CN108281296B - A method of improving metal-organic framework material chemical property in alkaline solution - Google Patents
A method of improving metal-organic framework material chemical property in alkaline solution Download PDFInfo
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- CN108281296B CN108281296B CN201810067352.7A CN201810067352A CN108281296B CN 108281296 B CN108281296 B CN 108281296B CN 201810067352 A CN201810067352 A CN 201810067352A CN 108281296 B CN108281296 B CN 108281296B
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title claims abstract description 20
- 239000000126 substance Substances 0.000 title claims abstract description 20
- 239000012670 alkaline solution Substances 0.000 title claims abstract description 16
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 59
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 36
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 36
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 35
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910002706 AlOOH Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 10
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005864 Sulphur Substances 0.000 abstract description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004411 aluminium Substances 0.000 abstract description 2
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 oxygen nickel cobalt aluminum Chemical compound 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 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
-
- 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
-
- 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)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses the methods for improving metal-organic framework material chemical property in alkaline solution a kind of in capacitor technology field, the self-assembled nanometer material for only needing the shorter time that structural integrity can be made, have excellent performance, complex device is not needed, it is low in cost, the self-assembled nanometer material specific surface area of synthesis is big, is evenly distributed, with good inner porosity, excellent chemical property, superelevation specific capacitance (2291.6Fg‑1), have extended cycle life, good cycling stability, energy density it is high, reproducibility graphene oxide effectively increases the conductive capability of ZIF-67, and the cobalt ions that nickel aluminum hydrotalcite is then used as " sanctuary " Lai Rongna to dissolve from ZIF-67, further recombination forms nickel cobalt aluminium ternary hydrotalcite, the electric conductivity for effectively compensating for ZIF-67 is poor, and in alkaline electrolyte the shortcomings that poor chemical stability, such method is readily applicable to other unstable metal organic frames in alkaline solution or applies the loss for preventing sulphur in lithium-sulfur cell.
Description
Technical field
The present invention relates to capacitor technology field, specific field is a kind of raising metal-organic framework material in alkaline solution
The method of middle chemical property.
Background technique
Supercapacitor is a kind of new type of energy storage device between traditional capacitor and battery, by electrode material
Carry out storage energy with faraday's redox reaction of the quick ion adsorption desorption of electrolyte interface or completely reversibility, according to energy storage
Supercapacitor can be divided into double layer capacitor and faraday's capacitor with the difference shifted to new management mechanisms；ZIF-67 is by multiple tooth organic
Ligand and metal are formed by complexing, are had non-periodic pore network structure, are belonged to metal-organic framework material, because of its tool
Have the advantages that adjustable aperture, the specific surface area of superelevation, the skeleton structure of multiplicity, surface can introduce modification, has attracted and ground
Study carefully the great interest of personnel, and is widely used in absorption, separation, catalysis, the carrier of metal nanoparticle and supercapacitor
Equal fields, however, the electric conductivity due to ZIF-67 is poor, and poor chemical stability causes frame to be easy in alkaline electrolyte
The disadvantages of collapsing, so that application of the ZIF-67 in terms of supercapacitor is limited by very large.
Summary of the invention
The purpose of the present invention is to provide a kind of raising metal-organic framework material chemical properties in alkaline solution
Method, to solve the problems mentioned in the above background technology.
To achieve the above object, the invention provides the following technical scheme: a kind of raising metal-organic framework material is in alkalinity
The method of chemical property in solution, method the following steps are included:
(1) cobalt nitrate, 2-methylimidazole methanol solution and reproducibility graphene oxide are prepared using in-situ synthesis attached
The metal organic frame on reproducibility graphene oxide, obtain reproducibility graphene oxide/metal organic frame solution；
(2) aluminium isopropoxide is added in distilled water, 25~35min is stirred under 80~100 DEG C of constant temperatures, adjusts solution
PH to 2~5, after the reaction was continued 3h, obtain translucent colloidal sol, dried at being 60~100 DEG C in temperature it is stand-by, then will drying
Obtained powder is uniformly mixed with water, and 10mL dilute nitric acid solution is added after stirring 1h at being 80~100 DEG C in temperature, 80~
2~8h is stirred under 100 DEG C of constant temperatures obtains AlOOH colloidal sol；
(3) the AlOOH colloidal sol prepared in step (2) is had with the reproducibility graphene oxide/metal prepared in step (1)
The mixing of machine frame solution, is vigorously stirred 12~18h, is centrifugated mixed liquor, is rinsed using ethyl alcohol, be placed in and dry at room temperature, obtained
To in reproducibility graphene oxide/metal organic frame/aluminum oxyhydroxide nanometer sheet；
(4) the reproducibility graphene oxide/metal organic frame/aluminum oxyhydroxide nanometer sheet prepared in step (3) is logical
Cross ultrasonic method and be vigorously stirred that method is evenly dispersed in deionized water, add the nickel nitrate stirring 20 of urea and 3mL~
Then mixed solution is placed in autoclave in 80~120 DEG C of 18~30h of reaction, is centrifugated mixed liquor, makes by 30min
It is washed with deionized 3 times, it is sliding that reproducibility graphene oxide/metal organic frame/nickel aluminum water is dried to obtain at 60~80 DEG C
Stone, i.e. electrode material for super capacitor.
Preferably, in cobalt nitrate described in step (1) and the 2-methylimidazole methanol solution 2-methylimidazole mole
Than for 1:1.
Preferably, the quality of aluminium isopropoxide described in step (2) is 10~13g, the powder and the water quality ratio 1:5
~20.
Preferably, the volume of AlOOH colloidal sol described in step (3) is 10~20mL, the reproducibility graphene oxide/gold
The volume for belonging to organic frame solution is 5~10mL.
Preferably, the volume of deionized water described in step (4) is 20~40mL, the quality of the urea is 0.2~
0.5g, the concentration of the nickel nitrate are 0.3~0.5mol/L.
The beneficial effects of the present invention are: a kind of side for improving metal-organic framework material chemical property in alkaline solution
Method, the present invention provides a kind of methods for improving metal-organic framework material chemical property in alkaline solution, only need shorter
Time structural integrity can be made, have excellent performance self-assembled nanometer material, do not need complex device, low in cost, synthesis
Self-assembled nanometer material specific surface area it is big, be evenly distributed, have good inner porosity, excellent chemical property,
Specific capacitance (the 2291.6Fg of superelevation-1), have extended cycle life, good cycling stability, energy density it is high, reproducibility graphene oxide has
Effect improves the conductive capability of ZIF-67, and the cobalt that nickel aluminum hydrotalcite is then used as " sanctuary " Lai Rongna to dissolve from ZIF-67 from
Son, further recombination forms nickel cobalt aluminium ternary hydrotalcite, and the electric conductivity for effectively compensating for ZIF-67 is poor, and in alkaline electrolysis
In liquid the shortcomings that poor chemical stability, such method, which is readily applicable to other unstable metals in alkaline solution, machine frame
Frame or apply the loss that sulphur is prevented in lithium-sulfur cell.
Detailed description of the invention
Fig. 1 is the circle of circulation 2000 prepared by embodiment of the present invention front and back reproducibility graphene oxide/ZIF-67/ nickel aluminum water
The SEM and TEM of talcum scheme；
Fig. 2 is reproducibility graphene oxide/ZIF-67/ nickel after material prepared of the embodiment of the present invention and its circular response
The EDS of aluminum hydrotalcite schemes；
Fig. 3 is reproducibility graphene oxide/ZIF-67/ nickel aluminum hydrotalcite infrared spectroscopy prepared by the embodiment of the present invention
Figure；
Fig. 4 is the figure of reproducibility graphene oxide/ZIF-67/ nickel aluminum hydrotalcite XPS prepared by the embodiment of the present invention；
Fig. 5 is reproducibility graphene oxide/ZIF-67/ nickel aluminum hydrotalcite XRD diagram prepared by the embodiment of the present invention；
Fig. 6 (A)-(D) is reproducibility graphene oxide/ZIF-67/ nickel aluminum hydrotalcite prepared by the embodiment of the present invention
CV figure；
Fig. 7 (A)-(B) is reproducibility graphene oxide/ZIF-67/ nickel aluminum hydrotalcite prepared by the embodiment of the present invention
Permanent charge and discharge cycles stability test figure, Fig. 7 (C) are impedance diagram, and Fig. 7 (D) is cyclical stability figure.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair
The range of bright protection.
Embodiment:
(1) nickel foam is cut into area is 1 × 4cm2Size, then successively spends acetone and deionized water carries out ultrasound and washes
It washs, is dried in vacuo, 5g cobalt nitrate, 5g2- methylimidazole methanol solution and 3g reproducibility graphene oxide are used into in-situ synthesis
Prepare the ZIF-67 being attached on reproducibility graphene oxide；
(2) 11.3g aluminium isopropoxide is added in 100mL distilled water, 30min is stirred under 85 DEG C of constant temperatures, adjusts molten
The pH value of liquid after the reaction was continued 3h, obtains translucent colloidal sol to 3, dried at 80 DEG C it is stand-by, the powder for then obtaining drying with
Water is uniformly mixed with mass ratio 1:20, and 10mL dilute nitric acid solution is added after 1h is stirred at 85 DEG C, continues constant temperature under the conditions of 85 DEG C
Stirring 6h obtains AlOOH colloidal sol；
(3) 6mL prepared in the 20mLAlOOH colloidal sol prepared in step (2) and step (1) is attached to reproducibility oxidation
ZIF-67 solution mixing on graphene, vigorous agitation 12h are centrifugated mixed liquor, are rinsed using ethyl alcohol, be placed in and do at room temperature
It is dry, reproducibility graphene oxide/ZIF-67/ aluminum oxyhydroxide nanometer sheet is synthesized using LBL self-assembly (LBL) technology；
(4) reproducibility graphene oxide made from step (3)/ZIF-67/ aluminum oxyhydroxide nanometer sheet is passed through into ultrasonic method
It is dispersed in the deionized water of 30mL with the method for being vigorously stirred, adds the urea of 0.3g and the nickel nitrate of 3mL0.5mol/L,
Then mixed solution is placed in autoclave at 100 DEG C and heats for 24 hours, be centrifugated mixed liquor, uses by stirring 20 minutes
Deionization is washed 3 times, and dry 12h, obtains product reproducibility graphene oxide/ZIF-67/ nickel aluminum hydrotalcite at 60 DEG C.This reality
The electrochemical property test of electrode material in example is applied using three electrode assemblies, reproducibility graphene oxide/ZIF-67/ nickel aluminum water is sliding
Stone is working electrode, and platinized platinum is saturated calomel as reference electrode, makees electrolyte with KOH solution, test in room as auxiliary electrode
Temperature is lower to be carried out.
With reference to the accompanying drawings and embodiments, the present invention is described further:
As shown in Figure 1, (A1) indicates reaction pre reduction graphene oxide/ZIF-67 SEM, ZIF-67 even compact
It is attached to reproducibility surface of graphene oxide, (A2) indicates reproducibility graphene oxide/ZIF-67 SEM after reaction, by right
Than can be seen that unstability of the ZIF-67 in alkaline solution leads to its structure collapse to form laminated structure；(B1) it indicates
Pre reduction graphene oxide/ZIF-67 TEM is reacted, (B2) indicates reproducibility graphene oxide/ZIF-67 after reaction
TEM, by comparison it can also be seen that cube ZIF-67 after the reaction converted in-situ be it is laminar structured；(C1) indicate anti-
Pre reduction graphene oxide/ZIF-67/ nickel aluminum hydrotalcite TEM is answered, (C2) indicates reproducibility graphene oxide/ZIF- after reaction
The TEM of 67/ nickel aluminum hydrotalcite, by comparison it can be seen that unstability of the ZIF-67 in alkaline solution causes its skeleton to collapse
It collapses, the Co of dissolution2+Recombination forms sheet reproducibility oxygen nickel cobalt aluminum hydrotalcite in nickel aluminum hydrotalcite；
As shown in Fig. 2, reproducibility graphene oxide/ZIF-67/ nickel aluminum hydrotalcite EDS map, it can be seen that Al, Ni,
C, the elements such as O, Co are evenly distributed in reproducibility graphene oxide/ZIF-67/ nickel aluminum hydrotalcite；
As shown in figure 3, reproducibility graphene oxide/ZIF-67/ nickel aluminum hydrotalcite infared spectrum, it can be found that being located at
1690cm-1The C-O key at place, O-H (3440cm in compound-1) and CO3 2-(1420cm-1And 780cm-1) at peak illustrate moisture
Son and CO3 2-Hydrotalcite layers are successfully distributed in, meanwhile, it is located at 800cm-1Absorption peak below is due to metallic atom and oxygen
The group (M-O) of atom；
As shown in figure 4, reproducibility graphene oxide/ZIF-67/ nickel aluminum hydrotalcite XPS map, it can be seen that compound
In have an Al, Ni, C, O, Co element, from spectrogram it can be seen that the spin(-)orbit energy gap of Co2p be 16.1eV (798.16eV and
782.02eV), it was demonstrated that the chemical valence of cobalt ions is divalent, the spin(-)orbit energy gap of A-Co2p (after circular response) before reacting
For 15.4eV (780.07eV and 795.5eV) and 16.7eV (780.07eV and 795.5eV), illustrate there is Co2+And Co3+Mixing
Valence state can be construed to after non-fully Reversible redox reaction, Co2+Fraction part is oxidized to Co3+, and from
It can be seen that the complete Ni later of circular response in other figures2+And Al3+Amount have reduction, result above proves, free Co2+With
Co3+Instead of the Ni of part2+And Al3+, to prove Co2+Successfully it is doped in hydrotalcite；
As shown in figure 5, reproducibility graphene oxide/ZIF-67/ nickel aluminum hydrotalcite XRD diagram, these reproducibilities aoxidize stone
There are two big characteristic diffraction peaks about at 2 θ=24 ° and 44 ° in black alkene, corresponds respectively to typical SP2Hydridization graphitic carbon
(002) and (101) is as can be seen from the figure before circular response, and 2Theta is 11.59 °, and 23.14 °, 34.95 °,
Diffraction maximum at 39.40 °, 46.89 °, 60.85 ° and 62.44 ° respectively corresponds (003) of hydrotalcite, (006), (012),
(015), (018), the characteristic diffraction peak of (110) and (113) crystal face, with going out for the diffraction maximum of standard card JCPDS-15-0087
Peak position is almost the same, in addition, the diffraction maximum of reproducibility graphene oxide and ZIF-67 are in reproducibility graphene oxide/ZIF-
Do not occur in 67/ nickel aluminum hydrotalcite, may be promoted due to hydrotalcite growth in situ reproducibility graphene oxide removing or
Destruction of the ZIF-67 of person's layered laminate graphene and cube in the preparation process of compound, is as can be seen from the figure recycling
Go out peak position after reaction to have occurred and significantly deviate to the left, cell parameter becomes larger, illustrate/nickel aluminum hydrotalcite sample in successfully
It is mixed with Co2+It is self-assembly of ternary hydrotalcite；
If Fig. 6 (A) shows that a pair of redox peaks exist between -0.2 and 0.6V, corresponding OH-With Ni2+/Ni3+Between
The redox reaction of high reversible shows as typical faraday and bears capacitor model, reproducibility graphene oxide/ZIF-67 exhibition
A pair of relatively weak peak is shown, Fig. 6 (C) indicates reproducibility graphene oxide/ZIF-67/ nickel aluminum hydrotalcite image, anode
Positive extreme direction is biased at peak, and cathode peak turns to negative direction, it means that at the interface of electrode and electrolyte relatively low resistance and
Quick redox reaction, with reproducibility graphene oxide/ZIF-67 and reproducibility graphene oxide/nickel aluminum hydrotalcite phase
Than reproducibility graphene oxide/ZIF-67/ nickel aluminum hydrotalcite shows highest specific capacitance and peak point current, it means that higher
Charge storage；
It is electrode material for super capacitor under the current density of 1A/g-10A/g, with 6mol/ shown in (B) such as Fig. 7 (A)
LKOH is the charge-discharge performance test curve of electrolyte solution, aoxidizes stone with reproducibility graphene oxide/ZIF-67 and reproducibility
Black alkene/nickel aluminum hydrotalcite is compared, and reproducibility graphene oxide/ZIF-67/ nickel aluminum hydrotalcite shows highest specific capacitance, is
2291.6F/g, curve have apparent bending, illustrate that energy storage mechnism is that faraday bears capacitor model, with the increase of current density,
Material specific capacitance reduces, but declines gesture and gently illustrate that electrode material has outstanding multiplying power property, and Fig. 7 (C) is shown can this spy's spectrum
Figure, as seen from the figure, the interior resistance ratio of electrode material for super capacitor reproducibility graphene oxide/ZIF-67/ nickel aluminum hydrotalcite
It is smaller, have quick ion and electronics transfer, show good chemical property, Fig. 7 (D) be reproducibility graphene oxide/
ZIF-67/ nickel aluminum hydrotalcite pass through 1000 circle charge-discharge tests, preceding 200 circle when capacitive character slightly promoted, this phenomenon can
To be construed to reproducibility graphene oxide/ZIF-67/ nickel aluminum hydrotalcite converted in-situ as reproducibility graphene oxide/nickel cobalt aluminum water
Talcum still shows biggish specific capacitance by the rear electrode material of 1000 circles, and capacitive character is left 90.3%, fall
It is smaller, illustrate it with good electrochemical stability.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (5)
1. a kind of method for improving metal-organic framework material chemical property in alkaline solution, it is characterised in that: its method
The following steps are included:
(1) cobalt nitrate, 2-methylimidazole methanol solution and reproducibility graphene oxide are attached to using in-situ synthesis preparation
Metal organic frame on reproducibility graphene oxide obtains reproducibility graphene oxide/metal organic frame solution；
(2) aluminium isopropoxide is added in distilled water, 25~35min is stirred under 80~100 DEG C of constant temperatures, adjusts the pH of solution
To 2~5, after the reaction was continued 3h, translucent colloidal sol is obtained, dries stand-by at being 60~100 DEG C in temperature, then obtains drying
Powder be uniformly mixed with water, temperature be 80~100 DEG C at stir 1h after be added 10mL dilute nitric acid solution, at 80~100 DEG C
2~8h is stirred under constant temperature obtains AlOOH colloidal sol；
(3) the reproducibility graphene oxide/metal prepared in the AlOOH colloidal sol prepared in step (2) and step (1) there is into machine frame
The mixing of frame solution, is vigorously stirred 12~18h, is centrifugated mixed liquor, is rinsed using ethyl alcohol, be placed in and dry at room temperature, obtained
Reproducibility graphene oxide/metal organic frame/aluminum oxyhydroxide nanometer sheet；
(4) the reproducibility graphene oxide/metal organic frame/aluminum oxyhydroxide nanometer sheet prepared in step (3) is passed through super
Sound method and it is vigorously stirred that method is evenly dispersed in deionized water, the nickel nitrate for adding urea and 3mL stirs 20~30min, so
Mixed solution is placed in autoclave in 80~120 DEG C of 18~30h of reaction afterwards, mixed liquor is centrifugated, uses deionization
Water washing 3 times, reproducibility graphene oxide/metal organic frame/nickel aluminum hydrotalcite is dried to obtain at 60~80 DEG C.
2. a kind of side for improving metal-organic framework material chemical property in alkaline solution according to claim 1
Method, it is characterised in that: the molar ratio of 2-methylimidazole in cobalt nitrate described in step (1) and the 2-methylimidazole methanol solution
For 1:1.
3. a kind of side for improving metal-organic framework material chemical property in alkaline solution according to claim 1
Method, it is characterised in that: the quality of aluminium isopropoxide described in step (2) is 10~13g, the powder and the water quality ratio 1:5
~20.
4. a kind of side for improving metal-organic framework material chemical property in alkaline solution according to claim 1
Method, it is characterised in that: the volume of AlOOH colloidal sol described in step (3) is 10~20mL, the reproducibility graphene oxide/gold
The volume for belonging to organic frame solution is 5~10mL.
5. a kind of side for improving metal-organic framework material chemical property in alkaline solution according to claim 1
Method, it is characterised in that: the volume of deionized water described in step (4) is 20~40mL, the quality of the urea is 0.2~
0.5g, the concentration of the nickel nitrate are 0.3~0.5mol/L.
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