CN207602416U - A kind of structure of self-supporting super capacitor electrode material - Google Patents
A kind of structure of self-supporting super capacitor electrode material Download PDFInfo
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- CN207602416U CN207602416U CN201720972881.2U CN201720972881U CN207602416U CN 207602416 U CN207602416 U CN 207602416U CN 201720972881 U CN201720972881 U CN 201720972881U CN 207602416 U CN207602416 U CN 207602416U
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Abstract
A kind of structure of self-supporting super capacitor electrode material, using the flexible base material of high conductivity as conducting bracket, one layer of vertical arrangement, the active material nanometer sheet with fake capacitance performance for the structure that is cross-linked with each other are grown on its surface, one layer of conducting polymer is uniformly coated again on active material nanometer sheet surface.Again with compared with high electrochemical stability while electrode material prepared by the utility model is with high power capacity, it is applied successfully to electrode of super capacitor and shows excellent performance.
Description
Technical field
The utility model belongs to electrochemical energy storage field, is related to a kind of with high power capacity high stability self-supporting super capacitor
The structure of device electrode material.
Background technology
Ultracapacitor is as a kind of emerging energy storage device, because it has relative to the higher power density of battery, soon
The charging and discharging capabilities of speed, high service life and environmental-friendly and be concerned.But its energy density is far below battery, limits
It is as the application in terms of main power source.Therefore, how by design with efficient electrode material come improve its energy density into
For urgent problem to be solved at this stage.
Transition metal oxide, hydroxide, sulfide etc. are widely used due to they have high theoretical specific capacitance
In electrode material for super capacitor.But since the design of its single structure causes its efficient capacitive property that cannot give full play of
Come.Or electrode is prepared using traditional handicraft, because needing to add in binding agent so as to reduce its chemical property.
Fake capacitance material with high power capacity and the carbon material of high conductivity carry out to compound to be a kind of extensive use carry
The method of high material electrochemical performance.The addition of carbon material can not only improve the electric conductivity of fake capacitance material, reduce material
Resistance can also improve the electrochemical stability of material to a certain extent.Such as：Shen et al.（Adv. Energy Mater.
2015, 5, 1400977）NiCo is grown in carbon foam2S4Composite material prepared by nanometer sheet is used as electrode of super capacitor,
The specific capacitance of 1231 F/g (2 A/g) is obtained in three-electrode system, and is still maintained after the circle of charge and discharge cycles 2000
90.4% efficiency.Wen et al.（J. Power. Sources 2016, 320, 28–36）By NiCo2S4With multi-wall carbon nano-tube
Manage compound, up to 2080 F/g (1 A/g), charge and discharge cycles 2000 still maintain its specific capacitance after enclosing in three-electrode system
83% efficiency.It can be seen that the introducing of carbon material can greatly promote the chemical property of material.But the specific capacitance obtained is still
Well below NiCo2S4The theoretical specific capacitance of itself.The reason is that NiCo2S4Itself microstructure design it is unreasonable so that
The synergistic effect performance of two kinds of materials cannot have effectively been given play to after compound with carbon material.
On the other hand, in prolonged charge and discharge cycles, the microstructure of electrode material can be destroyed cause its performance,
Service life declines.While preparing with high performance electrode material, the electrochemical stability of material how to be kept equally to close very much
Key.It is that one kind effectively prevent material structure to collapse raising material settling out by coating one layer of thin protective layer in active material surface
The method of property.Lu et al.（Adv. Energy Mater. 2016, 4, 1300994）One layer is coated in TiN nanowire surfaces
Carbon, its stability is increased to 85% by original 10% after 15000 cycles.In addition to carbon coating, Zhou et al.（Nano
Lett. 2013, 13, 2078−2085）By polymerizeing one layer of conducting polymer PPy in CoO nanowire surfaces, can not only carry
The stability of high material, because PPy itself has fake capacitance effect, the capacitive property of composite material also increases.
Utility model content
The purpose of this utility model is to provide a kind of structure of self-supporting super capacitor electrode material.It is answered by material
The method of conjunction, structure design and conducting polymer cladding, prepares the electrode material for super capacitor for having both high power capacity high stability.
The effective material for having fake capacitance performance in customary preparation methods that solves is combined insecure, random growth, internal resistance with substrate
Greatly, the problem of active material utilization is not high has both high electrochemical stability while high power capacity is kept, and is prepared for design
High-efficiency energy-storage material provides a kind of effective method.
The utility model is achieved through the following technical solutions.
A kind of self-supporting super capacitor electrode material structure described in the utility model, it is characterized in that with high conductivity
Flexible base material grows on its surface one layer of vertical arrangement, the structure that is cross-linked with each other has fake capacitance as conducting bracket
The active material nanometer sheet of energy uniformly coats one layer of conducting polymer again on active material nanometer sheet surface.
Preferably, the flexible base material with high conductivity is carbon nano-fiber, carbon cloth, wire or metal foil
Etc. flexible substrates.
Preferably, the active material with fake capacitance performance is transition metal oxide, hydroxide or sulfide.
Preferably, the conducting polymer is polypyrrole（PPy）, polyaniline（PANI）It is or poly-（3,4- dioxoethyls）Thiophene
Fen（PEDOT）.
A kind of self-supporting super capacitor electrode material structure described in the utility model can be prepared by the following method,
Include the following steps.
（1）It chooses or prepares the flexible base material with high conductivity, as conducting bracket.
（2）In step（1）Active material of the substrate material surface growth with fake capacitance performance, structure are vertical row
Cloth, the nano-chip arrays being cross-linked with each other.
（3）In step（2）Obtained one layer of conducting polymer of active material nanometer sheet coated with uniform.
A kind of self-supporting super capacitor electrode material structure described in the utility model compared with the conventional method, have with
Lower technological merit.
（1）The nano-chip arrays structure for active material with fake capacitance performance is designed to vertical arrangement, being cross-linked with each other
It is grown in highly conductive flexible base material surface.On the one hand, the intrinsic structure of flexible substrates is not destroyed, after compound
Its mechanical stability can still be kept；On the other hand, two-dimensional structure, the nanometer sheet of vertical arrangement are not only opposite with zero dimension and one-dimensional knot
Structure has higher quality percentage under same volume, and can also be maximized with the contact area of electrolyte, makes active matter
Matter can fully react to improve the utilization rate of active material with electrolyte.
（2）Because during multiple charge and discharge and high current charge-discharge, the microstructure of active material can by destroy from
And influence the stability of electrode.The size of the two-dimensional nano piece of the orthogonal array is larger, and the structure to improve nanometer sheet is steady
Qualitative, the utility model proposes coat one layer of conducting polymer thin film in nanometer sheet in situ Polymerization.Conducting polymer coats
Nanometer sheet can be fixed on nanometer sheet is stronger in substrate, makes the integrality of its holding structure in charge and discharge process.With this
It keeps having both excellent electrochemical stability while its high power capacity, have to the super capacitor material for preparing efficient stable good
Good enlightenment.
Description of the drawings
Fig. 1 is the utility model electrode material structure diagram.1 is the flexible base material of high conductivity；2 be with counterfeit
The active material nanometer sheet of capacitive property；3 be conducting polymer.
Fig. 2 is the structure diagram of the active material nanometer sheet with fake capacitance performance in Fig. 1.
Fig. 3 is step e in the utility model embodiment）Obtained carbon nano-fiber/vulcanization nickel cobalt/film of poly pyrrole is compound
The scanning electron microscope diagram of electrode.
Fig. 4 is step c in the utility model embodiment）, step d）With step e）The cycle of the combination electrode respectively obtained
Stability contrast figure.
Specific embodiment
It is new to this practicality below in conjunction with drawings and examples in order to which the superiority for making the utility model is more clearly understood
Type is further elaborated.It should be appreciated that specific embodiment described herein is used only for explaining the utility model, and
It is not used in restriction the utility model.In addition, the technological means involved by each embodiment described in embodiment can be more
Sample is not limited in the experimental technique means.
Embodiment 1.
A kind of self-supporting super capacitor electrode material structure is propped up using the flexible base material 1 of high conductivity as conduction
Frame grows one layer of vertical arrangement, the active material nanometer sheet 2 with fake capacitance performance for the structure that is cross-linked with each other on its surface,
Active material nanometer sheet surface uniformly coats one layer of conducting polymer 3 again.
The flexible base material of the high conductivity is carbon nano-fiber, has the active material nanometer of fake capacitance performance
Sheet material is transition metal oxide, and conducting polymer is polypyrrole.
Embodiment 2.The preparation process of self-supporting super capacitor electrode material structure.
a）By polyacrylonitrile（PAN）Add in dimethylformamide（DMF）In solution, stirred 12 hours at 60 DEG C and obtain electricity
Solution is spun, nano fibrous membrane is prepared with electrostatic spinning technique.
b）By step a）Obtained tunica fibrosa is first small with the pre-oxidation 2 of the heating rate of 5 DEG C/min under 250 DEG C of air atmospheres
When, then be carbonized 0.5 hour with the heating rate of 5 DEG C/min under 1000 DEG C of nitrogen atmospheres and obtain carbon nanofiber membrane.From scanning
It can be seen that even in fiber diameter distribution, surface are smooth in electron micrograph.
c）By step b）Obtained carbon nanofiber membrane（1×2 cm）It is used as working electrode, immerses 50 mL electric depositing solutions
In, using Ag/AgCl electrodes as reference electrode, platinum plate electrode is to electrode, carries out electrochemical deposition, then clear with deionized water
It washes, 60 DEG C are dried to obtain carbon nano-fiber/nickel cobalt double-hydroxide membrane electrode.It can be seen that from electron scanning micrograph
Vertical arrangement, the nanometer sheet being cross-linked with each other are evenly coated at fiber surface, and nanometer sheet surface is smooth.
d）By step c）Obtained carbon nano-fiber/nickel cobalt double-hydroxide immerses the thioacetamide 50 containing 50 mM
In mL aqueous solutions, be put into 120 DEG C of hydrothermal reaction kettle and react 3 hours, deionized water cleaning, 60 DEG C be dried to obtain carbon nano-fiber/
Vulcanize nickel cobalt membrane electrode.It can be seen that nanometer sheet surface becomes coarse from electron scanning micrograph.
e）By step d）Obtained carbon nano-fiber/vulcanization nickel cobalt immerses 5 min in pyrrole monomer, is then immersed in 100 mL
Containing 8 grams of iron chloride, 0.3 M hydrochloric acid aqueous solution in, reacted 1 minute at 4 DEG C, with 0.3 M hydrochloric acid solutions and 0.1 M
Sodium chloride solution repeated washing three times, then with deionized water is cleaned three times, 60 DEG C be dried to obtain carbon nano-fiber/vulcanization nickel cobalt/
Polypyrrole Film Electrodes.It can be seen that nanometer sheet surface significantly becomes more coarse, and nanometer sheet from electron scanning micrograph
Become thicker.
The electrospun solution mass fraction is 10 wt%.The electrospinning condition is 17 kV, 1 mL h-1.The electricity
Deposition solution contains 10 mM metal ions（Co2+/Ni2+It is 2:1）.The electrodeposition condition is -1.2V voltage ranges, 30
mV s-1Sweep 120 circle of cycle under speed.
The utility model improves the capacitive property of material and cyclical stability by structure design and surface modification.It will reason
By the high fake capacitance material of capacity（NiCo2S4）It is designed to nanometer chip architecture and vertical-growth is in highly conductive carbon nano-fiber table
Face allows electrolyte that faraday's reaction storage energy fully to occur with active material.Because the size of two-dimensional nano piece is bigger,
To ensure that entire nanometer sheet gives full play to fake capacitance effect, in one layer of ultra-thin polypyrrole of its in situ Polymerization（PPy）Film, with
Improve the electric conductivity and electrochemical stability of whole nanometer sheet.In addition to this, polypyrrole itself has fake capacitance effect, can be into one
Step improves the capacitive property of composite material.
The utility model is not limited to above-described embodiment, and specifically, flexible base material is not limited to electrospinning carbon and receives
Rice fiber or carbon cloth, metal（Nickel, copper, titanium etc.）Silk, metal（Nickel, copper, titanium etc.）Foil etc. has the flexibility of high conductivity
Substrate；Active material with fake capacitance performance is not limited to cobalt sulfide nickel or transition metal oxide, hydroxide
Object, sulfide；Conducting polymer is not limited to polypyrrole or polyaniline, poly-（3,4- dioxoethyls）Thiophene
（PEDOT）Wait conducting polymers.It can consider with reference to different substrates, fake capacitance material and conducting polymer, with this
Utility model mentality of designing prepares efficient electrode material for super capacitor.
The above is only the preferred embodiment of the utility model only, is not intended to limit the utility model, all at this
Any modification, improvement and replacement made within the mentality of designing and principle of utility model etc., should be included in the utility model
Protection domain within.
Claims (4)
1. a kind of self-supporting super capacitor electrode material structure, it is characterized in that using the flexible base material of high conductivity as leading
Electric stent grows one layer of vertical arrangement, the active material nanometer sheet with fake capacitance performance for the structure that is cross-linked with each other on its surface,
One layer of conducting polymer is uniformly coated again on active material nanometer sheet surface.
2. a kind of self-supporting super capacitor electrode material structure according to claim 1, it is characterized in that described have height
The flexible base material of electric conductivity is carbon nano-fiber, carbon cloth, wire or metal foil.
3. a kind of self-supporting super capacitor electrode material structure according to claim 1, it is characterized in that described with counterfeit
The active material of capacitive property is transition metal oxide, hydroxide or sulfide.
4. a kind of self-supporting super capacitor electrode material structure according to claim 1, it is characterized in that described conductive poly-
Conjunction object is polypyrrole, polyaniline or poly- (3,4- dioxoethyls) thiophene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107658140A (en) * | 2017-08-07 | 2018-02-02 | 南昌大学 | The structure and preparation method of a kind of self-supporting super capacitor electrode material |
| CN112735844A (en) * | 2020-12-25 | 2021-04-30 | 浙江工业大学 | Method for preparing flexible foam carbon-based composite electrode material by electrochemical deposition method |
-
2017
- 2017-08-07 CN CN201720972881.2U patent/CN207602416U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107658140A (en) * | 2017-08-07 | 2018-02-02 | 南昌大学 | The structure and preparation method of a kind of self-supporting super capacitor electrode material |
| CN112735844A (en) * | 2020-12-25 | 2021-04-30 | 浙江工业大学 | Method for preparing flexible foam carbon-based composite electrode material by electrochemical deposition method |
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