CN110911177A - Preparation method of asymmetric molybdenum disulfide/graphene micro supercapacitor - Google Patents
Preparation method of asymmetric molybdenum disulfide/graphene micro supercapacitor Download PDFInfo
- Publication number
- CN110911177A CN110911177A CN201911225136.1A CN201911225136A CN110911177A CN 110911177 A CN110911177 A CN 110911177A CN 201911225136 A CN201911225136 A CN 201911225136A CN 110911177 A CN110911177 A CN 110911177A
- Authority
- CN
- China
- Prior art keywords
- molybdenum disulfide
- graphene
- ink
- asymmetric
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 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
- 238000007641 inkjet printing Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 238000004146 energy storage 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
- 238000010586 diagram Methods 0.000 description 1
- 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
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses 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 to respectively obtain molybdenum disulfide ink and graphene ink; (b) respectively placing molybdenum disulfide ink and graphene ink in an ink box of an ink-jet printer, and respectively printing a molybdenum disulfide micro electrode and a graphene micro electrode; (c) and simultaneously placing the molybdenum disulfide micro electrode and the graphene micro electrode in neutral electrolyte to form the asymmetric molybdenum disulfide/graphene micro supercapacitor. The ink is prepared from the thin-layer folded molybdenum disulfide powder with high thin layer rate, the electrode printed by ink-jet printing has high precision and excellent performance, is environment-friendly and pollution-free, and the asymmetric miniature supercapacitor device has good electrochemical performance, can realize a wider stable voltage window and has high precision, thereby being suitable for industrial mass 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911225136.1A CN110911177B (en) | 2019-12-04 | 2019-12-04 | Preparation method of asymmetric molybdenum disulfide/graphene micro supercapacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911225136.1A CN110911177B (en) | 2019-12-04 | 2019-12-04 | Preparation method of asymmetric molybdenum disulfide/graphene micro supercapacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110911177A true CN110911177A (en) | 2020-03-24 |
| CN110911177B CN110911177B (en) | 2021-05-14 |
Family
ID=69821866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911225136.1A Active CN110911177B (en) | 2019-12-04 | 2019-12-04 | Preparation method of asymmetric molybdenum disulfide/graphene micro supercapacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110911177B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114634732A (en) * | 2022-03-21 | 2022-06-17 | 中国科学院化学研究所 | Two-dimensional material water-based ink and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130045427A1 (en) * | 2011-08-19 | 2013-02-21 | Nanoteck Instruments, Inc. | Prelithiated current collector and secondary lithium cells containing same |
| CN106257609A (en) * | 2016-08-22 | 2016-12-28 | 河南师范大学 | A kind of method preparing monolayer 1T phase molybdenum bisuphide/graphene composite material |
| CN108122685A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | Stacked ultracapacitor that a kind of inkjet printing is prepared and preparation method thereof |
| US20180355194A1 (en) * | 2017-06-09 | 2018-12-13 | Virginia Commonwealth University | Flexible, biodegradable, and biocompatible supercapacitors |
-
2019
- 2019-12-04 CN CN201911225136.1A patent/CN110911177B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130045427A1 (en) * | 2011-08-19 | 2013-02-21 | Nanoteck Instruments, Inc. | Prelithiated current collector and secondary lithium cells containing same |
| CN106257609A (en) * | 2016-08-22 | 2016-12-28 | 河南师范大学 | A kind of method preparing monolayer 1T phase molybdenum bisuphide/graphene composite material |
| CN108122685A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | Stacked ultracapacitor that a kind of inkjet printing is prepared and preparation method thereof |
| US20180355194A1 (en) * | 2017-06-09 | 2018-12-13 | Virginia Commonwealth University | Flexible, biodegradable, and biocompatible supercapacitors |
Non-Patent Citations (2)
| Title |
|---|
| DAVID J. FINN等: "Inkjet deposition of liquid-exfoliated graphene and MoS2 nanosheets for printed device applications", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
| YUANLONG SHAO等: "1T-Molybdenum disulfide/ reduced graphene oxide hybrid fibers as high strength fibrous electrodes for wearable energy storage", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114634732A (en) * | 2022-03-21 | 2022-06-17 | 中国科学院化学研究所 | Two-dimensional material water-based ink and preparation method and application thereof |
| CN114634732B (en) * | 2022-03-21 | 2023-10-31 | 中国科学院化学研究所 | Two-dimensional material water-based ink and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110911177B (en) | 2021-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sethi et al. | Facile solvothermal synthesis and high supercapacitor performance of NiCo2O4 nanorods | |
| Mensing et al. | 2D and 3D printing for graphene based supercapacitors and batteries: A review | |
| Zhang et al. | MXene printing and patterned coating for device applications | |
| Majumdar et al. | Recent advancements of copper oxide based nanomaterials for supercapacitor applications | |
| Wang et al. | Inkjet printing of δ-MnO2 nanosheets for flexible solid-state micro-supercapacitor | |
| Li et al. | Layer-by-layer inkjet printing GO film anchored Ni (OH) 2 nanoflakes for high-performance supercapacitors | |
| Raj et al. | Two-dimensional planar supercapacitor based on zinc oxide/manganese oxide core/shell nano-architecture | |
| Chen et al. | Inkjet printing of single-walled carbon nanotube/RuO 2 nanowire supercapacitors on cloth fabrics and flexible substrates | |
| Luo et al. | Rapid synthesis of three-dimensional flower-like cobalt sulfide hierarchitectures by microwave assisted heating method for high-performance supercapacitors | |
| Su et al. | Scalable fabrication of MnO 2 nanostructure deposited on free-standing Ni nanocone arrays for ultrathin, flexible, high-performance micro-supercapacitor | |
| Hu et al. | A hierarchical nanostructure consisting of amorphous MnO2, Mn3O4 nanocrystallites, and single-crystalline MnOOH nanowires for supercapacitors | |
| CN102282706B (en) | High efficiency energy conversion and storage systems using carbon nanostructured materials | |
| Li et al. | Rational design of porous MnO2 tubular arrays via facile and templated method for high performance supercapacitors | |
| US10395851B2 (en) | Method for preparing aqueous MnO2 ink and capacitive energy storage devices comprising MnO2 | |
| CN111934030B (en) | Flexible planar micro energy storage device and preparation method thereof | |
| Luo et al. | Fixing graphene-Mn3O4 nanosheets on carbon cloth by a poles repel-assisted method to prepare flexible binder-free electrodes for supercapacitors | |
| CN107946091B (en) | A kind of paper base flexible flat supercapacitor preparation method | |
| US11492720B2 (en) | High-performance solid-state supercapacitors and microsupercapacitors derived from printable graphene inks | |
| Kumar et al. | Single-step growth of pyramidally textured NiO nanostructures with improved supercapacitive properties | |
| Le et al. | Inkjet-printed graphene for flexible micro-supercapacitors | |
| Wang et al. | Synthesis of hollow NiO nanostructures and their application for supercapacitor electrode | |
| Uke et al. | Tri-Ethanolamine-Ethoxylate assisted hydrothermal synthesis of nanostructured MnCo2O4 with superior electrochemical performance for high energy density supercapacitor application | |
| CN107275113A (en) | The method that double medium agent jet plasmas prepare flexible super capacitor combination electrode | |
| CN110911177B (en) | Preparation method of asymmetric molybdenum disulfide/graphene micro supercapacitor | |
| Chen et al. | A facile laser assisted paste-tear approach to large area, flexible and wearable in-plane micro-supercapacitors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |