CN105977040A - Metal organic skeleton electrode material of supercapacitor and preparation method of the electrode material - Google Patents
Metal organic skeleton electrode material of supercapacitor and preparation method of the electrode material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses metal organic skeleton electrode material of a supercapacitor and a preparation method of the electrode material. According to the metal organic skeleton electrode material of the supercapacitor, two different transition metal ions and organic ligands are prepared according to a certain mole and added to an anhydrous N,N-dimethyl formamide (DMF) organic solvent to be mixed, and bimetal MOFs is obtained through an oil bath heating reaction. The structure is decomposed, and unstable MOFs of bimetal MOFs is removed so that another stable HP-MOFs is obtained, and HP-MOFs can be used as the organic skeleton electrode material of the supercapacitor. The advantages of the organic skeleton electrode material of the supercapacitor are that the material has the advantages of high stability and large specific area and is hierarchical and porous. Besides, the method has advantages of being simple in technological process without high temperature and high voltage, high in operability, less in material consumption, high in yield rate and low in cost.
Description
Technical field
The present invention relates to technical field of electrochemistry, particularly with regard to being applied to the electrode material of ultracapacitor, tool
Body says it is metallic organic framework electrode material and the preparation method of this electrode material of a kind of ultracapacitor.
Background technology
Ultracapacitor, also referred to as electrochemical capacitor, be a kind of electrification between traditional capacitor and secondary cell
Learning energy storage device, its capacity is up to the most thousand of hundreds of farads.Compared to current rechargeable battery, ultracapacitor has ratio
The outstanding advantage such as energy height, specific power height, operating temperature range width, length in service life.At present, ultracapacitor is as storage
Can apply at hybrid-power bus by parts, extended-range electric bus, fuel cell car, urban track traffic, pure electronic
On automobile, main and other energy members parallel operations, it is provided that the high power of vehicle launch demand.For ultracapacitor, electricity
The effect of pole can not be substituted, and what current electrode material existed technical problem is that the sides such as specific surface area, electrical conductivity and chemical stability
Face, in order to strengthen the practicality of ultracapacitor, improves electrode material very urgent.
Metal organic frame (MOFs) be the novel nano porous that recently occurs can the material of 26S Proteasome Structure and Function of cutting.
Under normal circumstances, the aperture of MOFs material is respectively less than 2 nm, is limiting down their actual application.Although
There is certain methods can prepare the MOFs of large hole gap, but synthesis has height structural controllability and the layering porous of stability
MOFs(HP-MOFs) remain highly difficult.
At present, it is single metal MOFs that metal organic frame the most not only limits to, and a lot of bimetallic MOFs are successfully closed
Become.Such as, and manganese (Mn)-cobalt (Co) bimetallic MOFs [New Journal of Chemistry, 2016,40 (6): 5531-
5536.] and nickel (Ni)-cobalt (Co) bimetallic MOFs [Advanced Functional Materials, 2016,26 (7):
1098-1103.] all it is successfully synthesized, and it is applied to absorption and lithium battery energy storage battery field.The bimetallic MOFs of present invention synthesis,
One of which MOFs is more stable, and another kind of MOFs (acid, alkali or aqueous solution) structure under certain condition can be disintegrated.Such as:
Although MOF-5 is stable at some solvents, but water and acid can cause subsiding and decomposing of its structure, and this is to have been demonstrate,proved
Real [Physical Chemistry Chemical Physics, 2008,10 (32): 4732-4739].On the contrary, one
A little MOFs but have chemistry, heat and mechanical stability, as UiO-66 (Zr), even it can keep its structural stability to exist
In acid solution.These difference in stability can be utilized, synthesize bimetallic MOFs, make one of which by certain condition
MOFs structure is disintegrated, thus realizes increasing MOFs aperture and the purpose of surface area.
Summary of the invention
One of the technical problem to be solved in the present invention is to provide the organic backbone electrode material of a kind of ultracapacitor, should
Electrode material is a kind of transition metal organic backbone electrode material, has good stability and to have layering porous, specific surface area big
Advantage.
The two of the technical problem to be solved in the present invention are to provide the organic backbone electrode material of a kind of above-mentioned ultracapacitor
Preparation method.It is simple that the method has technical process, it is not necessary to High Temperature High Pressure, workable, and material consumption is few, and yield is high, becomes
This low advantage.
One of technical solution of the present invention:
The organic backbone electrode material of a kind of ultracapacitor, it is characterised in that pressed by two kinds of transition metal ionss, organic ligands
It is 1 0.1 ~ 5 0.5 ~ 10 to configure in molar ratio, joins in anhydrous DMF (DMF) organic solvent mixed
Close, join in anhydrous DMF organic solvent and mix, obtain above two transition gold through oil bath reacting by heating
The bimetallic MOFs belonged to, and make its structure disintegrate, remove wherein unstable MOFs, thus obtain another kind of stable
HP-MOFs, this HP-MOFs are the organic backbone electrode material that can be used for high-performance super capacitor.
Preferred as technique scheme,
Two kinds of described transition metal ionss are preferable over each group of Zn-Zr, Fe-Zr, Ni-Zr, Mn-Zr, Zn-Co, Fe-Co, Mn-Co
In conjunction one group.
Described organic ligand is p-phthalic acid, phthalic acid, benzoic acid, trimesic acid and derivant thereof or two
Methylimidazole. and derivant thereof.
The two of the technical solution of the present invention:
The preparation method of the organic backbone electrode material of above-mentioned ultracapacitor, specifically includes following steps:
1. it is 1 0.1 ~ 5 0.5 ~ 10 according to mol ratio, weighs the slaine of two kinds of different transition metal ionss and organic respectively
Two kinds of transition metal salts and organic ligand are joined in anhydrous DMF (DMF) and at ultrasound wave by part
Reason, is transferred to flask by solution after supersound process, at 80 DEG C ~ 200 DEG C constant temperature oil bath reacting by heating 12 ~ 48h；
2. be cooled to room temperature, by gained solution centrifugal, and with anhydrous DMF (DMF) and if acetone clean
Dry time, obtain bimetallic mixing MOFs；
3. above-mentioned bimetallic mixing MOFs is placed in the strong acid of pH=1, stirs 30 ~ 60min, by centrifugation, wash so that it is structure
Disintegrating, after removing wherein unstable MOFs, vacuum dried obtain HP-MOFs, this HP-MOFs is and can be used as high property
The organic backbone electrode material of energy ultracapacitor.
Compared with prior art, the invention have the advantages that
It is big that layering Porous transition metal organic backbone electrode material the most of the present invention has layering porous, specific surface area
Advantage, its specific surface area is up to 874 m2/g。
Bath oiling the most of the present invention is simple and practical, it is not necessary to High Temperature High Pressure.
3. the transition metal organic framework material prepared by the present invention has excellence as electrode material for super capacitor
High rate performance, cyclical stability and higher energy density.The layering Porous transition metal organic backbone prepared by the present invention
After material mixes with mass ratio 7:2:1 with conductive black and politef (PVDF), it is slurred with N-first class two ketopyrrolidine
Material is also uniformly coated onto nickel foam surface, and as working electrode after 80 DEG C of dry 12h, platinized platinum is as to electrode, hydrargyrum-mercury oxide
For reference electrode, electrolyte is 6M potassium hydroxide solution, uses three-electrode system, test voltage window 0.1 ~ 0.6V, tester
Device is Shanghai occasion China CHI 660C electrochemical workstation.It is 0.1A/g in electric current density, is up to 1114F/g than electric capacity.By this
The HP-MOFs of invention preparation is as positive electrode, and commercialization Graphene is negative material, assembles Asymmetric Supercapacitor, electricity
Pressure window is 0 ~ 1.6V, and test instrunment is Shanghai occasion China CHI 660C electrochemical workstation, electric discharge ratio under 0.3A/g constant current
Electric capacity is more than 100F/g, energy density 32W/Kg, power density 240Wh/Kg.
Detailed description of the invention
Embodiment 1:
Zn-Zr bimetallic MOFs prepares HP-MOFs, specifically comprises the following steps that
1., according to mol ratio 1 0.1 0.5, accurately weigh 2.33 g Zirconium tetrachloride., 0.29 g zinc nitrate hexahydrate and 0.83 g
P-phthalic acid, after joining in the beaker filling 400 mL dry DMF, ultrasonic 30min, it is transferred to the solution in beaker burn
Bottle, heats magnetic agitation reaction 12h in 180 DEG C of oil bath pans；
2. it is cooled to room temperature, by gained solution centrifugal, and cleans several times with dry DMF and acetone, obtain the double gold of Zn-Zr
Belong to MOFs；
3. gained Zn-Zr bimetallic MOFs is placed in the strength hydrochloric acid of 100 mL pH=1, magnetic agitation 30min, after being centrifuged,
By gained solid respectively with DMF and washing with acetone.Last products therefrom is dried in 60 DEG C of baking ovens, obtains HP-MOFs.
Under electric current density is 0.1A/g, this material discharging is 960 F/g than electric capacity.
Embodiment 2:
Fe-Zr bimetallic MOFs prepares HP-MOFs, specifically comprises the following steps that
1., according to mol ratio 1 0.5 1.5, accurately weigh 2.33 g Zirconium tetrachloride., 1.35 g ferric chloride hexahydrates and 2.49g adjacent
Phthalic acid, after adding in the beaker filling 400 mL dry DMF, ultrasonic 30min, the solution in beaker is transferred to flask,
Magnetic agitation reaction 24h is heated in 180 DEG C of oil bath pans；
2. it is cooled to room temperature, by gained solution centrifugal, and cleans several times with dry DMF and acetone, obtain the double gold of Fe-Zr
Belong to MOFs；
3. gained Fe-Zr bimetallic MOFs is placed in the strong nitric acid of 100 mL (pH=1), magnetic agitation 30min, after being centrifuged, will
Gained solid is respectively with DMF and washing with acetone.Last products therefrom is dried in 60 DEG C of baking ovens, obtains HP-MOFs.
Under electric current density is 0.1A/g, this material discharging is 888F/g than electric capacity.
Embodiment 3:
Ni-Zr bimetallic MOFs prepares HP-MOFs, specifically comprises the following steps that
1., according to mol ratio 115, accurately weigh 2.33g Zirconium tetrachloride., 2.37g Nickel dichloride hexahydrate and 8.3 g benzoic acid,
Join in the beaker filling 400 mL dry DMF, ultrasonic 30 min, the solution in beaker is transferred to flask, in 180 DEG C of oil
Bath heats magnetic agitation reaction 36h；
2. it is cooled to room temperature, by gained solution centrifugal, and cleans several times with DMF and acetone, obtain Ni-Zr bimetallic
MOFs；
3. gained Ni-Zr bimetallic MOFs is placed 100 mL HCl(pH=1) in, magnetic agitation 30min, after being centrifuged, by institute
Obtain solid respectively with dry DMF and washing with acetone.Last products therefrom is dried in 60 DEG C of baking ovens, obtains HP-MOFs.
Under electric current density is 0.1A/g, this material discharging is 823 F/g than electric capacity.
Embodiment 4:
Co-Zr bimetallic MOFs prepares HP-MOFs, specifically comprises the following steps that
1., according to mol ratio 123, accurately weigh 2.33g Zirconium tetrachloride., 2.37g cobalt chloride hexahydrate and 6.3 g equal benzene front three
Acid, joins in the beaker filling 400 mL dry DMF, and the solution in beaker is transferred to flask, in 180 by ultrasonic 30 min
DEG C oil bath pan heats magnetic agitation reaction 48h；
2. it is cooled to room temperature, by gained solution centrifugal, and cleans several times with DMF and acetone, obtain Co-Zr bimetallic
MOFs；
3. gained Co-Zr bimetallic MOFs is placed 100 mL HCl(pH=1) in, magnetic agitation 30min, after being centrifuged, by institute
Obtain solid respectively with dry DMF and washing with acetone.Last products therefrom is dried in 60 DEG C of baking ovens, obtains HP-MOFs.
Under electric current density is 0.1A/g, this material discharging is 657 F/g than electric capacity.
Embodiment 5:
Mn-Zr bimetallic MOFs prepares HP-MOFs, specifically comprises the following steps that
1., according to mol ratio 138, accurately weigh 2.33g Zirconium tetrachloride., 5.97 g tetra-chloride hydrate manganese and 13.3 g to benzene two
Formic acid, joins in the beaker filling 400 mL dry DMF, and the solution in beaker is transferred to flask by ultrasonic 30 min, in
180 DEG C of oil bath pans heat magnetic agitation reaction 24h；
2. it is cooled to room temperature, by gained solution centrifugal, and cleans several times with dry DMF and acetone, obtain the double gold of Mn-Zr
Belong to MOFs；
3. gained Mn-Zr bimetallic MOFs is placed 100 mL HCl(pH=1) in, magnetic agitation 30min, after being centrifuged, by institute
Obtain solid respectively with DMF and washing with acetone.Last products therefrom is dried in 60 DEG C of baking ovens, obtains HP-MOFs.
Under electric current density is 0.1A/g, this material discharging is 646 F/g than electric capacity.
Embodiment 6:
Mn-Co bimetallic MOFs prepares HP-MOFs, specifically comprises the following steps that
1., according to mol ratio 123, accurately weigh 2.91 g cabaltous nitrate hexahydrates, 1.97 g tetra-chloride hydrate manganese and 2.46 g
Methylimidazole, joins in the beaker filling 400 mL dry DMF, ultrasonic 30min, is transferred to the solution in beaker burn
Bottle, heats magnetic agitation reaction 48h in 180 DEG C of oil bath pans；
2. it is cooled to room temperature, by gained solution centrifugal, and cleans several times with dry DMF and acetone, obtain the double gold of Mn-Co
Belong to MOFs；
3. gained Mn-Co bimetallic MOFs is transferred to 100 mL HCl(pH=1) in, magnetic agitation 30min, after being centrifuged, will
Gained solid is respectively with DMF and washing with acetone.Last products therefrom is dried in 60 DEG C of baking ovens, obtains HP-MOFs.
Under electric current density is 0.1A/g, this material discharging is 726F/g than electric capacity.
Embodiment 7:
Zn-Co bimetallic MOFs prepares HP-MOFs, specifically comprises the following steps that
1., according to mol ratio 112, accurately weigh 2.37g cabaltous nitrate hexahydrate, 2.97 g zinc nitrate hexahydrates and 1.64 g bis-
Methylimidazole., joins in the beaker filling 400 mL dry DMF, and the solution in beaker is transferred to flask by ultrasonic 30min,
Magnetic agitation reaction 12h is heated in 180 DEG C of oil bath pans；
2. it is cooled to room temperature, by gained solution centrifugal, and cleans several times with DMF and acetone, obtain
Zn-Co bimetallic mixing MOFs；
3. gained Zn-Co bimetallic MOFs is transferred to 100 mL HCl(pH=1) in, magnetic agitation 30min, after being centrifuged, will
Gained solid is respectively with DMF and washing with acetone.Last products therefrom is dried in 60 DEG C of baking ovens, obtains HP-MOFs.
Under electric current density is 0.1A/g, this material discharging is 1031F/g than electric capacity.
Embodiment 8:
Fe-Co bimetallic mixing MOFs prepares HP-MOFs, specifically comprises the following steps that
1., according to mol ratio 15 10, accurately weigh 2.37 g cabaltous nitrate hexahydrates, 13.5 g ferric chloride hexahydrates and 8.2 g
Methylimidazole, joins in the beaker filling 400 mL dry DMF, ultrasonic 30min, is transferred to the solution in beaker burn
Bottle, heats magnetic agitation reaction 36h in 180 DEG C of oil bath pans；
2. it is cooled to room temperature, by gained solution centrifugal, and cleans several times with dry DMF and acetone, obtain the double gold of Fe-Co
Belong to MOFs；
3. gained Fe-Co bimetallic mixing MOFs is transferred to 100 mL HCl(pH=1) in, magnetic agitation 30min, centrifugal
After, by gained solid respectively with DMF and washing with acetone.Last products therefrom is dried in 60 DEG C of baking ovens, obtains HP-MOFs.
Under electric current density is 0.1A/g, this material discharging is 768F/g than electric capacity.
Above content is to combine concrete preferred implementation further description made for the present invention, it is impossible to assert
Being embodied as of the present invention is confined to these explanations.For general technical staff of the technical field of the invention,
Substitute or obvious modification without departing from making some equivalents on the premise of present inventive concept, and performance or purposes are identical, then should
It is considered as belonging to the protection domain that claims that the present invention submitted to determine.
Claims (5)
1. the organic backbone electrode material of a ultracapacitor, it is characterised in that be with organic by two kinds of transition metal ionss
Part is 1 0.1 ~ 5 0.5 ~ 10 to configure in molar ratio, joins in anhydrous DMF organic solvent mixed
Close, obtain the bimetallic MOFs of above two transition metal through oil bath reacting by heating, and make its structure disintegrate, remove wherein
Unstable MOFs, thus obtain another kind of stable HP-MOFs, this HP-MOFs and be and can be used for high-performance super capacitor
Organic backbone electrode material.
The organic backbone electrode material of a kind of ultracapacitor the most as claimed in claim 1, it is characterised in that described two kinds
Transition metal ions is preferable over one group during Zn-Zr, Fe-Zr, Ni-Zr, Mn-Zr, Zn-Co, Fe-Co, Mn-Co respectively combine.
The organic backbone electrode material of a kind of ultracapacitor the most as claimed in claim 1, it is characterised in that described is organic
Part is p-phthalic acid, phthalic acid, benzoic acid, trimesic acid and derivant thereof or methylimidazole and derives
Thing.
4. a preparation method for the organic backbone electrode material of the ultracapacitor described in claim 1, specifically includes following
Step:
(1) it is 1 0.1 ~ 5 0.5 ~ 10 according to mol ratio, weighs the slaine of two kinds of different transition metal ionss and organic respectively
Two kinds of transition metal salts and organic ligand are joined in anhydrous DMF organic solvent and mix and ultrasonic by part
Process, solution after supersound process is transferred to flask, at 80 DEG C ~ 200 DEG C constant temperature oil bath reacting by heating 12 ~ 48h；
(2) it is cooled to room temperature, by gained solution centrifugal, and cleans several times with anhydrous DMF and acetone,
Obtain bimetallic MOFs；
(3) gained bimetallic MOFs is transferred in the strong acid solution of pH=1, stirs 30 ~ 60min, by centrifugation, wash so that it is
Structure is disintegrated, and after removing wherein unstable MOFs, vacuum dried obtains HP-MOFs.
5. the preparation method of organic backbone electrode material as claimed in claim 4, it is characterised in that described pH=1's is strong
Acid, this strong acid includes hydrochloric acid, nitric acid, sulphuric acid, perchloric acid, Fluohydric acid., hydroiodic acid.
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