CN106653400B - A kind of preparation method of flexible composite electrode material - Google Patents
A kind of preparation method of flexible composite electrode material Download PDFInfo
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- CN106653400B CN106653400B CN201611235311.1A CN201611235311A CN106653400B CN 106653400 B CN106653400 B CN 106653400B CN 201611235311 A CN201611235311 A CN 201611235311A CN 106653400 B CN106653400 B CN 106653400B
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- carbon nanotube
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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 a kind of flexible composite electrode material preparation methods, first with Ozonation, carry out purifying and acidification to multi-walled carbon nanotube, obtain the f-MWCNT of functionalization；F-MWCNT, KMnO are weighed in proportion4And aniline；In deionized water by the stock dispersion weighed, ultrasonic, obtain finely dispersed presoma mixed liquor；Gained mixed liquor is transferred in water heating kettle, is heated to 160~200 DEG C, and keep 15~for 24 hours after, filter, washing, drying to obtain MWCNT/MnO2/ PANI combination electrode materials.The flexible composite electrode material that method through the invention obtains has preferable capacitive properties, impedance is small, pressure drop is small, highest specific capacitance is up to 364.1F/g, after cycle 1000 times, specific capacitance still maintains original 87.3%, can be used for the electrode material of ultracapacitor and ion battery, the elctro-catalyst of lithium-air battery.
Description
Technical field
The invention belongs to materialogy fields, are related to a kind of inorganic-organic composite material, specifically a kind of flexible compound
The preparation method of electrode material.
Background technology
With the further development of society, environment and energy problem become more and more prominent.Therefore there is an urgent need to one by people
Plant environmental-friendly and sustainable energy storage form.As a kind of emerging energy storage device, ultracapacitor, that is, electrochemistry electricity
Container is a kind of new type of energy storage device between traditional capacitor and secondary cell.Compared with traditional capacitor, electrochemistry
Capacitor has a higher specific capacity, and storable than energy is 10-100 times of traditional capacitor；Compared with battery, have than
The advantages that power is high, energy density is big, the charging time is short, discharging efficiency is high and has extended cycle life.In mechanics of communication, electric vehicle
There is application prospect of crucial importance and wide with fields such as aerospace science and techniques of defence.
The capacitive property of ultracapacitor depends primarily on electrode material, the material currently used for electric chemical super capacitor
Mainly there are three classes, various carbon materials；Transition metal oxide, such as ruthenic oxide, manganese dioxide and nickel oxide；It is conductive
Polymer material etc..Carbon material is to realize energy storage using the interfacial electric double layer formed between electrode and electrolyte, this
Kind energy storage carries out activation polarization to realize by electrolyte solution, and there is no generation electrochemical reactions, therefore with good
Good cyclical stability and higher specific power density, and carbon nanotube is the one-dimensional tubular nanometer knot curled by graphene
Structure, with sp between carbon atom therein2Hybrid form is bonded so that carbon nanotube both has very high mechanical strength, it may have
Very high conductivity and chemical property is a kind of advanced flexible energy storage material, but since low specific capacitance and energy is close
Degree limits its application in practice.The one kind of manganese dioxide as Typical transition metal oxide, resource is extensive, and price is low
Honest and clean, friendly to environment, electro-chemical activity is high, and theoretical specific capacitance can reach 1370F/g, be a kind of very promising electrode material
Material, but its lower electric conductivity limits its practical application.Conducting polymer be utilize redox reaction, it is doped and
Doped mutual change is gone to bring storage energy, therefore conducting polymer not only all exists in interface but also in whole volume
Highdensity charge has big specific capacitance, and polyaniline is easy to get with raw material, convieniently synthesized, conductivity is high, unique doping machine
, there is prodigious development potentiality in the characteristics of processed in conducting high polymers object field, but since it is in energy storage process
Redox reaction so that cyclical stability is very poor, hinders its application in practice.It follows that the carbon materials of one-component
When material is used as ultracapacitor, specific capacitance is not high；The metal oxide of one-component be used as ultracapacitor when, conductivity compared with
It is low, electrochemistry cyclicity is undesirable；When the conducting polymer of one-component is used as ultracapacitor, cyclical stability is poor.In order to
Overcome deficiency existing for the above homogenous material, is badly in need of research and development multi-element composite material to improve the performance of ultracapacitor.
Currently, disclosing one kind in patent CN102280263A using carbon nanotube/manganese oxide composite material as electrode
Electrochemical capacitor, the composite material is using the method synthesis of magnetron sputtering and chemical vapor deposition, and more single oxygen
Change the conductive stronger and higher advantage of specific capacitance of manganese electrode, but the method is not only of high cost, preparation process is complicated, and
It should not accomplish scale production.
A kind of superhigh-capacitance capacitor with composite carbon nanotube is disclosed in patent CN1388540A, the electrode is adopted
With six kinds of material preparations：Carbon nanotube and transition metal oxide compound, carbon nanotube and conducting polymer series compound,
Carbon nanotube and transition metal oxide, conducting polymer combination product, carbon nanotube and transition metal oxide, activity simultaneously
Charcoal series combination product, carbon nanotube and conducting polymer series, activated carbon series combination product or carbon nanotube simultaneously simultaneously
With transition metal oxide, conducting polymer, activated carbon series combination product simultaneously.But the metal oxygen used in above-mentioned compound
Compound is only the oxide of nickel and cobalt, and the chemical property without investigating composite nano materials, makes it in practical applications
Feasibility it is hindered.
Invention content
For above-mentioned technical problem in the prior art, the present invention provides a kind of preparation sides of flexible composite electrode material
The preparation method of method, this flexible composite electrode material will solve the manufacturing cost of ultracapacitor in the prior art
The relatively low technical problem of height, complex process, specific capacitance.
The present invention provides a kind of preparation methods of flexible composite electrode material, include the following steps：
1) a step of Ozonation prepares the f-MWCNT of functionalization, trifluoro second is dispersed in by multi-walled carbon nanotube
In acid solution, the material ratio of multi-walled carbon nanotube and trifluoroacetic acid solution is 0.1g：20 ~ 40mL, Bubbling method be passed through flow be 30 ~
The ozone of 50ml/min after being heated to reflux 10 ~ 15h at 70 ~ 90 DEG C, obtains the f-MWCNT of functionalization；
2) f-MWCNT, KMnO are weighed4And aniline, f-MWCNT, KMnO4Material ratio with aniline is (0.05~0.08) g:
(0.1~0.3) g:(200~500) μ L；
3) by step 2）In the stock dispersion that weighs in deionized water, 30~60min of ultrasound, obtain it is finely dispersed before
Drive body mixed liquor；
4) by step 3）Gained presoma mixed liquor is transferred in water heating kettle, is heated to 160~200 DEG C, and keep 15~for 24 hours
Afterwards, it filters, wash, drying to obtain MWCNT/MnO2/ PANI combination electrode materials.
The present invention utilizes simple one kettle way, prepares multi-walled carbon nanotube/manganese dioxide/polyaniline ternary flexible compound
Electrode material.This composite material couples three kinds of common electrode material for super capacitor, polyaniline（PANI）With good
Electric conductivity can enhance the utilization rate of carbon nanotube/manganese dioxide active material；Carbon nanotube/manganese dioxide is not only composite wood
Material rigidity plays a supportive role, and electronics can be promoted axially to convey, and can both utilize the electric double layer electricity of carbon in this way
The Faraday pseudo-capacitance of manganese dioxide and polyaniline can be utilized again by holding, and collaboration plays the chemical property of three, to have
Effect improves the specific capacity of ultracapacitor.
The method for preparing combination electrode material of the present invention is simple, can be completed using one kettle way, the KMnO of use4Itself
As oxidant, without others reductant-oxidant, environmental-friendly, equipment requirement is low, can be carried out under lower temperature conditions,
Short preparation period is suitble to industrialized production.The present invention can be used for the electrode material of ultracapacitor and ion battery, lithium-air
The elctro-catalyst of battery.Such electrode material has preferable capacitive properties, and impedance is small, and pressure drop is small, and highest specific capacitance is reachable
364.1F/g, after recycling 1000 times, specific capacitance still maintains original 87.3%.
The present invention prepares carbon nanotube/manganese dioxide/polyaniline trielement composite material using one kettle way, that is, uses simple
Synthetic technology prepares high-performance super capacitor electrode material.Three kinds of unitary electrode materials are overcome in supercapacitor applications side
Deficiency on face, gives full play to the synergistic effect of carbon material, transition metal oxide and conducting polymer, and advantage is mutually tied
It closes, defect mutually weakens, and greatly improves the chemical property of material.
The present invention is compared with prior art, and technological progress is significant.Carbon nanotube/manganese dioxide of the present invention/poly-
Aniline trielement composite material, preparation process is simple controllable, low temperature, quickly, condition is more mild, equipment requirement is low, raw material at
This is cheap, and after assembling, gained composite material has good cycle performance and high-specific capacitance super, is a kind of ideal super
Capacitor electrode material is especially suitable for industrialized production.
Description of the drawings
Fig. 1 is the SEM figures of 1 gained carbon nanotube of embodiment/manganese dioxide/polyaniline ternary composite electrode material.
Specific implementation mode
Embodiment 1
1) multi-walled carbon nanotube 0.1g is dispersed in 30mL trifluoroacetic acids by the f-MWCNT of Ozonation preparation functionalization
In solution, Bubbling method is passed through the ozone that flow is 40ml/min, after being heated to reflux 12h at 80 DEG C, obtains the f- of functionalization
MWCNT；
2) f-MWCNT, KMnO are weighed4And aniline, f-MWCNT, KMnO4Material ratio with aniline is 0.066g: 0.15g
:200μL；
3) by step 2）In the stock dispersion that weighs in 40 ml deionized waters, ultrasonic 60min is obtained finely dispersed
Presoma mixed liquor；
4) by step 3）Gained presoma mixed liquor is transferred in water heating kettle, is heated to 180 DEG C, and after holding for 24 hours, filter,
Washing, drying to obtain MWCNT/MnO2/ PANI combination electrode materials.
Pattern test, acquired results such as Fig. 1 are carried out to products obtained therefrom using Hitachi S-4800.MnO2To be rodlike, carbon nanometer
Pipe uniformly divides wherein, and macromolecule PANI has higher adhesive effect, and three is formed to stable complex.
Utilize the chemical property of CHI660E model electrochemical workstation test samples.With constant current charge charging method
Under 0.5A/g current densities, it is 364.1F/g to measure specific capacitance.
Embodiment 2
1) multi-walled carbon nanotube 0.1g is dispersed in 30mL trifluoroacetic acids by the f-MWCNT of Ozonation preparation functionalization
In solution, Bubbling method is passed through the ozone that flow is 40ml/min, after being heated to reflux 12h at 80 DEG C, obtains the f- of functionalization
MWCNT；
2) f-MWCNT, KMnO are weighed4And aniline, f-MWCNT, KMnO4Material ratio with aniline is 0.066g: 0.15g
:300μL；
3) by step 2）In the stock dispersion that weighs in 40 ml deionized waters, ultrasonic 60min is obtained finely dispersed
Presoma mixed liquor；
4) by step 3）Gained presoma mixed liquor is transferred in water heating kettle, is heated to 180 DEG C, and after holding for 24 hours, filter,
Washing, drying to obtain MWCNT/MnO2/ PANI combination electrode materials.
Utilize the chemical property of CHI660E model electrochemical workstation test samples.With constant current charge charging method
Under 0.5 A/g current densities, it is 317.3 F/g to measure specific capacitance.
Embodiment 3
1) multi-walled carbon nanotube 0.1g is dispersed in 30mL trifluoroacetic acids by the f-MWCNT of Ozonation preparation functionalization
In solution, Bubbling method is passed through the ozone that flow is 40ml/min, after being heated to reflux 12h at 80 DEG C, obtains the f- of functionalization
MWCNT；
2) f-MWCNT, KMnO are weighed4And aniline, f-MWCNT, KMnO4Material ratio with aniline is 0.066g: 0.15g
:400μL；
3) by step 2）In the stock dispersion that weighs in 40ml deionized waters, ultrasonic 60min, obtain it is finely dispersed before
Drive body mixed liquor；
4) by step 3）Gained presoma mixed liquor is transferred in water heating kettle, is heated to 180 DEG C, and after holding for 24 hours, filter,
Washing, drying to obtain MWCNT/MnO2/ PANI combination electrode materials.
Utilize the chemical property of CHI660E model electrochemical workstation test samples.With constant current charge charging method
Under 0.5A/g current densities, it is 308.9 F/g to measure specific capacitance.
Claims (1)
1. a kind of preparation method of flexible composite electrode material, it is characterised in that include the following steps：
1）The step of one Ozonation prepares the f-MWCNT of functionalization, it is molten to be dispersed in trifluoroacetic acid by multi-walled carbon nanotube
In liquid, the material ratio of multi-walled carbon nanotube and trifluoroacetic acid solution is 0.1g：20 ~ 40mL, Bubbling method be passed through flow be 30 ~
The ozone of 50ml/min after being heated to reflux 10 ~ 15h at 70 ~ 90 DEG C, obtains the f-MWCNT of functionalization；
2）Weigh f-MWCNT, KMnO4And aniline, f-MWCNT, KMnO4Material ratio with aniline is (0.05~0.08) g:
(0.1~0.3) g:(200~500) μ L；
3）By step 2）In the stock dispersion that weighs in deionized water, 30~60min of ultrasound obtains finely dispersed presoma
Mixed liquor；
4）By step 3）Gained presoma mixed liquor is transferred in water heating kettle, is heated to 160~200 DEG C, and keep 15~for 24 hours after,
It filters, washing, drying to obtain MWCNT/MnO2/ PANI combination electrode materials.
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| CN106653400B true CN106653400B (en) | 2018-11-13 |
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| CN108461726B (en) * | 2018-03-12 | 2020-09-29 | 陕西科技大学 | Polycrystalline manganese dioxide/carbon nanotube composite material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101547858A (en) * | 2006-10-18 | 2009-09-30 | 新加坡科技研究局 | Method of functionalizing a carbon material |
| CN105244186A (en) * | 2015-10-15 | 2016-01-13 | 扬州大学 | Preparation method of carbon-based ternary complex |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101547858A (en) * | 2006-10-18 | 2009-09-30 | 新加坡科技研究局 | Method of functionalizing a carbon material |
| CN105244186A (en) * | 2015-10-15 | 2016-01-13 | 扬州大学 | Preparation method of carbon-based ternary complex |
Non-Patent Citations (1)
| Title |
|---|
| 基于碳纳米管构筑用作超级电容器电极的纳米复合材料;李立;《中国优秀硕士学位论文全文数据库工程科技II辑》;20120315;第42-299页 * |
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Granted publication date: 20181113 |