor or an integrated supercapacitor, such as S (1 sx 2P to 2 sx 2P), P (3 sx 2P to 1 sx 1P);
wherein n refers to the number of the super capacitors in series connection; m refers to the number of supercapacitors in parallel: s means serial connection; p refers to parallel connection: an refers to a single or integrated supercapacitor.
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| CN113161158A (en) * | 2021-04-30 | 2021-07-23 | 中国科学院半导体研究所 | Flexible micro capacitor and preparation method thereof |
| CN113161154A (en) * | 2021-04-30 | 2021-07-23 | 中国科学院半导体研究所 | Flexible capacitor device and method of making the same |
| CN113410064A (en) * | 2021-05-27 | 2021-09-17 | 华南理工大学 | Planar electrode and preparation method and application thereof |
| CN113410064B (en) * | 2021-05-27 | 2023-02-14 | 华南理工大学 | Planar electrode and preparation method and application thereof |
| CN113690061A (en) * | 2021-09-03 | 2021-11-23 | 北京航空航天大学 | Carbon-based supercapacitor electrode and laser-acid modification synergistic preparation method and application thereof |
| CN113690061B (en) * | 2021-09-03 | 2022-05-06 | 北京航空航天大学 | Carbon-based supercapacitor electrode and laser-acid modification synergistic preparation method and application thereof |
| CN113916414A (en) * | 2021-09-30 | 2022-01-11 | 中国科学院重庆绿色智能技术研究院 | Leather-based mechanical sensor and preparation method thereof |
| CN113916414B (en) * | 2021-09-30 | 2024-04-26 | 中国科学院重庆绿色智能技术研究院 | Leather-based mechanical sensor and preparation method thereof |
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Application publication date: 20200529 |