CN106328386A - Preparation method and application of combination electrode material and combination electrode - Google Patents
Preparation method and application of combination electrode material and combination electrode Download PDFInfo
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- CN106328386A CN106328386A CN201610786061.4A CN201610786061A CN106328386A CN 106328386 A CN106328386 A CN 106328386A CN 201610786061 A CN201610786061 A CN 201610786061A CN 106328386 A CN106328386 A CN 106328386A
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- combination electrode
- electrode 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
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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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- 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 provides a preparation method and application of a combination electrode material and a combination electrode. The preparation of the combination electrode material includes: adding 2,4,6-trihydroxybenzene-1,3,5-tricarbaldehyde, p-phenylenediamine, and nickel nano wires into a solvent, and performing ultrasonic dispersion to form a suspension A; performing liquid nitrogen refrigeration, vacuum pumping, and degassing treatment on the suspension A, performing sealing and heating reaction, and obtaining a crude product B; and performing centrifugation on the crude product B, collecting insoluble substances, and obtaining the combination electrode material after washing and drying. The preparation of the combination electrode includes: mixing the combination electrode material, conductive carbon black and polyvinylidene fluoride, adding N-methyl-2-pyrrolidone, grinding the mixture, and dropping the mixture on a glassy carbon electrode, and performing drying to obtain the combination electrode. The combination electrode material prepared by the method is a porous structure and the specific surface area is large; and the overall conductivity of the electrode material can be greatly improved through the adding of the nickel nano wires, and the combination electrode material is an excellent electrode material of supercapacitors.
Description
Technical field
The invention belongs to the preparing technical field of capacitor electrode material, particularly to a kind of combination electrode material, be combined
The preparation method and application of electrode.
Background technology
Ultracapacitor is that a kind of power density is big, and the novel energy-storing device of life cycle length, it has ordinary capacitor concurrently
The advantage that power density is big and secondary cell energy density is high, it is possible to make up traditional capacitor capacity little low with cell power density
Shortcoming, have broad application prospects in fields such as electric automobile, information technology, space flight and aviation.
The electrode material preparing ultracapacitor at present needs to have high-specific surface area and electric conductivity concurrently simultaneously.Through existing skill
The literature search of art finds, Donglin JIANG in 2012 etc. are at " Chemical Society Reviews " volume 41 6010-
Delivering Covalent Organic Framework (covalency organic frame) by page 6022, covalency organic frame is by organic structure ele
Connected by covalent bond and formed, be the class plane macromolecule with regular loose structure, there is bigger specific surface area, knot
The multiformity of structure and regulatable physicochemical properties.It has huge in novel energy-storing devices field such as ultracapacitors
Potential application foreground, but the electric conductivity of covalent organic frame material is the most on the low side at present, can not meet far away needs.Because needing
Design preparation has the combination electrode material of high-specific surface area and high conductivity concurrently simultaneously, improves ultracapacitor chemical property.
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 combination electrode material, the system of combination electrode
Preparation Method and application.
It is an object of the invention to be achieved through the following technical solutions:
The invention provides the preparation method of a kind of combination electrode material, comprise the following steps:
By 1,3,5-trifonnyl 1,3,5-trihydroxybenzene, p-phenylenediamine, nickel nano wire add in solvent, and ultrasonic disperse is formed and suspends
Liquid A；
Suspending liquid A is processed through liquid nitrogen freezing-evacuation-degassing, seals, then reacting by heating, obtain crude product B；
After centrifugal for crude product B, collect insoluble matter, wash, be dried, obtain described combination electrode material.
Preferably, described 1,3,5-trifonnyl 1,3,5-trihydroxybenzene are 3:2 with the mol ratio of p-phenylenediamine.
Preferably, the long 20nm-230nm of thorn of described nickel nanowire surface；Nickel nanowire length is 200um, average diameter
For 350nm.
Preferably, described nickel nano wire consumption is 1,3,5-trifonnyl 1,3,5-trihydroxybenzene and p-phenylenediamine gross mass
40%.The consumption of described nickel nano wire is too high, can cause the surface cannot complete coated porous material；Consumption is too low, can cause whole
Individual conductivity of composite material declines to a great extent.
Preferably, described solvent is the mixed solution of dimethyl acetylamide, o-Dimethylbenzene and acetum.
Preferably, the volume ratio of described dimethyl acetylamide, o-Dimethylbenzene and acetum is 3:3:1.
Preferably, the concentration of described acetum is 3mol/L.
Preferably, the reaction temperature of described reacting by heating is 150 DEG C, and the response time is 96 hours.
Present invention also offers the preparation method of a kind of combination electrode, comprise the following steps:
The mixing of the combination electrode material prepared by preceding method, conductive black, Kynoar, grinds, and adds N-methyl
Drop on glass-carbon electrode after ketopyrrolidine, then grinding, dry, obtain described combination electrode.
Preferably, described combination electrode material, conductive black, the mass ratio of Kynoar are 30:65:5.
Preferably, described drying temperature is 40 DEG C, dries 12 hours.
Present invention also offers combination electrode prepared by a kind of preceding method application in ultracapacitor.
Compared with prior art, the present invention has a following beneficial effect:
1, the method for the present invention synthesizes a kind of novel composite electrode material first, has the highest specific surface area, crystallinity
Good, stability height, the addition of nickel nano wire simultaneously can improve monolithic conductive, is a kind of excellent electrode of super capacitor material
Material.
2, the method green non-pollution of the present invention, the requirement to equipment is simple, is suitable for industrialization large-scale production.
Accompanying drawing explanation
By the detailed description non-limiting example made with reference to the following drawings of reading, the further feature of the present invention,
Purpose and advantage will become more apparent upon:
Fig. 1 is the X ray diffracting spectrum of the combination electrode material of embodiment 1 preparation；
Fig. 2 is the SEM stereoscan photograph of the combination electrode material of embodiment 1 preparation；
Fig. 3 is the TEM transmission electron microscope photo of the combination electrode material of embodiment 1 preparation；
Fig. 4 is the cyclic voltammetry curve of the ultracapacitor of embodiment 1 preparation；
Fig. 5 is the cycle charge discharge electrical test results of the ultracapacitor of embodiment 1 preparation；
Fig. 6 is the volume test result of the ultracapacitor of embodiment 1 preparation.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following example will assist in the technology of this area
Personnel are further appreciated by the present invention, but limit the present invention the most in any form.It should be pointed out that, the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement.These broadly fall into the present invention
Protection domain.
Embodiment 1
Present embodiments providing the preparation method of a kind of combination electrode material, combination electrode, step is as follows:
Step one, takes the p-phenylenediamine (C of 48mg6H8N2), the 2 of 63mg, 4,6-trihydroxy-1,3,5-benzene trioxins
(C9H6O6), the nickel nano wire of 44.4mg, add the dimethyl acetylamide of 1.5mL, the o-Dimethylbenzene of 1.5mL, the 3mol/ of 0.5mL
L acetic acid, puts in the heat resistant glass reaction tube of 10mL, and ultrasonic disperse forms suspending liquid A in 5 minutes；
Step 2, suspending liquid A is through 4 liquid nitrogen freezing-evacuation-de-airing step, 150 DEG C of reacting by heating 96 after sealing
Hour, obtain crude product B；After centrifugal for described crude product, collect insoluble matter, each clearly with the n-butyl alcohol of 2ml and the acetone solvent of 2ml
Wash 3 times, be dried, obtain crude product C, i.e. combination electrode material；
Step 3, by crude product C (30%), conductive black Super P (65%), Kynoar PVDF (5%) presses matter
Amount ratio mixes, and is placed in mortar and is fully ground uniformly, adds the N-Methyl pyrrolidone of 400 μ l, grind to form prepared Chinese ink shape；With shifting
Liquid rifle takes 1 μ L, drops on glass-carbon electrode；The glass-carbon electrode scribbling active substance is placed in vacuum drying oven, sets 40 DEG C and dry 12
Hour；Obtain combination electrode.
It is the NaSO of 1mol/L by combination electrode at electrolyte4Electrolyzer (two other electrode respectively: platinum electrode,
Calomel electrode) in, voltage is that-0.3V reduces 12 hours；After reducing 12 hours, at the H of 1mol/L2SO4Solution is surveyed cyclic voltammetric
Curve, cyclical stability.
The X ray diffracting spectrum of combination electrode material prepared by the present embodiment is as it is shown in figure 1, show that it has higher crystalline
Property, there is covalency organic frame and the characteristic peak of nickel nano wire, completely the same with simulation result of calculation；SEM electromicroscopic photograph such as Fig. 2
Shown in；TEM electromicroscopic photograph is as shown in Figure 3；Fig. 4, Fig. 5 are respectively cyclic voltammetry curve and cycle charge discharge electrical test results, from figure
In can be seen that and use the combination electrode prepared of combination electrode material of the present invention to have good cyclical stability, Fig. 6 is 2A/g
Rate of charge under volume test result, can calculate capacity from data is 437F/g.Described combination electrode material is one
Plant excellent electrode material for super capacitor.
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 uses CNT to substitute nickel nano wire.
Combination electrode cyclical stability prepared by this comparative example 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
Identical, the difference is that only: this comparative example add solvent be: the dimethyl acetylamide of 0.5mL, the o-Dimethylbenzene of 1.5mL,
The 3mol/L acetic acid of 1.5mL.
The solvent using this comparative example cannot prepare combination electrode material.
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
Identical, the difference is that only: in this comparative example, crude product C (45%), Super P (55%), PVDF (5%) mixes.
Combination electrode prepared by this comparative example volume test result under the rate of charge of 2A/g only calculates capacity
45F/g。
In sum, the method for the present invention synthesizes a kind of novel composite electrode material first, have the highest specific surface area,
Good crystallinity, stability are high, and the addition of nickel nano wire simultaneously can improve monolithic conductive, is a kind of excellent ultracapacitor
Electrode material；The method green non-pollution of the present invention, the requirement to equipment is simple, is suitable for industrialization large-scale production.
The concrete application approach of the present invention is a lot, and the above is only the preferred embodiment of the present invention.It should be pointed out that, above
Embodiment is merely to illustrate the present invention, and is not limited to protection scope of the present invention.Common skill for the art
For art personnel, under the premise without departing from the principles of the invention, it is also possible to make some improvement, these improvement also should be regarded as this
Bright protection domain.
Claims (10)
1. the preparation method of a combination electrode material, it is characterised in that comprise the following steps:
By 1,3,5-trifonnyl 1,3,5-trihydroxybenzene, p-phenylenediamine, nickel nano wire add in solvent, and ultrasonic disperse forms suspending liquid A；
Suspending liquid A is processed through liquid nitrogen freezing-evacuation-degassing, seals, then reacting by heating, obtain crude product B；
After centrifugal for crude product B, collect insoluble matter, wash, be dried, obtain described combination electrode material.
The preparation method of combination electrode material the most according to claim 1, it is characterised in that described 1,3,5-trifonnyl
1,3,5-trihydroxybenzene is 3:2 with the mol ratio of p-phenylenediamine.
The preparation method of combination electrode material the most according to claim 1, it is characterised in that described nickel nanowire surface
Sting long 20nm-230nm；Nickel nanowire length is 200um, and average diameter is 350nm.
4. according to the preparation method of the combination electrode material described in claim 1 or 3, it is characterised in that described nickel nano wire is used
Amount is 1,3,5-trifonnyl 1,3,5-trihydroxybenzene and the 40% of p-phenylenediamine gross mass.
The preparation method of combination electrode material the most according to claim 1, it is characterised in that described solvent is dimethyl second
The mixed solution of amide, o-Dimethylbenzene and acetum.
The preparation method of combination electrode material the most according to claim 1, it is characterised in that the reaction of described reacting by heating
Temperature is 150 DEG C, and the response time is 96 hours.
7. the preparation method of a combination electrode, it is characterised in that comprise the following steps:
The mixing of the combination electrode material method described in any one of claim 1-6 prepared, conductive black, Kynoar, grinds
Mill, drops on glass-carbon electrode after adding N-Methyl pyrrolidone, then grinding, dries, obtains described combination electrode.
The preparation method of combination electrode the most according to claim 7, it is characterised in that described combination electrode material, conduction
White carbon black, the mass ratio of Kynoar are 30:65:5.
The preparation method of combination electrode the most according to claim 7, it is characterised in that described drying temperature is 40 DEG C, dries
12 hours.
10. the combination electrode prepared according to method described in any one of the claim 7-9 application in ultracapacitor.
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| CN201610786061.4A CN106328386B (en) | 2016-08-30 | 2016-08-30 | The preparation method and application of combination electrode material, combination electrode |
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| CN201610786061.4A CN106328386B (en) | 2016-08-30 | 2016-08-30 | The preparation method and application of combination electrode material, combination electrode |
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| CN106328386A true CN106328386A (en) | 2017-01-11 |
| CN106328386B CN106328386B (en) | 2019-02-22 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114335408A (en) * | 2021-12-28 | 2022-04-12 | 上海交通大学 | Composite electrode and preparation method and application thereof |
| CN115015356A (en) * | 2022-06-02 | 2022-09-06 | 广州大学 | Solid ammonium ion selective electrode based on potassium tungsten bronze, preparation method and application |
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Patent Citations (8)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114335408A (en) * | 2021-12-28 | 2022-04-12 | 上海交通大学 | Composite electrode and preparation method and application thereof |
| CN115015356A (en) * | 2022-06-02 | 2022-09-06 | 广州大学 | Solid ammonium ion selective electrode based on potassium tungsten bronze, preparation method and application |
| 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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| CN106328386B (en) | 2019-02-22 |
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Granted publication date: 20190222 |