CN107195473B - A kind of preparation method of two dimension club shaped structure vanadium metal organic backbone electrode material - Google Patents
A kind of preparation method of two dimension club shaped structure vanadium metal organic backbone electrode material Download PDFInfo
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- CN107195473B CN107195473B CN201710627766.6A CN201710627766A CN107195473B CN 107195473 B CN107195473 B CN 107195473B CN 201710627766 A CN201710627766 A CN 201710627766A CN 107195473 B CN107195473 B CN 107195473B
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Abstract
A kind of preparation method of two dimension club shaped structure vanadium metal organic backbone electrode material, belongs to the production technical field of electrode material for super capacitor.The para-phthalic sodium of the vanadic sulfate of preheating and preheating is dissolved in N, dinethylformamide, then mixture is heated to reflux to react, the solid phase that negating should generate is dried in vacuo after being washed with methanol, obtains two-dimentional club shaped structure vanadium metal organic backbone electrode material.Using easily synthetic method is heated to reflux, raw material is easy to get the present invention, equipment cost is cheap, easy to operate, time-consuming short.Compared with prior art, preparation method is simple, is suitable for large-scale production, while prepared material has good cyclical stability.
Description
Technical field
The invention belongs to the production technical fields of electrode material for super capacitor.
Background technique
The energy be the mankind depend on for existence, society and sustainable economic development material base.In recent years, with society and warp
The high speed development of Ji, people increasingly increase the demand of the energy, consume in the production of the mankind, life process and largely can not
Regenerated fossil energy, such as: coal, petroleum, natural gas, while some toxic, pernicious gases and greenhouse gases are produced, it causes
Serious energy crisis and environmental problem so that the living environment of the mankind receive it is serious threaten, society and it is economical can
Sustainable development is faced with formidable challenges.In face of the crisis of fossil energy exhaustion, finds novel alternative energy source and improve depositing for the energy
Storage and utilization efficiency have become very urgent project.
Supercapacitor is a kind of novel energy memory device between battery and traditional capacitor, and traditional quiet
Electric capacitor is compared with battery, and supercapacitor is high with power density, charge-discharge velocity is fast, good cycling stability, uses temperature
Spend the features such as range is wide, highly-safe, environmental-friendly low with maintenance cost.Supercapacitor is once appearance just by the wide of people
General concern, the application succeeded in numerous areas, as: serving as memory stick, laptop, timer electronic product
Backup power supply, the accessory power supply of main power source, solar battery as electronic toy.With electric car and oil electricity or pneumoelectric
The rise and development of hybrid vehicle research, supercapacitor and all kinds of power batteries are answered with the use of composition composite power source
It is used for the activation system of automobile, or directly as the electrical source of power of automobile.Total rule of supercapacitor industry in 2009
About 27.5 hundred million dollars of mould, stopped according to estimation by 2014, the every annual of the market value of supercapacitor is with 21.4% increasing rate.With
The continuous development of supercapacitor technologies, the market share of supercapacitor also will constantly expand.
Metal organic framework represents a major class quantity, the multifarious material of the Nomenclature Composition and Structure of Complexes.Metal organic framework can be with
At relatively low temperatures by cheap, prepared by the synthetic method of high yield.Hydro-thermal solvent-thermal method is the most common method, in addition may be used also
It is synthesized by microwave, ultrasonic wave, electrochemistry and the method for diffusion.Metal organic framework can pass through relatively relatively inexpensive forerunner
Body preparation.The inorganic salts such as nitrate, sulfate and chlorate are as typical metal ion presoma.Organic linker is generally adopted
With multiple tooth organic ligand, such as carboxylate, azole and nitrile.In many synthesis, structure directing agent is often used in side
Structural unit is helped to assemble to form metal organic framework without participating among the structural formula of final compound.
Compared with the high-specific surface area of inorganic porous material, some metal organic frameworks show a kind of flexible structure, it
Can behave as dynamic behaviour, with external factor such as guest molecule, temperature, pressure etc. and change.Metal organic framework it is whole
A frame is that have coordinate bond or other weak mutual synergisms (hydrogen bond, pi-pi bond, Van der Waals for) to support.Therefore,
Configuration flexibility is usually in a mild condition that this condition allows those metal organic frameworks according to the reversible tune of external factor
The size of knothole gap.This flexibility is to explore catalysis, gas separation, medicament storage and transport, imaging and sensing.Photoelectricity and energy
The performances such as source storage provide new possibility.Although the structure of metal organic framework, synthesis, property and the application in various fields
It was discussed in detail in many literature reviews, but their applications in electrochemical field are not yet by play-by-play
It crosses.The research of metal organic framework in this respect is just gradually spread out recently, the important application in electrochemistry be energy stores and
It converts (supercapacitor, battery, fuel cell), the reduction of high oxidation object and toxic compounds.According to definition, electrochemistry is related to
And electronics is in the transfer and storage of electrode and electrolyte interface.Most of metal-organic framework materials are due to its weaker electric conductivity
Them can be made to exclude except preferentially as electrode material and catalysis material.However metal organic framework is by successful conduct
The electrode material of rechargeable battery also contemplates the method for overcoming their insulating property (properties)s.Metal organic framework internal metal ion
Redox behavior a kind of approach of electronics transfer can be provided, in addition the adjustment of polymeric inner bridge conjoined structure may be led
Cause better electronics transfer.
So far, application of the metal organic framework in electrochemistry is main: 1, as the electrode material of battery, including
Do the anode of lithium ion battery, cathode, the anode of lithium-sulfur cell；2, occur in fuel cell or electrolyzer certain is important
The elctro-catalyst of reaction；3, as electrode material for super capacitor etc..Front have metal-organic framework materials are used for it is super
Capacitor electrode material, but its high rate performance and cyclical stability need to be improved, therefore it is organic to prepare high performance metal
Skeleton electrode material has very big application value.
Summary of the invention
It is an object of the invention to provide a kind of two-dimentional club shaped structure vanadium metal organic backbone electrode material for supercapacitor
The preparation method of material.
The technical scheme is that: the para-phthalic sodium of the vanadic sulfate of preheating and preheating is dissolved in N, N- dimethyl methyl
Then mixture is heated to reflux and reacted by amide, the solid phase that negating should generate is dried in vacuo after being washed with methanol,
Obtain two-dimentional club shaped structure vanadium metal organic backbone electrode material.
The present invention is using easily synthetic method is heated to reflux, and raw material is easy to get, equipment cost is cheap, easy to operate, consumption
When it is short.Compared with prior art, preparation method is simple, be suitable for large-scale production, while prepared material have it is good
Cyclical stability.The present invention passes through to be formed on the basis of using vanadium metal organic backbone high capacitance activity and high conductivity
Two-dimentional club shaped structure carrys out increasing specific surface area, and the product obtained is made to have outstanding super capacitor performance.In the electric current of 0.5 A/g
Under density, specific capacitance can reach 513 F/g；Under the high current density of 10 A/g, specific capacitance still can reach 425 F/g；1
Under the current density of A/g, by 10000 charge and discharge cycles, capacity is 92.8% originally.
Further, the temperature of the vanadic sulfate of preheating of the present invention is 80 DEG C.The para-phthalic sodium of the preheating
Temperature be 80 DEG C.At such a temperature, it is sufficiently dry can not only to have guaranteed vanadic sulfate and para-phthalic sodium, but also can guarantee sulphur
The chemical property of sour vanadyl and para-phthalic sodium does not change.And use dry vanadic sulfate and para-phthalic sodium can
To reduce the generation of the side reaction in subsequent anhydrous n,N-Dimethylformamide system in heating reaction, improves reaction and produce
Rate.
The molar ratio of the vanadic sulfate and para-phthalic sodium is 1: 1.Under conditions of the feed ratio, sulfuric acid oxygen
Vanadium and para-phthalic sodium meet atom economy, and abundant conducive to reaction carries out and two kinds of raw materials make full use of.
The feed ratio of the total amount and N,N-dimethylformamide of the vanadic sulfate and para-phthalic sodium be 1mmol: 5~
10 mL.Under conditions of the feed ratio, vanadic sulfate, para-phthalic sodium can be completely dissolved in n,N-Dimethylformamide
In.
The mixing temperature of the reaction is 160 DEG C.Under the conditions of the temperature, most useful for being formed, two-dimentional club shaped structure vanadium is golden
Belong to organic backbone.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of the two-dimentional club shaped structure vanadium metal organic backbone electrode material of preparation.
Fig. 2 is the constant current charge-discharge diagram of the two-dimentional club shaped structure vanadium metal organic backbone electrode material of preparation.
Fig. 3 is the stable circulation performance figure of the two-dimentional club shaped structure vanadium metal organic backbone electrode material of preparation.
Specific embodiment
One, two-dimentional club shaped structure vanadium metal organic backbone electrode material is prepared:
Illustrate: drug used in the present invention is commercial product or laboratory conventional medication.
Embodiment 1: vanadic sulfate and para-phthalic sodium are heated 12 hours under conditions of before at 80 DEG C, will
The para-phthalic sodium of the vanadic sulfate of 2.0 mmol and 2.0 mmol are added in round-bottomed flask, and 20 mL N, N- are then added
Dimethylformamide, oil bath heat the mixture to 160 DEG C, back flow reaction 72 hours, occur yellow solid phase in solution, by solid phase
It is repeatedly washed with methanol, it is then 12 hours dry under vacuum under conditions of 80 DEG C, it is organic to obtain two-dimentional club shaped structure vanadium metal
Skeleton electrode material.
Embodiment 2: vanadic sulfate and para-phthalic sodium are heated 12 hours under conditions of before at 80 DEG C, will
The para-phthalic sodium of the vanadic sulfate of 2.0 mmol and 2.0 mmol are added in round-bottomed flask, and 30 mL N, N- are then added
Dimethylformamide, oil bath heat the mixture to 160 DEG C, back flow reaction 72 hours, occur yellow solid phase in solution, by solid phase
It is repeatedly washed with methanol, solid phase is taken to wash, obtain two-dimentional club shaped structure vanadium gold within dry 12 hours under vacuum under conditions of 80 DEG C
Belong to organic backbone electrode material.
Embodiment 3: vanadic sulfate and para-phthalic sodium are heated 12 hours under conditions of before at 80 DEG C, will
The para-phthalic sodium of the vanadic sulfate of 2.0 mmol and 2.0 mmol are added in round-bottomed flask, and 40 mL N, N- are then added
Dimethylformamide, oil bath heat the mixture to 160 DEG C, back flow reaction 72 hours, occur yellow solid phase in solution, by solid phase
It is repeatedly washed with methanol, solid phase is taken to wash, obtain two-dimentional club shaped structure vanadium gold within dry 12 hours under vacuum under conditions of 80 DEG C
Belong to organic backbone electrode material.
Two, supercapacitor is prepared:
Take two dimension club shaped structure vanadium metal organic backbone electrode material 80mg made of above each example respectively with acetylene black
15mg, polytetrafluoroethylene (PTFE) 5mg mixing, and carried out being fully ground mixing respectively with mortar, 3~5mL isopropanol is then added dropwise, will mix
It closes solution and carries out 10~15min of ultrasonic treatment.
Then mixed solution is dropped evenly in three pieces of nickel foams respectively, tabletting after spontaneously drying 1~2 day obtains electricity
Pole piece sample.
Again respectively using three pieces of electrode samples as working electrode, using saturated calomel electrode as reference electrode, it is with platinum plate electrode
To electrode, using 1mol/L metabisulfite solution as electrolyte, assembling experiment supercapacitor carries out constant current charge-discharge test.
The constant current charge-discharge of the two-dimentional club shaped structure vanadium metal organic backbone electrode material of preparation is as shown in Fig. 2, can by Fig. 2
See: the electrode material tests charge-discharge performance under 0.5,1,2,5 and 10 A/g current density, the specific capacitance being calculated
The F/g of respectively 572,520,516,505 and 495.
The stable circulation performance of the two-dimentional club shaped structure vanadium metal organic backbone electrode material of preparation is as shown in figure 3, by Fig. 3
It can be seen that: specific capacitance residue 92.8% after being recycled 10000 times under 1 A/g current density.
Claims (6)
1. a kind of preparation method of two dimension club shaped structure vanadium metal organic backbone electrode material, it is characterised in that: by the sulphur of preheating
Sour vanadyl and the para-phthalic sodium of preheating are dissolved in n,N-Dimethylformamide, and mixture is then heated to reflux and is carried out instead
It answers, the solid phase that negating should generate is dried in vacuo after being washed with methanol, obtains two-dimentional club shaped structure vanadium metal organic backbone electrode
Material.
2. preparation method according to claim 1, it is characterised in that: the temperature of the vanadic sulfate of the preheating is 80 DEG C.
3. preparation method according to claim 1, it is characterised in that: the temperature of the para-phthalic sodium of the preheating is 80
℃。
4. preparation method according to claim 1, it is characterised in that: the vanadic sulfate and para-phthalic sodium feed intake
Molar ratio is 1: 1.
5. the preparation method according to claim 4, it is characterised in that: the total amount of the vanadic sulfate and para-phthalic sodium
Feed ratio with N,N-dimethylformamide is 1mmol: 5~10 mL.
6. preparation method according to claim 1, it is characterised in that: the mixing temperature of the reaction is 160 DEG C.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525121A (en) * | 2014-12-03 | 2015-04-22 | 浙江大学 | Adsorbent for olefin/alkane mixed gas separation and preparation method and application thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525121A (en) * | 2014-12-03 | 2015-04-22 | 浙江大学 | Adsorbent for olefin/alkane mixed gas separation and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Fabian Carson等.Framework Isomerism in Vanadium Metal−Organic Frameworks:MIL-88B(V) and MIL-101(V).《Crystal Growth & Design》.2013,第13卷全文. * |
| The coordinatively saturated vanadium MIL-47 as a low leaching heterogeneous catalyst in the oxidation of cyclohexene;Karen Leus等;《Journal of Catalysis》;20111019;第285卷;全文 * |
| Vanadium metal–organic frameworks: structures and applications;Pascal Van Der Voort等;《New Journal of Chemistry》;20131104;第38卷(第5期);全文 * |
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