CN107316756A - A kind of preparation method of cladding Cu MOF ultra-thin nano material of manganese dioxide - Google Patents
A kind of preparation method of cladding Cu MOF ultra-thin nano material of manganese dioxide Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000005253 cladding Methods 0.000 title claims abstract description 4
- 229910006364 δ-MnO2 Inorganic materials 0.000 claims abstract description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- RBUHEOMIOUHQDN-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid;sodium Chemical compound [Na].OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 RBUHEOMIOUHQDN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 4
- 230000004044 response Effects 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000002604 ultrasonography Methods 0.000 claims abstract description 3
- 239000013084 copper-based metal-organic framework Substances 0.000 claims description 41
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims 1
- 235000021050 feed intake Nutrition 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000003990 capacitor Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 description 16
- 229910001868 water Inorganic materials 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- -1 test result shows Substances 0.000 description 1
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
- H01G11/46—Metal oxides
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- H01G11/84—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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
A kind of preparation method of cladding Cu MOF ultra-thin nano material of manganese dioxide, belongs to the technical field of electric chemical super capacitor application.Potassium permanganate and ethyl acetate are mixed and carry out heating response, is madeδ‑MnO2Material, through being dissolved in ethanol, is obtainedδ‑MnO2Standard liquid；Willδ‑MnO2After standard liquid is mixed with ethanol, cupric salt under ultrasound condition, then with trimesic acid sodium solution hybrid reaction, obtain after reactive material washs with deionized water and ethanol, produce nano material.Raw material environmental protection of the present invention, cost are low, preparation technology is simple, easily operated control, suitable for continuous large-scale production, preparation process environmental protection, obtained nano material has the advantages that low environment-friendly, cost, high capacitance, high-energy-density, and it has preferable redox ability and higher capacitance value.
Description
Technical field
The invention belongs to the technical field of electric chemical super capacitor application.
Background technology
Water is Source of life.No matter in which system, water is conducive to environmental protection, reusable edible etc. it is excellent
Point.Meanwhile, also there is the water electrochemical capacitor of exception（ECs）.
ECs typically has three kinds of electrolyte to be respectively the aqueous solution, organic bath and solid electrolyte.In nearest research
In, common electrolyte account for because cost is low, and non-ignitable, environment-friendly advantage is easy to assembly in atmosphere, particularly macroion
The advantage of electrical conductivity.As electrode micropore is fully contacted, Water-Electrolyte is better than other two kinds of electrolyte really.Meanwhile, it is higher
Ionic conductivity can reach than water base and nonaqueous electrolytic solution basic and higher power density.In summary, it appears that aobvious
The electrolyte so used in ECs is the aqueous solution.However, temperature range of the water from freezing point to boiling point is very narrow, so as to cause
Very low or high ECs temperature and perform poor.Bigger shortcoming is that the maximum decomposition voltage of Water-Electrolyte is 1.23 V, and it is not
A wide electrochemical window can be provided, to realize high-energy and power-performance.Therefore, the maximum functional electricity of Water-Electrolyte is widened
Pressure turns into the task of top priority.
In order to solve the electrochemical stability window of narrow current potential（1.23 V）Limitation, it is necessary to find suitable method.
It is the pH value for eliminating oxygen and adjustment electrolyte according to Luo Jiayan seminar common way.They find, O2With
H2O can be with the chemical material of the negative pole of redox state.Suppress liberation of hydrogen ability because the basicity of water has, make water reduction potential
Move down, they maintain chemical stability, by adjusting pH value and O2In the case of.Yamada seminar provides
Another new method, they have found high pressure（∼2.3-3.1v）Water-soluble lithium ion battery is molten as electrolyte with lithium hydrate
Body.In addition, being reported according to Suo seminar, water lithium ion battery can operate more than 1000 cycles in 2.3V.They find,
Between electrode surface and electrolyte, it is alternate to there is a protection, forbids electronics to conduct but allows ionic conduction.This can be effectively
Avoid H2, O2Or OH-Precipitated in fine and close solid-state.These remarkable technologies provide the chance of more perfect electrochemical window, especially
It is the storage to electric capacity.
In addition to widening potential electrochemical stability windows, the selection of electrode material is also very important, because making
Energy density can be improved with appropriate capacitance material.In recent years, the integration of nano material and structure has become the note that induces one
Purpose.This new material has novel physics, chemical property, including crystal structure and the big interior surface areas of MOFs, even
With the dimensional effect of skin effect and macro quanta tunnel effect to nano material.Up to the present, this research field has been
There are some remarkable examples.Lu seminar reports an assembly strategy, successfully realizes nano-particle and ZIF-8 is several
The incorporation of type.And the nano composite material obtained by the conclusion that they obtain includes/ZIF-8 benefit.2010, according to
Jiang seminar, they have studied a gold/galactic nucleus core/shell nanoparticles for the first time（NPS）It is fixed on MOF.As support,
The change of the functional group of the big specific surface area of MOFs offers and hole wall, coordinates the catalytic performance of gold/galactic nucleus core/shell nanoparticles, realizes
The catalytic activity than alloy more superior and metal nanoparticle.Equally, the ultracapacitor of high-energy-density, Ke Yikao are realized
Consider the mixing nano composite material for combining MOFs and nano material.
The content of the invention
Existing background technology and deficiency for more than, the present invention propose there is preferable redox ability and higher electricity
The Cu-MOF@of capacitanceδ-MnO2The preparation method of nano material.
Cu-MOF@of the present inventionδ-MnO2The preparation method of nano material, is carried out according to the following steps：
1）Potassium permanganate and ethyl acetate are mixed and carry out heating response, is madeδ-MnO2Material；
2）Willδ-MnO2Material is dissolved in ethanol, is obtainedδ-MnO2Standard liquid；
3）Willδ-MnO2After standard liquid is mixed with ethanol, cupric salt under ultrasound condition, then with trimesic acid sodium solution
Mixing is reacted, until Cu-MOF is grown inδ-MnO2On piece；
4）By step 3）After acquisition reactive material is washed with deionized water and ethanol, Cu-MOF is producedδ-MnO2Nano material.
MnO2It is a kind of promising capacitance material, has the advantages that environment-friendly, cost is low, can be super used in electrochemistry
In the neutral aqueous solution of level capacitor.The Cu-MOF@of the present inventionδ-MnO2Nano material is by magnetic agitation method and supercritical ultrasonics technology
It is prepared from, the raw material environmental protection of use, cost are low, and preparation technology is simple, it is easy to operational control, suitable for continuous extensive raw
Production, preparation process environmental protection.
Using Cu-MOF@made from above methodδ-MnO2Nano material has low environment-friendly, cost, high capacitance, height
The advantage of energy density, it has preferable redox ability and higher capacitance value, has well in ultracapacitor
Application prospect.
Ultracapacitor of the present invention Cu-MOF δ-MnO2Nano composite material is used as the gentle electrode material of environment.Through examination
Checking is bright：In Na2SO4In electrolyte solution, the charging and discharging of electrode, occurred in that in two electrode systems a solid film with
Suppress the electrolysis of water, simultaneous electrochemical window is stable in 0-2.0 V.
Further, cupric salt of the present invention is Cu (NO3)2、CuCl2、CuSO4Or Cu (CH3COO)2.Through experiment card
It is bright, by the acid group of this several metal salt institutes band is easily sloughed, it is more easy to obtain required product, therefore preferentially use this several metal
Salt is the cupric salt in present invention process.
The molar ratio of the trimesic acid sodium and cupric salt is 2: 3.Under this ratio, can equably it generate
Cu-MOF, and can also be covered by well in the fold of manganese dioxide ultrathin nanometer piece.
Brief description of the drawings
The Cu-MOF@that accompanying drawing 1 is prepared for the present inventionδ-MnO2The scanning electron microscope (SEM) photograph of nano-electrode material.
The Cu-MOF@that accompanying drawing 2 is prepared for the present inventionδ-MnO2The transmission electron microscope picture of nano-electrode material.
The Cu-MOF@that accompanying drawing 3 is prepared for the present inventionδ-MnO2The XRD of nano-electrode material.
The Cu-MOF@that accompanying drawing 4 is prepared for the present inventionδ-MnO2The infrared spectrogram of nano-electrode material.
The Cu-MOF@that accompanying drawing 5 is prepared for the present inventionδ-MnO2The small multiplying power ESEM of the solid film of nano-electrode material
Figure.
The Cu-MOF@that accompanying drawing 6 is prepared for the present inventionδ-MnO2The big multiplying power ESEM of the solid film of nano-electrode material
Figure.
The Cu-MOF@that accompanying drawing 7 is prepared for the present inventionδ-MnO2Nano-electrode material is applied to two electrodes of ultracapacitor
The constant current charge-discharge figure of system.
The Cu-MOF@that accompanying drawing 8 is prepared for the present inventionδ-MnO2Nano-electrode material is applied to three electrodes of ultracapacitor
The constant current charge-discharge figure of system.
Embodiment
First, Cu-MOF@δ-MnO2The preparation of nano material：
0.002M, 150mL potassium permanganate solution and 99.8%, 40mL ethyl acetate is taken to be blended in a flask.Then condense
Backflow stirs solution at a temperature of 85 DEG C, and this process is constant, until there is substantial amounts of brown particles to be formed, and represents reaction
Terminate.Obtained afterwards several times after being rinsed respectively with deionized water and ethanolδ-MnO2Material.
Again 15 mL ethanol and produced aboveδ-MnO2Material is added in centrifuge tube, obtains 10g/L'sδ-MnO2Mark
Quasi- suspension.
Then, in room temperature, by 1.0mL standardδ-MnO2Suspension and 30mL the ethanol magnetic agitation in beaker are mixed,
Add 0.1 M, 3.0mL Cu (NO3)2The aqueous solution, through it is ultrasonic must be lower 10 minutes, reach it is well mixed after, trimesic acid
Sodium solution 0.1M, 2mL are added dropwise to wherein.One hour of whipping process sustained response, it is grown in Cu-MOFδ-MnO2Piece
On.Gu mutually solid after reaction at least wash three times respectively through deionized water and ethanol, Cu-MOF@are obtainedδ-MnO2Raw material.
Above Cu (NO3)2The aqueous solution can also use CuCl2、CuSO4Or Cu (CH3COO)2The aqueous solution is replaced, as a result identical.
2nd, Cu-MOF@δ-MnO2The character analysis and result of nano material：
Fig. 1 is obtained Cu-MOF@δ-MnO2The scanning electron microscope (SEM) photograph of nano material, test result shows that Cu-MOF particles are successful
Ground length existsδ-MnO2In the fold of nanometer sheet.
Fig. 2 is obtained Cu-MOF@δ-MnO2The transmission electron microscope picture of nano material, test result shows, Cu-MOF particles
Successfully growδ-MnO2In the fold of nanometer sheet.With Cu-MOF@δ-MnO2The sem test result one of nano material
Cause.
Fig. 3 is obtained Cu-MOF@δ-MnO2The XRD of nano material, from figure, can find Cu-MOF andδ-MnO2's
Characteristic peak, this also suffices to show that the material of preparation is really Cu-MOF@δ-MnO2Composite.
Fig. 4 is obtained Cu-MOF@δ-MnO2Electrode material infrared spectrogram, found in figure Cu-MOF andδ-MnO2's
Characteristic peak, it is sufficient to which it is really Cu-MOF@to prove the material preparedδ-MnO2Composite.
Fig. 5 and Fig. 6 show Cu-MOF@δ-MnO2The SEM tests for the solid film that nano material is generated in test process.
From Fig. 5,6：The solid film prevents the electrolysis of water well, can prevent entering for electronics by the proton in electrolyte
Enter.
With obtained Cu-MOF@δ-MnO2Electrode material is as working electrode, using platinum electrode as to electrode, with saturation
Calomel electrode is reference electrode, three-electrode system is constituted, with 1M Na2SO4In electrolyte, to carry out constant current charge-discharge examination
Test.As a result as shown in fig. 7, obtained Cu-MOF@δ-MnO2The curve of electrode material constant current charge-discharge in three-electrode system
In inverted triangle shape, and almost symmetry, this illustrates that the material has preferable redox ability.Capacitance can be calculated by the figure
683Fg can be reached-1；It can be seen that the good chemical property of this material.
With obtained Cu-MOF@δ-MnO2Electrode material is positive electrode, using activated carbon as negative electrode, carries out constant current charge and discharge
The experiment of electricity.As a result as shown in figure 8, obtained Cu-MOF@δ-MnO2Electrode material constant current charge-discharge in two electrode systems
Curve be in inverted triangle shape, and almost symmetry, this illustrates that the material has preferable redox ability.Electrochemical window in test process
Mouth can reach 2V and in the absence of the electrolysis of water.It can thus be seen that sample Cu-MOF@δ-MnO2Electrode material can widen water electrolysis
The operating voltage of matter.
Tested more than：By Cu-MOF@produced by the present inventionδ-MnO2Application of micron in ultracapacitor,
Have the advantage that：
1st, it is successfully realized the compound of MOF and inorganic matter.
2nd, one layer of solid film is formd so that potential window can reach 0-2.0V.
3rd, composite capacitance can reach 683Fg in three-electrode system-1。
Claims (3)
1. a kind of preparation method of cladding Cu-MOF ultra-thin nano material of manganese dioxide, it is characterised in that comprise the following steps：
1）Potassium permanganate and ethyl acetate are mixed and carry out heating response, is madeδ-MnO2Material；
2）Willδ-MnO2Material is dissolved in ethanol, is obtainedδ-MnO2Standard liquid；
3）Willδ-MnO2After standard liquid is mixed with ethanol, cupric salt under ultrasound condition, then it is mixed with trimesic acid sodium solution
Conjunction is reacted；
4）By step 3）After acquisition reactive material is washed with deionized water and ethanol, Cu-MOF is producedδ-MnO2Nano material.
2. preparation method according to claim 1, it is characterised in that the cupric salt is Cu (NO3)2、CuCl2、CuSO4
Or Cu (CH3COO)2。
3. preparation method according to claim 1, it is characterised in that the trimesic acid sodium and cupric salt feed intake
Mol ratio is 2: 3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110034287A (en) * | 2019-04-10 | 2019-07-19 | 扬州大学 | ZIF-67 coats potassium phosphomolybdate microballoon composite material and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110034287A (en) * | 2019-04-10 | 2019-07-19 | 扬州大学 | ZIF-67 coats potassium phosphomolybdate microballoon composite material and preparation method |
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