CN106328386B - The preparation method and application of combination electrode material, combination electrode - Google Patents
The preparation method and application of combination electrode material, combination electrode Download PDFInfo
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- CN106328386B CN106328386B CN201610786061.4A CN201610786061A CN106328386B CN 106328386 B CN106328386 B CN 106328386B CN 201610786061 A CN201610786061 A CN 201610786061A CN 106328386 B CN106328386 B CN 106328386B
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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 present invention provides the preparation method and application of a kind of combination electrode material, combination electrode, the preparation of the combination electrode material includes: that 1,3,5- trifonnyl 1,3,5-trihydroxybenzene, p-phenylenediamine, nickel nano wire are added in solvent, and ultrasonic disperse forms suspending liquid A；Suspending liquid A is vacuumized into-degassing process by liquid nitrogen frozen-, is sealed, then heating reaction, obtains crude product B；After crude product B centrifugation, collect insoluble matter, washing, it is dry to get.The preparation of the combination electrode includes: to mix combination electrode material, conductive black, Kynoar, and N-Methyl pyrrolidone is added, then after grinding drop on glass-carbon electrode, drying to get.The combination electrode material of the method for the present invention preparation is porous structure and has very high specific surface area, while the addition of nickel nano wire can greatly improve the overall conductivity of electrode material, is a kind of excellent electrode material for super capacitor.
Description
Technical field
It is the invention belongs to the preparation technical field of capacitor electrode material, in particular to a kind of combination electrode material, compound
The preparation method and application of electrode.
Background technique
Supercapacitor is that a kind of power density is big, and the long new type of energy storage device of life cycle, it has ordinary capacitor concurrently
The advantage that power density is big and secondary cell energy density is high, it is small low with cell power density to can make up for it traditional capacitor capacity
The shortcomings that, it has broad application prospects in fields such as electric car, information technology, space flight and aviation.
The electrode material of preparation supercapacitor needs while having both high-specific surface area and electric conductivity at present.By existing skill
The literature search of art finds that Donglin JIANG in 2012 etc. is in " Chemical Society Reviews " 6010- of volume 41
Page 6022 deliver Covalent Organic Framework (covalent organic frame), and covalent organic frame is by organic structure ele
It is formed and being covalently keyed, is a kind of plane macromolecule with regular porous structure, there is biggish specific surface area, knot
The diversity of structure and regulatable physicochemical properties.It has huge in the new type of energy storage device such as supercapacitor field
Potential application foreground, but the electric conductivity of current covalent organic frame material is also relatively low, is far from satisfying needs.Because needing
Design preparation while the combination electrode material for having both high-specific surface area and high conductivity, improve supercapacitor chemical property.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide the systems of a kind of combination electrode material, combination electrode
Preparation Method and application.
The purpose of the present invention is what is be achieved through the following technical solutions:
The present invention provides a kind of preparation methods of combination electrode material, comprising the following steps:
1,3,5- trifonnyl 1,3,5-trihydroxybenzene, p-phenylenediamine, nickel nano wire are added in solvent, ultrasonic disperse, which is formed, to suspend
Liquid A；
Suspending liquid A is vacuumized into-degassing process by liquid nitrogen frozen-, is sealed, then heating reaction, obtains crude product B；
After crude product B centrifugation, insoluble matter is collected, washing, drying are to get the combination electrode material.
Preferably, described 1, the molar ratio of 3,5- trifonnyl 1,3,5-trihydroxybenzene and p-phenylenediamine is 3:2.
Preferably, the long 20nm-230nm of thorn of the nickel nanowire surface；Nickel nanowire length is 200um, average diameter
For 350nm.
Preferably, the nickel nano wire dosage is 1,3,5- trifonnyl 1,3,5-trihydroxybenzene and p-phenylenediamine gross mass
40%.The dosage of the nickel nano wire is excessively high, and will lead to surface can not complete coated porous material；Dosage is too low, will lead to whole
A conductivity of composite material declines to a great extent.
Preferably, the solvent is the mixed solution of dimethyl acetamide, ortho-xylene and acetum.
Preferably, the volume ratio of the dimethyl acetamide, ortho-xylene and acetum is 3:3:1.
Preferably, the concentration of the acetum is 3mol/L.
Preferably, the reaction temperature of the heating reaction is 150 DEG C, and the reaction time is 96 hours.
The present invention also provides a kind of preparation methods of combination electrode, comprising the following steps:
The combination electrode material, conductive black, Kynoar of preceding method preparation are mixed, N- methyl is added in grinding
Pyrrolidones, then dripped on glass-carbon electrode after grinding, it dries to get the combination electrode.
Preferably, the combination electrode material, conductive black, Kynoar mass ratio be 30:65:5.
Preferably, the drying temperature is 40 DEG C, is dried 12 hours.
The present invention also provides a kind of application of the combination electrode of preceding method preparation in supercapacitor.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1, method of the invention synthesizes a kind of novel composite electrode material for the first time, has very high specific surface area, crystallinity
Good, stability height, while overall conductivity can be improved in the addition of nickel nano wire, is a kind of excellent electrode of super capacitor material
Material.
2, method green non-pollution of the invention, the requirement to equipment is simple, is suitble to industrialization large-scale production.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is the X ray diffracting spectrum of combination electrode material prepared by embodiment 1；
Fig. 2 is the SEM stereoscan photograph of combination electrode material prepared by embodiment 1；
Fig. 3 is the TEM transmission electron microscope photo of combination electrode material prepared by embodiment 1；
Fig. 4 is the cyclic voltammetry curve of supercapacitor prepared by embodiment 1；
Fig. 5 is the cyclic charging and discharging test result of supercapacitor prepared by embodiment 1；
Fig. 6 is the volume test result of supercapacitor prepared by embodiment 1.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
The preparation method of a kind of combination electrode material, combination electrode is present embodiments provided, steps are as follows:
Step 1 takes the p-phenylenediamine (C of 48mg6H8N2), the 2 of 63mg, 4,6- trihydroxies -1,3,5- benzene trioxin
(C9H6O6), the nickel nano wire of 44.4mg, be added the dimethyl acetamide of 1.5mL, the ortho-xylene of 1.5mL, 0.5mL 3mol/
L acetic acid is put into the heat resistant glass reaction tube of 10mL, 5 minutes formation suspending liquid As of ultrasonic disperse；
Step 2, suspending liquid A vacuumize-de-airing step by 4 liquid nitrogen frozens-, in 150 DEG C of heating reactions 96 after sealing
Hour, obtain crude product B；After crude product centrifugation, insoluble matter is collected, it is each clear with the n-butanol of 2ml and the acetone solvent of 2ml
It washes 3 times, it is dry, obtain crude product C, i.e. combination electrode material；
Step 3, by crude product C (30%), conductive black Super P (65%), Kynoar PVDF (5%) press matter
The mixing of amount ratio is placed in mortar and is fully ground uniformly, the N-Methyl pyrrolidone of 400 μ l is added, is ground into prepared Chinese ink shape；With shifting
Liquid rifle takes 1 μ L, drips on glass-carbon electrode；The glass-carbon electrode for being coated with active material is placed in vacuum drying oven, 40 DEG C is set and dries 12
Hour；Up to combination electrode.
By combination electrode in the NaSO that electrolyte is 1mol/L4Electrolytic cell (other two electrode is respectively: platinum electrode,
Calomel electrode) in, voltage is that -0.3V is restored 12 hours；After reduction 12 hours, in the H of 1mol/L2SO4Cyclic voltammetric is surveyed in solution
Curve, cyclical stability.
The X ray diffracting spectrum of combination electrode material manufactured in the present embodiment is as shown in Figure 1, show it with higher crystalline
Property, the characteristic peak with covalent organic frame and nickel nano wire is completely the same with simulation calculated result；SEM electromicroscopic photograph such as Fig. 2
It is shown；TEM electromicroscopic photograph is as shown in Figure 3；Fig. 4, Fig. 5 are respectively cyclic voltammetry curve and cyclic charging and discharging test as a result, from figure
In it can be seen that using the combination electrode of combination electrode material of the present invention preparation with good cyclical stability, Fig. 6 2A/g
Rate of charge under volume test as a result, from data can calculate capacity be 437F/g.The combination electrode material is one
The excellent electrode material for super capacitor of kind.
Comparative example 1
This comparative example provides the preparation method of a kind of combination electrode material, combination electrode, basic with the method for embodiment 1
Identical, the difference is that only: this comparative example substitutes nickel nano wire using carbon nanotube.
The combination electrode cyclical stability of this comparative example preparation declines to a great extent, and is not a kind of stable electrode of super capacitor
Material.
Comparative example 2
This comparative example provides the preparation method of a kind of combination electrode material, combination electrode, basic with the method for embodiment 1
It is identical, the difference is that only: the solvent that this comparative example is added are as follows: the dimethyl acetamide of 0.5mL, 1.5mL ortho-xylene,
The 3mol/L acetic acid of 1.5mL.
Combination electrode material can not be prepared using the solvent of this comparative example.
Comparative example 3
This comparative example provides the preparation method of a kind of combination electrode material, combination electrode, basic with the method for embodiment 1
It is identical, it the difference is that only: in this comparative example, crude product C (45%), Super P (55%), PVDF (5%) mixing.
Volume test result of the combination electrode of this comparative example preparation under the rate of charge of 2A/g, which calculates capacity, to be only had
45F/g。
In conclusion method of the invention synthesizes a kind of novel composite electrode material for the first time, have very high specific surface area,
Good crystallinity, stability are high, while overall conductivity can be improved in the addition of nickel nano wire, are a kind of excellent supercapacitors
Electrode material；Method green non-pollution of the invention, the requirement to equipment is simple, is suitble to industrialization large-scale production.
There are many concrete application approach of the present invention, the above is only a preferred embodiment of the present invention.More than it should be pointed out that
Embodiment is merely to illustrate the present invention, and the protection scope being not intended to restrict the invention.For the common skill of the art
For art personnel, without departing from the principle of the present invention, several improvement can also be made, these improvement also should be regarded as this hair
Bright protection scope.
Claims (10)
1. a kind of preparation method of combination electrode material, which comprises the following steps:
1,3,5- trifonnyl 1,3,5-trihydroxybenzene, p-phenylenediamine, nickel nano wire are added in solvent, ultrasonic disperse forms suspending liquid A；
Suspending liquid A is vacuumized into-degassing process by liquid nitrogen frozen-, is sealed, then heating reaction, obtains crude product B；
After crude product B centrifugation, insoluble matter is collected, washing, drying are to get the combination electrode material；
The solvent is the mixed solution of dimethyl acetamide, ortho-xylene and acetum；The dimethyl acetamide, neighbour two
The volume ratio of toluene and acetum is 3:3:1.
2. the preparation method of combination electrode material according to claim 1, which is characterized in that described 1,3,5- trifonnyls
The molar ratio of 1,3,5-trihydroxybenzene and p-phenylenediamine is 3:2.
3. the preparation method of combination electrode material according to claim 1, which is characterized in that the nickel nanowire surface
Pierce long 20nm-230nm；Nickel nanowire length is 200um, average diameter 350nm.
4. the preparation method of combination electrode material according to claim 1 or 3, which is characterized in that the nickel nano wire is used
Amount is the 40% of 1,3,5- trifonnyl 1,3,5-trihydroxybenzene and p-phenylenediamine gross mass.
5. the preparation method of combination electrode material according to claim 1, which is characterized in that the solvent is dimethyl second
The mixed solution of amide, ortho-xylene and acetum.
6. the preparation method of combination electrode material according to claim 1, which is characterized in that the reaction of the heating reaction
Temperature is 150 DEG C, and the reaction time is 96 hours.
7. a kind of preparation method of combination electrode, which comprises the following steps:
The combination electrode material, conductive black, Kynoar of the preparation of any one of claim 1-6 the method are mixed, ground
N-Methyl pyrrolidone is added in mill, then drips on glass-carbon electrode after grinding, and dries to get the combination electrode.
8. the preparation method of combination electrode according to claim 7, which is characterized in that the combination electrode material, conduction
Carbon black, Kynoar mass ratio be 30:65:5.
9. the preparation method of combination electrode according to claim 7, which is characterized in that the drying temperature is 40 DEG C, is dried
12 hours.
10. a kind of application according to the combination electrode of any one of claim 7-9 the method preparation in supercapacitor.
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| CN115015356B (en) * | 2022-06-02 | 2023-11-21 | 广州大学 | Potassium tungsten bronze-based solid ammonium ion selective electrode, preparation method and application |
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| CN104001547A (en) * | 2014-06-16 | 2014-08-27 | 上海师范大学 | Preparation method and application of environment-friendly core shell one-dimensional nanometer copper wire-organic metallic framework ZIF-8 composite catalyst |
| CN104319107A (en) * | 2014-10-28 | 2015-01-28 | 郑州轻工业学院 | Covalence organic frame/graphene composite materials, preparing method and application |
| CN104867540A (en) * | 2015-04-16 | 2015-08-26 | 浙江科创新材料科技有限公司 | Low-haze transparent conductive film and preparation method thereof |
| CN104927048A (en) * | 2015-05-22 | 2015-09-23 | 上海交通大学 | Microwave auxiliary preparation method of keto-enamine covalently linked organic framework |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102341186A (en) * | 2009-03-04 | 2012-02-01 | 施乐公司 | Electronic devices comprising structured organic films |
| CN104001547A (en) * | 2014-06-16 | 2014-08-27 | 上海师范大学 | Preparation method and application of environment-friendly core shell one-dimensional nanometer copper wire-organic metallic framework ZIF-8 composite catalyst |
| CN104319107A (en) * | 2014-10-28 | 2015-01-28 | 郑州轻工业学院 | Covalence organic frame/graphene composite materials, preparing method and application |
| CN104867540A (en) * | 2015-04-16 | 2015-08-26 | 浙江科创新材料科技有限公司 | Low-haze transparent conductive film and preparation method thereof |
| CN104927048A (en) * | 2015-05-22 | 2015-09-23 | 上海交通大学 | Microwave auxiliary preparation method of keto-enamine covalently linked organic framework |
| CN104974500A (en) * | 2015-07-10 | 2015-10-14 | 中国科学院理化技术研究所 | Polymer-based electric conduction material containing metal nano-wires and graphene oxide, and preparation method thereof |
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