CN105845458A - Graphene activated metal organic framework electrode material and preparation and applications thereof - Google Patents
Graphene activated metal organic framework electrode material and preparation and applications thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 44
- 239000007772 electrode material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000012621 metal-organic framework Substances 0.000 title abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 34
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000013110 organic ligand Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 4
- 239000003990 capacitor Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000002887 superconductor Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000001994 activation Methods 0.000 description 8
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011883 electrode binding agent Substances 0.000 description 5
- 239000011267 electrode slurry Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 4
- 229940011182 cobalt acetate Drugs 0.000 description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 4
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 4
- 239000013084 copper-based metal-organic framework Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229940078494 nickel acetate Drugs 0.000 description 4
- 239000013384 organic framework Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- -1 graphite Alkene Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000013239 manganese-based metal-organic framework Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
-
- 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
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses graphene activated metal organic framework electrode material and preparation and applications thereof. The preparation method comprises the steps that soluble salt containing metal ions and organic ligands are added in a solvent, and reaction temperature is controlled within 100 DEG C-150 DEG C and maintained for 24h-30h so that MOF structural material is obtained; and the MOF structural material is ultrasonically dispersed in the solvent and then graphene is added, and reaction is performed for 10-60min so that the graphene activated MOF electrode material is prepared. The metal organic framework material has the advantages of being porous, high in specific surface area, adjustable in structure and diverse in structure and is simple in the material preparation process; and the metal organic framework material has excellent cyclic stability and high specific discharge capacity when the metal organic framework material is applied to superconductor electrode material, and specific capacitance is 280F/g and thus stability is great.
Description
Technical field
The present invention relates to electrochemical material technical field, being specifically related to a kind of Graphene activated metal has machine frame
Frame electrode material and preparation thereof and application.
Background technology
Ultracapacitor because it is at high current charge-discharge, the aspect such as have extended cycle life and power density is big prominent
Go out performance so that it is become one of cutting edge technology of national great scientific and technical innovation, new energy field, more by
List in " national medium-term and long-term scientific development and technical development plan outline ", there is important strategy meaning
Justice and realistic meaning.Ultracapacitor can be applied in electronics, portable electronics, electric automobile, space flight
The field such as aviation, defence and military.In ultracapacitor research, carbon-based material specific capacity is less, energy density
Relatively low, the metal oxide materials such as ruthenium base is expensive and toxic limits its commercialization.Therefore, compel
It is essential to prepare and there is height ratio capacity, excellent cyclical stability and eco-friendly Novel super electric capacity
Device electrode material.
Metal-organic framework materials (Metal-Organic-Framework, MOF) be by transition metal from
The crystalline material that sub and organic bridge ligand is constituted, as a kind of novel micropore organometallic polymer,
It has the specific surface area that comparison is high, big porosity, and modulated aperture.Additionally, in MOF
Metal ion redox reaction can occur, produce the contribution to pseudo capacitance, therefore it has
Prestige becomes jumbo electrode material for super capacitor.
At present, some are disclosed using MOF material as the report of electrode material, at patent (CN
105047435 A) in disclose a kind of manganese metallic organic framework electrode material and preparation method thereof, by will
Containing Mn2+Soluble-salt, organic acid and two tooth containing n-donor ligands join and deionized water utilize hydro-thermal
Reaction is prepared for manganese metallic organic framework (Mn-MOF) electrode material, has the chemical property of excellence,
It is up to 242F/g than electric capacity.But the materials conductive performance of this system is poor, causes energy density low, therefore
It is necessary to continue to explore new MOF electrode material.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of Graphene activated metal has
Machine skeleton electrode material and preparation thereof and application.Metal-organic framework materials of the present invention have porous,
The advantages such as specific surface area is big, structure is adjustable, structure diversity, material preparation process is simple；Use it for
During electrode material for super capacitor, there is the cyclical stability of excellence and higher specific discharge capacity, than electricity
Hold up to 280F/g, have good stability.
The main technical schemes of the present invention is:
The first object of the present invention is to provide the system of a kind of Graphene activated metal organic backbone electrode material
Preparation Method, including:
(1) soluble-salt containing metal ion and organic ligand 2,2'-bipyridyl-4,4'-dioctyl phthalate are added
Entering in solvent, stir, be transferred in reactor, reaction temperature is protected at controlling 100 DEG C-150 DEG C
Hold 24h-30h, by centrifugation, wash, be vacuum dried at 80 DEG C-100 DEG C, obtain MOF structural material；
(2) MOF structural material ultrasonic disperse (ultrasonic power in solvent that step (2) is prepared
It is respectively 100W and 40kHz with frequency), it is subsequently adding Graphene, reacts 10-60min, scrubbed,
It is dried, prepares the MOF electrode material of Graphene activation.
Further, the metal ion in described step (1) is Cu2+、Co2+、Ni2+、Fe2+Or Mn2+。
Further, the soluble-salt containing metal ion in described step (1) is acetate.
Further, in a solvent dense of the soluble-salt containing metal ion in described step (1)
Degree is 0.02M；Preferably, the described soluble-salt containing metal ion is nickel acetate, cobalt acetate or vinegar
Acid copper；Most preferably cobalt acetate.
Further, the solvent in described step (1) is selected from DMF, NMP, DMSO, deionization
The mixing of the one or two kinds of in water.
Further, the soluble-salt containing metal ion in described step (1) and organic ligand 2,2'-
The mol ratio of bipyridyl-4,4'-dioctyl phthalate is 5:1～1:5.
Further, the solvent in described step (2) is deionized water.
Further, the Graphene in described step (2) is graphene oxide or the number of plies going back less than 10
Former graphene powder.
Further, the mass ratio of the MOF structural material in described step (2) and Graphene is
5:1～200:1；Preferably, the mass ratio of MOF structural material and Graphene is 10:1～100:1.
The second object of the present invention is to provide a kind of Graphene activation gold being prepared gained by said method
Belong to organic backbone electrode material.
It is still another object of the present invention to provide above-mentioned Graphene activated metal organic backbone electrode material to exist
Prepare the application in ultracapacitor.
The electrode material that the present invention provides is metal-organic framework materials (MOF), in order to improve material
Electric conductivity, utilizes Graphene to carry out activation and reduces electrode material internal resistance.This metal-organic framework material
Monomer component is 2,2'-bipyridyl-4,4'-dioctyl phthalate, and this part can be coordinated bonding with many kinds of metal ions.
Compared with prior art, Graphene activated metal organic backbone electrode material prepared by the present invention, with
Time possessed the function of MOF material and Graphene, both there is bigger specific surface area, aperture is adjustable,
Electric conductivity is also superior to same type of material simultaneously, is applied to ultracapacitor and shows high specific capacity, and energy is close
Degree is big, and cyclical stability is good.
Accompanying drawing explanation
Fig. 1 is MOF material N in embodiment 12Adsorption/desorption isotherms；
Fig. 2 is the Ni-MOF crystal structure figure in embodiment 1；
Fig. 3 is ultracapacitor cycle performance figure in embodiment 2.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out
Clearly and completely describe, it is clear that described embodiment is only a part of embodiment of the present invention, and not
It it is whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under creative work premise, broadly falls into the scope of protection of the invention.
Embodiment 1
Weigh 1mmol nickel acetate, 1mmol 2,2'-bipyridyl-4,4'-dioctyl phthalate organic ligand and 50mL respectively
DMF solution stirs, and is transferred in reactor, and reaction temperature keeps 24h, warp at controlling 120 DEG C
Cross centrifuge washing, be vacuum dried at 85 DEG C, obtain Ni-MOF structural material, by test N2Absorption
It is 1869m that desorption isotherm obtains BET2/g.As in figure 2 it is shown, Ni-MOF is along the crystalline substance in [100] direction
Body structure chart, it can be seen that 2,2'-bipyridyl-4, it is parallel that 4'-dioctyl phthalate organic ligand is parallel to (010) crystal face
Stacking, and be firmly coordinated with nickel acetate.
Weigh 2.0g above-mentioned Ni-MOF structural material and put in beaker, add 40mL deionized water and carry out
Ultrasonic wave dispersion (ultrasonic power and frequency are respectively 100W and 40kHz), adds 100mg graphite
Alkene, ultrasonic reaction 30min, it is dried process through washing and obtains the organic bone of metal of Graphene activation process
Frame electrode material GNS--Ni-MOF.
By GNS--Ni-MOF electrode material, binding agent and conductive black according to the quality of 85:10:5
Ratio is dispersed in NMP, is then coated onto in nickel foam by twin rollers by electrode slurry, utilizes 3M
The KOH aqueous solution assemble button cell as electrolyte, battery performance test equipment is that blue electricity battery is surveyed
Examination instrument, potential region is 0～1.0V, and specific capacity is 248F/g after tested.
Comparative example 1
Weigh 1mmol nickel acetate, 1mmol 2,2'-bipyridyl-4,4'-dioctyl phthalate organic ligand and 50mL respectively
DMF solution stirs, and is transferred in reactor, and reaction temperature keeps 24h, warp at controlling 120 DEG C
Cross centrifuge washing, be vacuum dried at 85 DEG C, obtain Ni-MOF structural material.
By prepared Ni-MOF electrode material, binding agent and conductive black according to the quality of 85:10:5
Ratio is dispersed in NMP, is then coated onto in nickel foam by twin rollers by electrode slurry, utilizes 3M
The KOH aqueous solution assemble button cell as electrolyte, battery performance test equipment is that blue electricity battery is surveyed
Examination instrument, potential region is 0～1.0V, and specific capacity is 224F/g after tested.
Embodiment 2
Weigh 1mmol cobalt acetate, 1mmol 2,2'-bipyridyl-4,4'-dioctyl phthalate organic ligand and 50mL respectively
DMF solution stirs, and is transferred in reactor, and reaction temperature keeps 24h, warp at controlling 120 DEG C
Cross centrifuge washing, be vacuum dried at 85 DEG C, obtain Co-MOF structural material.
Weigh 2.0g above-mentioned Co-MOF structural material and put in beaker, add 40mL deionized water and carry out
Ultrasonic wave dispersion (ultrasonic power and frequency are respectively 100W and 40kHz), adds 20mg graphite
Alkene, ultrasonic reaction 30min, it is dried process through washing and obtains the organic bone of metal of Graphene activation process
Frame electrode material GNS--Co-MOF.
By GNS--Co-MOF electrode material, binding agent and conductive black according to the quality of 85:10:5
Ratio is dispersed in NMP, is then coated onto in nickel foam by twin rollers by electrode slurry, utilizes 3M
The KOH aqueous solution assemble button cell as electrolyte, battery performance test equipment is that blue electricity battery is surveyed
Examination instrument, potential region is 0～1.0V, and specific capacity can reach 280F/g after tested.
Ultracapacitor cycle performance prepared by the present embodiment is as it is shown on figure 3, front 100 primary current density
0.1A/g, current density 1.0A/g after 100 times.
Embodiment 3
Weigh 1mmol copper acetate, 2mmol 2,2'-bipyridyl-4,4'-dioctyl phthalate organic ligand and 50mL respectively
Nmp solution stirs, and is transferred in reactor, and reaction temperature keeps 24h, warp at controlling 120 DEG C
Cross centrifuge washing, be vacuum dried at 85 DEG C, obtain Cu-MOF structural material.
Weigh 2.0g above-mentioned Cu-MOF structural material and put in beaker, add 40mL deionized water and carry out
Ultrasonic wave dispersion (ultrasonic power and frequency are respectively 100W and 40kHz), adds 40mg oxidation
Graphene GO (mass fraction of graphene oxide solution is 1.0%), ultrasonic reaction 30min, pass through
Washing is dried and processes the metallic organic framework electrode material GO--Cu-MOF obtaining Graphene activation process.
By GO--Cu-MOF electrode material, binding agent and conductive black according to the mass ratio of 85:10:5
It is dispersed in NMP, then electrode slurry is coated onto in nickel foam by twin rollers, utilizes 3M's
The KOH aqueous solution assembles button cell as electrolyte, and battery performance test equipment is blue electricity battery testing
Instrument, potential region is 0～1.0V, and specific capacity is 232F/g after tested.
Embodiment 4
Weigh 1mmol manganese acetate, 4mmol 2,2'-bipyridyl-4,4'-dioctyl phthalate organic ligand and 50mL respectively
Nmp solution stirs, and is transferred in reactor, and reaction temperature keeps 24h, warp at controlling 120 DEG C
Cross centrifuge washing, be vacuum dried at 85 DEG C, obtain Mn-MOF structural material.
Weigh 2.0g above-mentioned Mn-MOF structural material and put in beaker, add 40mL deionized water and enter
Row ultrasonic wave dispersion (ultrasonic power and frequency are respectively 100W and 40kHz), adds 50mg oxygen
Functionalized graphene (mass fraction of graphene oxide solution is 1.0%), ultrasonic reaction 30min, Jing Guoxi
Wash to be dried and process the metallic organic framework electrode material GO--Mn-MOF obtaining Graphene activation process.
By GO--Mn-MOF electrode material, binding agent and conductive black according to the mass ratio of 85:10:5
It is dispersed in NMP, then electrode slurry is coated onto in nickel foam by twin rollers, utilizes 3M's
The KOH aqueous solution assembles button cell as electrolyte, and battery performance test equipment is blue electricity battery testing
Instrument, potential region is 0～1.0V, and specific capacity is 253F/g after tested.
Compare with embodiment through above-mentioned comparative example and understand, through Graphene activation process electrode material conductance
Rate strengthens, and utilizes cobalt acetate best as the effect of metal ion in embodiment 2, and specific capacity can reach
280F/g, stable circulation is good.
Claims (10)
1. a preparation method for Graphene activated metal organic backbone electrode material, including:
(1) soluble-salt containing metal ion and organic ligand 2,2'-bipyridyl-4,4'-dioctyl phthalate are added
In solvent, stirring, be transferred in reactor, reaction temperature keeps at controlling 100 DEG C-150 DEG C
24h-30h, by centrifugation, washs, is vacuum dried, obtains MOF structural material at 80 DEG C-100 DEG C；
(2) the MOF structural material ultrasonic disperse in solvent step (1) prepared, is subsequently adding stone
Ink alkene, reacts 10-60min, scrubbed, dry, prepares the MOF electrode material of Graphene activation.
The preparation of a kind of Graphene activated metal organic backbone electrode material the most according to claim 1
Method, it is characterised in that: the metal ion in described step (1) is Cu2+、Co2+、Ni2+、Fe2+
Or Mn2+。
The preparation of a kind of Graphene activated metal organic backbone electrode material the most according to claim 1
Method, it is characterised in that: the soluble-salt containing metal ion in described step (1) is acetate.
The preparation of a kind of Graphene activated metal organic backbone electrode material the most according to claim 1
Method, it is characterised in that: the soluble-salt containing metal ion in described step (1) is in a solvent
Concentration is 0.02M.
The preparation of a kind of Graphene activated metal organic backbone electrode material the most according to claim 1
Method, it is characterised in that: the solvent in described step (1) includes DMF, NMP, DMSO, goes
The mixing of the one or two kinds of in ionized water.
The preparation of a kind of Graphene activated metal organic backbone electrode material the most according to claim 1
Method, it is characterised in that: the soluble-salt containing metal ion in described step (1) and organic ligand
The mol ratio of 2,2'-bipyridyl-4,4'-dioctyl phthalate is 5:1～1:5.
The preparation of a kind of Graphene activated metal organic backbone electrode material the most according to claim 1
Method, it is characterised in that: the Graphene in described step (2) is that graphene oxide or the number of plies are less than 10
Reduced graphene powder.
The preparation of a kind of Graphene activated metal organic backbone electrode material the most according to claim 1
Method, it is characterised in that: MOF structural material and the mass ratio of Graphene in described step (2) are
5:1～200:1.
9. the method used described in any one of claim 1-8 prepares the Graphene activated metal of gained
Organic backbone electrode material.
Graphene activated metal organic backbone electrode material the most according to claim 9 is super in preparation
Application in level capacitor.
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN106935825A (en) * | 2017-03-21 | 2017-07-07 | 桂林电子科技大学 | A kind of graphene oxide/metal organic frame composite and its preparation method and application |
| CN108080034A (en) * | 2017-12-29 | 2018-05-29 | 济南大学 | One kind is based on Ni-based 3-dimensional metal organic framework method for preparing catalyst and application |
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| CN108441982A (en) * | 2018-02-13 | 2018-08-24 | 浙江工业大学 | A kind of preparation method of graphene/metal organic frame composite fibre |
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| CN109364995A (en) * | 2018-11-01 | 2019-02-22 | 安阳师范学院 | High dispersive graphene/Fe Base Metal organic framework composite material electrochemical sensor preparation method and application |
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| CN110350184A (en) * | 2019-06-26 | 2019-10-18 | 五邑大学 | A kind of high capacity NiMoO for cell positive material4The preparation method of energy storage material |
| CN110350184B (en) * | 2019-06-26 | 2022-07-19 | 五邑大学 | Preparation method of high-capacity NiMoO4 energy storage material for battery positive electrode material |
| CN110335762A (en) * | 2019-07-09 | 2019-10-15 | 南京邮电大学 | A kind of preparation of GO/Cu-HHTP composite material and its application in electrochemical energy storage |
| CN110387099A (en) * | 2019-07-18 | 2019-10-29 | 华南理工大学 | A kind of tealeaf residue graphene-CuCeMOF-PVB composite material and preparation method and application |
| WO2021007990A1 (en) * | 2019-07-18 | 2021-01-21 | 华南理工大学 | Tea leaf dregs graphene-cucemof-pvb composite material and preparation method and application therefor |
| CN110358235A (en) * | 2019-07-18 | 2019-10-22 | 华南理工大学 | A kind of passion fruit shell graphene-CeMOF-PVB composite material and preparation method and application |
| CN110420661A (en) * | 2019-08-15 | 2019-11-08 | 山东大学 | In-situ preparation MIL-101 (Fe) composite catalyzing material and the preparation method and application thereof on a kind of 3D-rGO |
| CN111085275A (en) * | 2019-12-31 | 2020-05-01 | 华南理工大学 | Reductive graphene oxide/metal organic framework composite material and preparation method and application thereof |
| CN111477471A (en) * | 2020-04-25 | 2020-07-31 | 榆林学院 | Preparation method of coal tar-based electrode material |
| CN111710529B (en) * | 2020-05-20 | 2022-04-05 | 上海应用技术大学 | Co/Mn-MOF/nitrogen-doped carbon-based composite material and preparation method and application thereof |
| CN111710529A (en) * | 2020-05-20 | 2020-09-25 | 上海应用技术大学 | Co/Mn-MOF/nitrogen-doped carbon-based composite material and preparation method and application thereof |
| CN111704732A (en) * | 2020-06-28 | 2020-09-25 | 南京工业大学 | Metal organic framework loaded graphene microspheres and preparation method and application thereof |
| CN112403440B (en) * | 2020-11-18 | 2022-03-18 | 山西大学 | Magnetic recyclable CoNi-MOFs @ GR adsorbent, preparation method and application to adsorption of organic dye |
| CN112403440A (en) * | 2020-11-18 | 2021-02-26 | 山西大学 | Magnetic recyclable CoNi-MOFs @ GR adsorbent, preparation method and application to adsorption of organic dye |
| CN114023960A (en) * | 2021-10-20 | 2022-02-08 | 上海大学(浙江·嘉兴)新兴产业研究院 | Metal coordination polymer organic positive electrode material and preparation method thereof |
| CN114188523A (en) * | 2021-12-13 | 2022-03-15 | 中南大学 | Graphene-loaded vanadium pentoxide composite material, preparation method thereof and application thereof in water-based zinc ion battery |
| CN114188523B (en) * | 2021-12-13 | 2024-02-02 | 中南大学 | Graphene-supported vanadium pentoxide composite material, preparation method thereof and application thereof in water-based zinc ion battery |
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