CN103646790B - The light that has of a kind of wire visits flexible super capacitor and the preparation method of performance - Google Patents
The light that has of a kind of wire visits flexible super capacitor and the preparation method of performance Download PDFInfo
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- CN103646790B CN103646790B CN201310716914.3A CN201310716914A CN103646790B CN 103646790 B CN103646790 B CN 103646790B CN 201310716914 A CN201310716914 A CN 201310716914A CN 103646790 B CN103646790 B CN 103646790B
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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 flexible asymmetric super-capacitor and the manufacture method of a kind of wire.Described capacitor includes the positive electrode of asymmetric capacitor, negative material and electrolyte, and wherein positive electrode is grown in line-shaped conductive substrate, negative material be coated in fiber after uniform winding in wire conductive substrates.Described manufacture method includes: growing cobaltosic oxide nano linear array on nickel wire or titanium silk by hydro-thermal method and be used as positive pole, the Graphene being coated on carbon fiber is used as negative pole, with PVA KOH colloidal sol as electrolyte；Positive and negative electrode is impregnated five minutes in PVA KOH colloidal sol；The carbon fiber winding scribbling Graphene is had on nickel wire or the titanium silk of Cobalto-cobaltic oxide in growth；Natural drying in atmosphere, removes the moisture in electrolyte, completes the preparation of capacitor.Linear flexible Asymmetric Supercapacitor voltage range prepared by the present invention is brought up to 0.0 1.5V by 0.0 original 0.5V, and its stored energy improves 1860% times.
Description
Technical field
The invention belongs to the field that energy device combines with optical detection, be specifically related to the tool of a kind of wire
Light is had to visit flexible super capacitor and the preparation method of performance.
Background technology
Along with the development of flexible electronic, flexible electronic device has become as what each major company vied each other
Market focus.In August, 2013, it is big that Technology of Flexibility is chosen as the whole world ten in 2013 by western medium
One of Progress & New Products, and in October, LG company successively announces success volume production Flexible Displays
Screen and flexible lithium ion battery, it can be seen that the life away from us of the epoch of flexible electronic product is more
Come the nearest.Meanwhile, along with market to electronic product miniaturization, integrated more and more obvious
Demand, the integrated research of electronic device has obtained increasing concern.Up to the present, a variety of
The integrated device that can realize several functions is obtained for well development, such as the lithium-ion electric of self-charging
Pond, the ultracapacitor of self-charging, self-driven pressure transducer and intelligent color-changing window etc..But this
Being essentially all plane structure a bit, volume is relatively big, does not meets integrated device miniaturization, flexibility
Road for development.Comparatively speaking, the structure of wire has the advantages such as volume is little, bending property is superior,
The marketization application that the flexible integration device of development wire is flexible to electronic product, integrated has critically important
Meaning.
Summary of the invention
It is an object of the invention to provide the Asymmetric Supercapacitor of a kind of wire.Its object is to carry
The running voltage of high ultracapacitor, energy density per unit volume, solve the problem that current capacitor specific energy is low.
The second object of the present invention is that the light that has providing a kind of flexibility visits the flexible super electricity of performance
Container.Use Graphene as the negative pole of Asymmetric Supercapacitor, utilize Graphene as light simultaneously
The sensitive material visited, by the change before and after illumination of the sensing capacitor leakage current, carrys out reflected optical signal,
Asymmetric Supercapacitor is made to have the performance of photo-detector.
According to an aspect of the present invention, it provides the flexible asymmetric super-capacitor of a kind of wire,
It includes the positive electrode of asymmetric capacitor, negative material and electrolyte, wherein positive electrode growth
In wire conductive substrates, negative material be coated in fiber after uniform winding in wire conductive substrates.
Wherein, described conductive substrates is nickel wire, titanium silk or carbon fiber, and described positive electrode is for having electricity
The semi-conducting material of capacitive energy, described negative material is to have capacitive property and the material of light spy performance simultaneously
Material.
Wherein, described positive electrode is Cobalto-cobaltic oxide, manganese dioxide, nickel oxide or cobalt acid nickel.
Wherein, described negative material is Graphene, CNT, carbon nano-fiber or carbon nano-particle.
Wherein, described negative material can be as the light-sensitive material of visible ray to infrared light, under light illumination,
Optical detection is carried out by the change of the leakage current of sensing capacitor.
According to a further aspect of the invention, its light that has providing a kind of wire visits the super capacitor of performance
The preparation method of device, comprising:
Step 1, use hydro-thermal method grow cobaltosic oxide nano linear array on nickel wire or titanium silk and are just being used as
Pole, the Graphene being coated on carbon fiber is used as negative pole, with PVA-KOH colloidal sol as electrolyte；
Step 2, positive and negative electrode is impregnated five minutes in PVA-KOH colloidal sol；
Step 3, then there is the nickel wire of Cobalto-cobaltic oxide in growth by scribbling the carbon fiber winding of Graphene
Or on titanium silk；
Step 4, in atmosphere natural drying, remove the moisture in electrolyte, complete the system of capacitor
Standby.
Wherein, in step 1, cobaltosic oxide nano linear array makes as follows:
Step 101, add 5mmol cobalt chloride hexahydrate and 20mmol urea element is dissolved in going of 50mL
In ionized water；
Step 102, take the above-mentioned solution of 40mL add 50mL autoclave in；
Step 103, nickel wire or titanium silk successively clean 15 minutes in deionized water, ethanol, acetone；
Step 104, cleaned nickel wire is put in above-mentioned autoclave；
Step 105, react 4 hours at 95 DEG C, clean with deionized water after taking-up, and be dried；
Step 106, by dried sample, anneal 80 minutes at 300 DEG C, be cooled to room temperature.
Wherein, graphene coated by following method: the Graphene of 10mg is dissolved in 20mL N-
In methylpyrrolidone solution, ultrasonic disperse 3 hours；Then by ready impregnated carbon fiber upper
State in solution 30 minutes, be dried 12 hours at 80 DEG C after taking-up.
Wherein, described ultracapacitor has storage energy and the function of optical detection.
There is advantages that
A. for current symmetry ultracapacitor voltage window than relatively low shortcoming, we construct base
In Cobalto-cobaltic oxide and the Asymmetric Supercapacitor of Graphene so that the voltage window of capacitor is by former
The 0.0-0.5V come brings up to 0.0-1.5V (see Fig. 6).
The biggest energy density that improve ultracapacitor.With symmetry based on Cobalto-cobaltic oxide
Ultracapacitor is compared, and its stored energy improves 1860% times.
The most this asymmetrical wire capacitor volume is little, flexible, simple in construction, to developing
The development of the flexible electronic device woven provide corresponding energy supply.
The most this asymmetrical ultracapacitor has the function of photo-detector, while storage energy,
Achieving the detection to visible ray, energy storage device is had multi-functional with other device integration realization by this
The research of electronic device has valuable help.
The most this wire have light visit function Asymmetric Supercapacitor when as photo-detector,
Having good bending property equally, same in the bent state have stable detection to visible ray
Energy.This has good enlightenment to the research and development of flexible integration device.
It addition, the present invention uses hydro-thermal method direct growth Cobalto-cobaltic oxide on nickel wire (or titanium silk),
Compared with traditional electrode preparation method, this direct growth structure on conductive substrates need not add
Adding additives, can effectively increase the electric transmission between active substance and colelctor electrode.And nanometer
The structure of linear array can increase the contact area of active substance and electrolyte so that active substance is permissible
Sufficiently react with electrolyte, the performance improving ultracapacitor is had very great help.
Accompanying drawing explanation
Fig. 1 is the structure chart of the ultracapacitor with light spy performance of wire in the present invention；
Fig. 2 is the scanning electron microscope diagram of the Cobalto-cobaltic oxide being grown on nickel wire of shooting under low power；
Fig. 3 be 1500 times amplify under the conditions of the scanning electron microscope of cobaltosic oxide nano linear array
Figure；
Fig. 4 is the scanning electron microscope diagram of the Graphene being coated on carbon fiber；
Fig. 5 is the true picture of the wire Asymmetric Supercapacitor utilizing the present invention to make；
Fig. 6 is the cyclic voltammetry result of asymmetric capacitor in the present invention.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with concrete real
Execute example, and referring to the drawings, the present invention is described in further detail.
Fig. 1 shows the knot of the ultracapacitor with light spy performance of a kind of wire disclosed by the invention
Composition.As it is shown in figure 1, it includes the positive electrode of asymmetric capacitor, negative material and electrolyte.
Described ultracapacitor is the flexible device of wire, can bend.Wherein, positive electrode growth is online
In shape conductive substrates, and negative material uniform winding is in described line-shaped conductive substrate.Leading of its wire
Electricity substrate can be nickel wire, titanium silk, carbon fiber etc..Its positive electrode can use Cobalto-cobaltic oxide,
Can also be simultaneously that other have the semi-conducting material of capacitive property, such as manganese dioxide, nickel oxide, cobalt
Acid nickel etc..Negative material can be Graphene, it is also possible to be that other have capacitive property and light simultaneously
Visit the material of performance, such as CNT, carbon nano-fiber, carbon nano-particle etc..Described negative pole material
Material can reach light spy as light-sensitive material by detecting the leakage current of asymmetric capacitor under light illumination
Purpose.
The ultracapacitor that the present invention proposes is Asymmetric Supercapacitor, has linear structure, and
While storing energy, it is also possible to there is the function of light-detecting device, it is possible to achieve to visible ray
Detection.
The invention allows for a kind of wire has the preparation method that light visits the ultracapacitor of performance.
Specifically include:
Step 1, with hydro-thermal method nickel wire (or titanium silk) upper growth cobaltosic oxide nano linear array (see
Fig. 2 and Fig. 3) it is used as positive pole, the Graphene being coated on carbon fiber (see Fig. 4) is used as negative pole,
With PVA-KOH colloidal sol as electrolyte.
Step 2, positive and negative electrode is impregnated five minutes in PVA-KOH colloidal sol；
Step 3, then with tweezers, the carbon fiber winding scribbling Graphene there is Cobalto-cobaltic oxide in growth
Nickel wire (or titanium silk) on.
Step 4, in atmosphere natural drying, remove the moisture in electrolyte, in case test.
As shown in Figures 2 and 3, the homoepitaxial one layer of length four oxygen at 1-2 micron on nickel wire
Change three cobalt nanowire arrays.The true picture such as Fig. 5 of the flexible asymmetric super-capacitor completed
Shown in.
The manufacturing process of each step above-mentioned is described below according to instantiation:
In the present invention, the preparation process of cobaltosic oxide nano linear array is as follows:
Step 1, add 5mmol cobalt chloride hexahydrate and 20mmol urea element be dissolved in 50mL go from
In sub-water；
Step 2, take the above-mentioned solution of 40mL add 50mL autoclave in；
Step 3, nickel wire successively clean 15 minutes in deionized water, ethanol, acetone；
Step 4, cleaned nickel wire is put in above-mentioned autoclave.
Step 5, react 4 hours at 95 DEG C, clean with deionized water after taking-up, and be dried.
Step 6, by dried sample, anneal 80 minutes at 300 DEG C, be cooled to room temperature.
The prepared length of cobaltosic oxide nano linear array, diameter etc. can by the time reacted,
The combined factors regulation and control such as the temperature of reaction.
The coating of Graphene: the Graphene of 10mg is dissolved in 20mLN-methylpyrrolidone solution,
Ultrasonic disperse 3 hours；Then by ready impregnated carbon fiber in above-mentioned solution 30 minutes.Take
It is dried 12 hours at 80 DEG C after going out.
The assembling of asymmetric capacitor: growth is had nickel wire and the coating of cobaltosic oxide nano linear array
There is the impregnated carbon fiber of Graphene in PVA-KOH sol-electrolyte 5 minutes；Then will with tweezers
The carbon fiber uniform winding being coated with Graphene has on the nickel wire of Cobalto-cobaltic oxide long, in atmosphere certainly
So it is dried, removes the moisture in electrolyte.Condenser voltage window after assembling at 0.0-1.5V,
As shown in Figure 6.Illustrate that this unsymmetric structure can improve the energy of capacitor storage to a great extent
Amount.
In another example, each preparation process of the ultracapacitor with light spy performance of described wire
As follows:
The synthetically prepared step of cobaltosic oxide nano linear array is as follows:
Step 1,5mmol cobalt chloride hexahydrate and 20mmol urea element are dissolved in the deionized water of 50mL
In；
Step 2, take the above-mentioned solution of 40mL add 50mL autoclave in；
Step 3, titanium silk successively clean 15 minutes in deionized water, ethanol, acetone；
Step 4, cleaned titanium silk is put in above-mentioned autoclave.
Step 5, react 4 hours at 95 DEG C, clean with deionized water after taking-up, and be dried.
Step 6, by dried sample, anneal 80 minutes at 300 DEG C, be cooled to room temperature.
The prepared length of cobaltosic oxide nano linear array, diameter etc. can by the time reacted,
The combined factors regulation and control such as the temperature of reaction.
The coating (ibid) of Graphene: the Graphene of 10mg is dissolved in 20mL N-crassitude
In ketone solution, ultrasonic disperse 3 hours；Then by ready impregnated carbon fiber in above-mentioned solution 30
Minute.It is dried 12 hours at 80 DEG C after taking-up.
The assembling of linear flexible asymmetric capacitor: growth is had the titanium of cobaltosic oxide nano linear array
Silk and be coated with the impregnated carbon fiber of Graphene in PVA-KOH sol-electrolyte 5 minutes；Then
The carbon fiber uniform winding being coated with Graphene with tweezers has on the titanium silk of Cobalto-cobaltic oxide long,
Natural drying in air, removes the moisture in electrolyte.Linear flexible after assembling is asymmetric super
Condenser voltage window is equally at 0.0-1.5V.
In wire flexible asymmetric super-capacitor, if negative material uses Graphene, with
Time this material can be as the light-sensitive material of visible ray to infrared light.Under light illumination, the electric leakage of capacitor
Stream can change, and by detecting these small changes, can reflect the size of intensity of illumination, enter
And reach the purpose that light is visited.
The present invention is not only limited to above-mentioned detailed description of the invention, and persons skilled in the art are according to this
Bright disclosure, can use other multiple detailed description of the invention to implement the present invention, therefore, every
Use design structure and the thinking of the present invention, capacitor is used as the work of optical detection examination, both fall within this
The scope of invention protection.
Particular embodiments described above, is carried out the purpose of the present invention, technical scheme and beneficial effect
Further describe it should be understood that the foregoing is only the specific embodiment of the present invention,
Be not limited to the present invention, all within the spirit and principles in the present invention, any amendment of being made,
Equivalent, improvement etc., should be included within the scope of the present invention.
Claims (4)
1. wire has the preparation method that light visits the ultracapacitor of performance, comprising:
Step 1, use hydro-thermal method grow cobaltosic oxide nano linear array on nickel wire or titanium silk and are just being used as
Pole, the Graphene being coated on carbon fiber is used as negative pole, with PVA-KOH colloidal sol as electrolyte；
Step 2, positive and negative electrode is impregnated five minutes in PVA-KOH colloidal sol；
Step 3, then there is the nickel wire of Cobalto-cobaltic oxide in growth by scribbling the carbon fiber winding of Graphene
Or on titanium silk；
Step 4, in atmosphere natural drying, remove the moisture in electrolyte, complete the system of capacitor
Standby.
2. the method for claim 1, wherein cobaltosic oxide nano linear array in step 1
Following making:
Step 101, add 5mmol cobalt chloride hexahydrate and 20mmol urea element is dissolved in going of 50mL
In ionized water；
Step 102, take the above-mentioned solution of 40mL add 50mL autoclave in；
Step 103, nickel wire or titanium silk successively clean 15 minutes in deionized water, ethanol, acetone；
Step 104, cleaned nickel wire is put in above-mentioned autoclave；
Step 105, react 4 hours at 95 DEG C, clean with deionized water after taking-up, and be dried；
Step 106, by dried sample, anneal 80 minutes at 300 DEG C, be cooled to room temperature.
The most the method for claim 1, wherein graphene coated by following method: will
The Graphene of 10mg is dissolved in 20mL N-Methyl pyrrolidone solution, ultrasonic disperse 3 hours；So
After by ready impregnated carbon fiber in above-mentioned solution 30 minutes, be dried 12 at 80 DEG C after taking-up
Hour.
4. the method as described in any one of claim 1-3, wherein, described ultracapacitor has storage
Deposit the function of energy and optical detection.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103971940B (en) * | 2014-05-14 | 2017-01-18 | 华中科技大学 | Flexible super capacitor and preparing method thereof |
| CN104211128A (en) * | 2014-09-05 | 2014-12-17 | 南开大学 | Preparation method of one-dimensional NiCo2O4 nanorod as supercapacitor material |
| CN104701028A (en) * | 2015-03-27 | 2015-06-10 | 吉林化工学院 | Preparation method of cobaltosic oxide micron beam shaped array structure of electrode material of super capacitor |
| CN104681299B (en) * | 2015-03-27 | 2017-11-14 | 吉林化工学院 | Electrode material for super capacitor of cobaltosic oxide porous nano linear array and preparation method thereof |
| CN104934234A (en) * | 2015-06-17 | 2015-09-23 | 苏州大学 | Preparation method for linear asymmetrical supercapacitor and supercapacitor prepared by same |
| CN104979103B (en) * | 2015-06-17 | 2017-12-15 | 苏州大学 | A kind of spiral yarn shaped Asymmetric Supercapacitor preparation method |
| CN105355459A (en) * | 2015-11-24 | 2016-02-24 | 华中科技大学 | Knittable asymmetric capacitor and preparation method thereof |
| CN106365210A (en) * | 2016-08-29 | 2017-02-01 | 浙江工业大学 | Preparation and application of shape-controlled cobaltosic oxide nano array |
| CN108257795B (en) * | 2018-01-10 | 2020-11-03 | 北京石墨烯研究院 | Method for improving capacitance of super capacitor |
| CN110648861B (en) * | 2019-09-12 | 2021-10-15 | 陕西国防工业职业技术学院 | In-situ growth of braided porous channel NiCo2O4Method of nanosheet |
| CN110600835B (en) * | 2019-09-24 | 2021-03-09 | 中国科学技术大学 | Stretchable flexible metal-air battery |
| CN114899016B (en) * | 2022-05-09 | 2023-08-04 | 武夷学院 | Preparation method of graphene oxide-based flexible supercapacitor |
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| CN102347147A (en) * | 2010-07-30 | 2012-02-08 | 北京大学 | Dye sensitization solar battery |
| CN102881463A (en) * | 2012-08-14 | 2013-01-16 | 北京大学 | Fibrous supercapacitor and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102347147A (en) * | 2010-07-30 | 2012-02-08 | 北京大学 | Dye sensitization solar battery |
| CN102881463A (en) * | 2012-08-14 | 2013-01-16 | 北京大学 | Fibrous supercapacitor and manufacturing method thereof |
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