CN110911177A - A kind of preparation method of molybdenum disulfide/graphene asymmetric micro supercapacitor - Google Patents
A kind of preparation method of molybdenum disulfide/graphene asymmetric micro supercapacitor Download PDFInfo
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 133
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000007639 printing Methods 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 44
- 239000006185 dispersion Substances 0.000 claims description 33
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 16
- 238000002347 injection Methods 0.000 claims description 10
- 239000007924 injection Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims 1
- 159000000002 lithium salts Chemical class 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 5
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- 230000000052 comparative effect Effects 0.000 description 7
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- 238000004146 energy storage Methods 0.000 description 4
- 238000007641 inkjet printing Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
- 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
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Abstract
本发明公开了一种二硫化钼/石墨烯非对称微型超级电容器的制备方法，包括如下步骤：(a)将薄层褶皱二硫化钼粉体、还原氧化石墨烯分别分散在混合醇溶剂中分别得到二硫化钼墨水、石墨烯墨水；(b)分别将二硫化钼墨水和石墨烯墨水放置于喷墨打印机的墨盒中，分别打印出二硫化钼微型电极、石墨烯微型电极；(c)将二硫化钼微型电极、石墨烯微型电极同时置于中性电解液中，形成二硫化钼/石墨烯非对称微型超级电容器。本发明采用高薄层率的薄层褶皱二硫化钼粉体制备墨水，喷墨打印出的电极精度高，性能优，对环境友好无污染，非对称微型超级电容器器件电化学性能好，能实现较宽稳定电压视窗，精度高，适于工业化规模生产。The invention discloses a preparation method of molybdenum disulfide/graphene asymmetric micro supercapacitor, comprising the following steps: (a) dispersing thin-layer wrinkled molybdenum disulfide powder and reduced graphene oxide in mixed alcohol solvent respectively Obtaining molybdenum disulfide ink and graphene ink; (b) respectively placing the molybdenum disulfide ink and the graphene ink in the ink cartridge of the inkjet printer, and printing out the molybdenum disulfide micro-electrode and the graphene micro-electrode respectively; (c) the Molybdenum disulfide micro-electrodes and graphene micro-electrodes are simultaneously placed in neutral electrolyte to form molybdenum disulfide/graphene asymmetric micro-supercapacitors. The invention adopts the thin layer wrinkled molybdenum disulfide powder with high thin layer rate to prepare the ink, the electrode printed by inkjet has high precision, excellent performance, is environmentally friendly and has no pollution, and the asymmetric micro super capacitor device has good electrochemical performance and can realize Wide and stable voltage window, high precision, suitable for industrial scale production.
Description
Technical Field
The invention relates to a preparation method of a molybdenum disulfide/graphene asymmetric miniature supercapacitor.
Background
With the arrival of the 5G era, electronic products are intelligent, fashionable, attractive, flexible, portable and wearable, and gradually become the latest development trend, and concept products including flexible OLED displays, folding screen mobile phones, electronic garments and the like gradually enter the consumer market. Although the new mobile phone screen launched in the market can be bent and folded, the energy storage device still adopts the traditional block lithium ion battery, and has large volume, heavy weight and inflexibility; for other concepts of wearable flexible electronic products, the lack of a high energy density flexible energy storage device remains a major bottleneck limiting their commercial applications. The super capacitor is an electrochemical energy storage device, and is known as a micro super capacitor with high power density, ultra-long cycle charge-discharge life (>100,000 times), use reliability and the like, so that the micro super capacitor is an ideal energy storage device of flexible wearable electronics. The existing preparation method of the miniature super capacitor has the problems of low electrode preparation precision, difficulty in realizing large-scale preparation and the like. Therefore, a method for manufacturing a flexible energy storage device with high precision and large scale is urgently needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the preparation method of the asymmetric miniature supercapacitor, which has the advantages of simple preparation process, environmental friendliness, no pollution, high electrode precision and excellent device performance.
The invention provides a preparation method of a molybdenum disulfide/graphene asymmetric miniature supercapacitor, which comprises the following steps:
(a) respectively dispersing the thin-layer folded molybdenum disulfide powder and the reduced graphene oxide in a mixed alcohol solvent, and performing ultrasonic treatment after stirring to respectively obtain molybdenum disulfide ink and graphene ink;
(b) respectively placing the molybdenum disulfide ink and the graphene ink in an ink box of an ink-jet printer, so as to respectively print a molybdenum disulfide micro electrode and a graphene micro electrode;
(c) and simultaneously placing the molybdenum disulfide microelectrode and the graphene microelectrode in neutral electrolyte to form the asymmetric molybdenum disulfide/graphene supercapacitor.
Specifically, in the step (a), the mixed alcohol is two selected from ethanol, isopropanol, n-butanol and tert-butanol.
Preferably, in the step (a), the mixed alcohol is isopropanol and n-butanol, and the volume ratio of the isopropanol to the n-butanol is 1: 18-22.
According to the invention, the mixed alcohol obtained by mixing isopropanol and n-butanol can realize the stable dispersion of the thin-layer folded molybdenum disulfide powder and the reduced graphene oxide in the molybdenum disulfide/graphene ink.
Specifically, in the step (a), the particle size of the thin-layer wrinkled molybdenum disulfide powder is 200-400 nanometers, and the particle size of the reduced graphene oxide is 500-1000 nanometers.
In the invention, the thin-layer folded molybdenum disulfide powder and the original graphene oxide are filtered and selected, so that the particle size range of particles is controlled.
Specifically, in the step (a), the stirring time is 10-60min, the ultrasonic time is 10-120min, and in the step (b), the distance between printing liquid drops is 30-120 microns, and the number of printing layers is 10-80.
Specifically, the preparation method of the thin-layer wrinkled molybdenum disulfide powder comprises the following steps:
(1) adding isopropanol into the molybdenum disulfide sheet layer aqueous dispersion to obtain mixed dispersion;
(2) placing the mixed dispersion liquid in a cell disruptor for ultrasonic treatment for 10-40min, and then placing the mixed dispersion liquid in a water bath for ultrasonic treatment for 20-120min to obtain a molybdenum disulfide sheet layer mixed dispersion liquid;
(3) and extruding the molybdenum disulfide lamellar mixed dispersion liquid in a stepping injection pump, applying a voltage of 5-20KV between a spray head and a collecting plate of the stepping injection pump, and electrically spraying the molybdenum disulfide lamellar mixed dispersion liquid on the surface of the collecting plate for deposition to obtain the thin-layer corrugated molybdenum disulfide powder.
Preferably, in the step (1), the molybdenum disulfide sheet layer is obtained by a liquid phase stripping method, the volume ratio of the molybdenum disulfide sheet layer aqueous dispersion to the isopropanol is 1:8-10, and in the step (3), the extrusion speed is 0.5 microliter-10 microliter/min.
Specifically, the inkjet printer is a Dimatix printer.
According to the invention, a Dimatix printer is adopted, so that high-precision printing of two different active material finger-type electrode structures of thin-layer folded molybdenum disulfide powder and reduced graphene oxide can be realized.
Specifically, the gap between the molybdenum disulfide microelectrode and the graphene microelectrode is 50-200 microns.
Specifically, the neutral electrolyte is one selected from lithium sulfate, sodium sulfate and magnesium sulfate.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: according to the invention, the self-made thin-layer folded molybdenum disulfide powder with high thin layer rate is adopted to prepare ink, and then the molybdenum disulfide micro electrode and the graphene micro electrode are prepared by adopting an ink-jet printing method, so that the molybdenum disulfide/graphene asymmetric micro supercapacitor device is prepared.
Drawings
FIG. 1 is a schematic diagram of a process for preparing molybdenum disulfide powder with thin-layer wrinkles by electric spraying; the digital picture of the inset is a multi-stage injection optical microscope picture of the tip of the needle head of the stepping injection pump under the irradiation of infrared laser;
FIG. 2 is a comparison of molybdenum disulfide powder raw materials, layered molybdenum disulfide and lamellar wrinkled molybdenum disulfide powder of the same quality;
FIG. 3(a) is an electron micrograph of a thin wrinkled molybdenum disulfide powder deposited on the surface of a collecting plate during electrospray;
FIG. 3(b) is a partial enlarged view of FIG. 3 (a);
FIG. 4 is a comparison graph of X-ray photoelectron spectra of molybdenum disulfide powder raw material, layered molybdenum disulfide and lamellar wrinkled molybdenum disulfide powder;
FIG. 5 is a comparison graph of Raman spectra of the molybdenum disulfide powder raw material, layered molybdenum disulfide and lamellar wrinkled molybdenum disulfide powder;
FIG. 6 is a digital photograph of molybdenum disulfide ink prepared in example 1;
FIG. 7 is a digital photograph of an inkjet printed molybdenum disulfide/graphene asymmetric miniature supercapacitor of example 1;
FIG. 8 is an electron microscope image of an inkjet printed molybdenum disulfide/graphene asymmetric supercapacitor of example 1;
FIG. 9 is a cyclic voltammetry curve of the asymmetric molybdenum disulfide/graphene supercapacitor of example 1 at different scan rates;
fig. 10 is a comparison graph of cyclic voltammetry curves of three asymmetric molybdenum disulfide/graphene supercapacitors in series according to example 4 and a single asymmetric molybdenum disulfide/graphene supercapacitor according to example 1.
Detailed Description
The invention discloses a preparation method of a molybdenum disulfide/graphene asymmetric miniature supercapacitor, which comprises the following steps:
(a) respectively dispersing thin-layer folded molybdenum disulfide powder (the particle size of the thin-layer folded molybdenum disulfide powder is 200-400 nanometers) and reduced graphene oxide (the particle size of the reduced graphene oxide is 500-1000 nanometers) in a mixed alcohol solvent, stirring for 10-60min by using magnetic force, and then performing water bath ultrasound for 10-120min to respectively obtain molybdenum disulfide ink and graphene ink; the mixed alcohol is two selected from ethanol, isopropanol, n-butanol and tert-butanol. In the invention, the mixed alcohol is isopropanol and n-butanol, and the volume ratio of the isopropanol to the n-butanol is 1: 1-20.
(b) Respectively placing molybdenum disulfide ink and graphene ink in an ink box of an ink-jet printer (Dimatix printer), setting the distance between printing liquid drops to be 30-120 micrometers, and setting the number of printing layers to be 10-80 layers, so as to respectively print a molybdenum disulfide micro electrode and a graphene micro electrode; the gap between the molybdenum disulfide micro-electrode and the graphene micro-electrode is 50-200 microns.
(c) And simultaneously placing the molybdenum disulfide micro electrode and the graphene micro electrode in neutral electrolyte (one of lithium sulfate, sodium sulfate and magnesium sulfate) to form the asymmetric molybdenum disulfide/graphene micro supercapacitor.
The preparation method of the thin-layer folded molybdenum disulfide powder comprises the following steps:
(1) adding isopropanol (the volume ratio of the molybdenum disulfide sheet layer aqueous dispersion to the isopropanol is 1:8-10) into the molybdenum disulfide sheet layer (the molybdenum disulfide sheet layer is obtained by adopting a liquid phase stripping method) aqueous dispersion to obtain mixed dispersion;
(2) placing the mixed dispersion liquid in a cell disruptor for ultrasonic treatment for 10-40min, and then placing the mixed dispersion liquid in a water bath for ultrasonic treatment for 20-120min to obtain a molybdenum disulfide sheet layer mixed dispersion liquid;
(3) and (3) placing the molybdenum disulfide sheet layer mixed dispersion liquid into a stepping injection pump to be extruded (the extrusion speed is 0.5 microliter-10 microliter/min), applying a voltage of 5-20KV between a spray head and a collecting plate of the stepping injection pump, and electrically spraying the molybdenum disulfide sheet layer mixed dispersion liquid to the surface of the collecting plate to deposit to obtain the thin-layer fold molybdenum disulfide powder.
In the invention, the method for stripping the molybdenum disulfide sheet layer by adopting the liquid phase is as follows: 3g of molybdenum disulfide crystals are dispersed in 3mL1.6M n-butyllithium solution and are kept stand for 2 days under the protective atmosphere of argon gas to form the lithium intercalated molybdenum disulfide. The product was washed with hexane and then ultrasonically stripped for 60 min.
The following provides a detailed description of preferred embodiments of the invention.
(a) respectively dispersing thin-layer corrugated molybdenum disulfide powder (the particle size of the thin-layer corrugated molybdenum disulfide powder is 200-400 nm) and reduced graphene oxide (the particle size of the reduced graphene oxide is 500-1000 nm) in a mixed alcohol solvent, stirring for 10min by magnetic force, and performing water bath ultrasound for 10min to respectively obtain molybdenum disulfide ink and graphene ink; the mixed alcohol is isopropanol and n-butanol, and the volume ratio of the isopropanol to the n-butanol is 1: 20.
(b) Respectively placing molybdenum disulfide ink and graphene ink in an ink box of a Dimatix printer, setting the distance between printing liquid drops to be 30 micrometers, and setting the number of printing layers to be 10, so as to respectively print a molybdenum disulfide micro electrode and a graphene micro electrode; the gap between the molybdenum disulfide microelectrode and the graphene microelectrode was 130 microns.
(c) And simultaneously placing the molybdenum disulfide micro electrode and the graphene micro electrode in neutral electrolyte magnesium sulfate to form the asymmetric molybdenum disulfide/graphene micro supercapacitor.
The preparation method of the molybdenum disulfide powder with the thin wrinkles comprises the following steps:
(1) adding isopropanol (the volume ratio of the molybdenum disulfide sheet layer aqueous dispersion to the isopropanol is 1:9) into the molybdenum disulfide sheet layer (the molybdenum disulfide sheet layer is obtained by adopting a liquid phase stripping method) aqueous dispersion to obtain mixed dispersion;
(2) placing the mixed dispersion liquid in a cell disruptor for ultrasonic treatment for 25min, and then placing the mixed dispersion liquid in a water bath for ultrasonic treatment for 70min to obtain a molybdenum disulfide sheet layer mixed dispersion liquid;
(3) and (3) placing the molybdenum disulfide sheet layer mixed dispersion liquid into a stepping injection pump to be extruded out (the extrusion speed is 0.5 microliter/min), applying a voltage of 5KV between a spray head and a collecting plate of the stepping injection pump, and spraying the molybdenum disulfide sheet layer mixed dispersion liquid to the surface of the collecting plate by using electricity to deposit, so as to obtain the thin-layer folded molybdenum disulfide powder.
Performing electrochemical performance test on the obtained molybdenum disulfide/graphene asymmetric micro supercapacitor, wherein the output voltage is 1.6V, and the energy density is 1 mu Wh/cm2Power density 104μW/cm2。
Comparative example 1A supercapacitor prepared by reducing graphene oxide by a laser method, with an output voltage of 1.0V and an energy density of 0.02. mu. Wh/cm2Power density 10. mu.W/cm2。
Comparative example 2A supercapacitor made of graphene quantum dots with an output voltage of 1V and an energy density of 7. mu. Wh/cm2Power density 70 μ W/cm2。
Comparative example 3A supercapacitor made of graphene/carbon nanotube composite with an output voltage of 1V and an energy density of 0.1. mu. Wh/cm2Power density 7000. mu.W/cm2。
Comparative example 4A supercapacitor made of a carbon derivative with an output voltage of 1V and an energy density of 1. mu. Wh/cm2Power density 2000. mu.W/cm2。
Comparative example 5A supercapacitor made by ink jet printing Mxene with an output voltage of 0.5V and an energy density of 0.1. mu. Wh/cm2Power density 200. mu.W/cm2。
Comparative example 6A supercapacitor made with vertical array graphene, output voltage 1V, energy density 1 uWh/cm2Power density 200. mu.W/cm2。
Comparing the thin-layer folded molybdenum disulfide powder prepared in the embodiment 1 with a molybdenum disulfide powder raw material and layered molybdenum disulfide, pictures with the same quality of the three are shown in fig. 2, the volume of the thin-layer folded molybdenum disulfide powder with the same quality is 40 times that of the molybdenum disulfide powder raw material and the layered molybdenum disulfide with the same quality, the thin-layer rate is high, and the stacking of molybdenum disulfide sheets is effectively avoided; the comparison graph of the X-ray photoelectron spectra of the three is shown in FIG. 4, the thin-layer wrinkled molybdenum disulfide powder prepared by the electric spraying method still has a high content of 1T metal phase; the comparison graph of the raman spectra of the three is shown in fig. 5, and it can be proved that the lamellar folded molybdenum disulfide has a high content of 1T metal phase. The process and the equipment are simple and are suitable for industrial scale production; meanwhile, the method has no pollution to the environment.
Example 1 self-made molybdenum disulfide powder with high lamella ratio and wrinkles was used to prepare ink, as shown in fig. 6. And preparing a molybdenum disulfide micro electrode and a graphene micro electrode by adopting an ink-jet printing method, so as to prepare the asymmetric molybdenum disulfide/graphene micro supercapacitor device, as shown in fig. 7. The preparation process is simple, the electrodes printed by ink jet printing have high precision and excellent performance, are environment-friendly and green, have no pollution, the molybdenum disulfide/graphene asymmetric miniature supercapacitor device has good electrochemical performance, can realize a wider stable voltage window, and electrochemical data are superior to comparative examples 1-6 as shown in figure 9, have high precision and high electrochemical energy storage characteristics, and are suitable for industrial mass production.
The embodiments are only for illustrating the technical concept and features of the present invention, and the purpose of the embodiments is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A preparation method of a molybdenum disulfide/graphene asymmetric micro supercapacitor is characterized by comprising the following steps:
(a) respectively dispersing the thin-layer folded molybdenum disulfide powder and the reduced graphene oxide in a mixed alcohol solvent, and performing ultrasonic treatment after stirring to respectively obtain molybdenum disulfide ink and graphene ink;
(b) respectively placing the molybdenum disulfide ink and the graphene ink in an ink box of an ink-jet printer, so as to respectively print a molybdenum disulfide micro electrode and a graphene micro electrode;
(c) and simultaneously placing the molybdenum disulfide microelectrode and the graphene microelectrode in neutral electrolyte to form the asymmetric molybdenum disulfide/graphene supercapacitor.
2. The preparation method of the asymmetric molybdenum disulfide/graphene micro supercapacitor according to claim 1, characterized in that: in the step (a), the mixed alcohol is two selected from ethanol, isopropanol, n-butanol and tert-butanol.
3. The preparation method of the asymmetric molybdenum disulfide/graphene micro supercapacitor according to claim 2, characterized in that: in the step (a), the mixed alcohol is isopropanol and n-butanol, and the volume ratio of the isopropanol to the n-butanol is 1: 18-22.
4. The preparation method of the asymmetric molybdenum disulfide/graphene micro supercapacitor according to claim 1, characterized in that: in the step (a), the particle size of the thin-layer folded molybdenum disulfide powder is 200-400 nanometers, and the particle size of the reduced graphene oxide is 500-1000 nanometers.
5. The preparation method of the asymmetric molybdenum disulfide/graphene micro supercapacitor according to claim 1, characterized in that: in the step (a), the stirring time is 10-60min, the ultrasonic time is 10-120min, in the step (b), the distance between printing liquid drops is 30-120 microns, and the number of printing layers is 10-80.
6. The preparation method of the asymmetric molybdenum disulfide/graphene micro supercapacitor according to claim 1, wherein the preparation method of the thin-layer wrinkled molybdenum disulfide powder comprises the following steps:
(1) adding isopropanol into the molybdenum disulfide sheet layer aqueous dispersion to obtain mixed dispersion;
(2) placing the mixed dispersion liquid in a cell disruptor for ultrasonic treatment for 10-40min, and then placing the mixed dispersion liquid in a water bath for ultrasonic treatment for 20-120min to obtain a molybdenum disulfide sheet layer mixed dispersion liquid;
(3) and extruding the molybdenum disulfide lamellar mixed dispersion liquid in a stepping injection pump, applying a voltage of 5-20KV between a spray head and a collecting plate of the stepping injection pump, and electrically spraying the molybdenum disulfide lamellar mixed dispersion liquid on the surface of the collecting plate for deposition to obtain the thin-layer corrugated molybdenum disulfide powder.
7. The method for preparing the asymmetric molybdenum disulfide/graphene micro supercapacitor according to claim 6, wherein in the step (1), the molybdenum disulfide layer is obtained by a lithium salt liquid phase stripping method, the volume ratio of the molybdenum disulfide layer aqueous dispersion to the isopropanol is 1:8-10, and in the step (3), the extrusion speed is 0.5 microliter-10 microliter/min.
8. The preparation method of the asymmetric molybdenum disulfide/graphene micro supercapacitor according to claim 1, characterized in that: the ink jet printer is a Dimatix printer.
9. The preparation method of the asymmetric molybdenum disulfide/graphene micro supercapacitor according to claim 1, characterized in that: the gap between the molybdenum disulfide micro-electrode and the graphene micro-electrode is 50-200 microns.
10. The preparation method of the asymmetric molybdenum disulfide/graphene micro supercapacitor according to claim 1, characterized in that: the neutral electrolyte is one selected from lithium sulfate, sodium sulfate and magnesium sulfate.
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