CN108806999A - Electrode material, ultracapacitor, electronic equipment and the method for preparing electrode material - Google Patents
Electrode material, ultracapacitor, electronic equipment and the method for preparing electrode material Download PDFInfo
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- CN108806999A CN108806999A CN201710308095.7A CN201710308095A CN108806999A CN 108806999 A CN108806999 A CN 108806999A CN 201710308095 A CN201710308095 A CN 201710308095A CN 108806999 A CN108806999 A CN 108806999A
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
This application provides a kind of electrode material, ultracapacitor, electronic equipment and the methods for preparing electrode material.The electrode material, including charge collector film layer and graduation array bilayer film layer, the graduation array bilayer film layer includes nano-scale sheet-like array film layer and the flower-shaped array film layer of micron-scale, wherein, the nano-scale sheet-like array film layer is the growth in situ in the charge collector film layer, and the flower-shaped array film layer of the micron-scale is arranged in the upper layer of the nano-scale sheet-like array film layer.Electrode material provided by the present application growth in situ nano-scale sheet-like array film layer in charge collector film layer, the flower-shaped array film layer of one layer of micron-scale is regenerated thereon, form graduation array bilayer film layer, there is a large amount of pore structure in array bilayer film layer of classifying, the contact area that the active material load quality and active material and electrolyte circle on charge collector unit area can be greatlyd improve, can effectively improve the specific capacity of electrode material.
Description
Technical field
This application involves energy storage fields, and more particularly, to electrode material, ultracapacitor, electronic equipment and system
The method of standby electrode material.
Background technology
Ultracapacitor is a kind of novel energy-storing system of fast development in recent ten years.Compared with battery system, tool
There are the advantages such as fast charging and discharging, long circulation life.Electrode material is the important component of ultracapacitor, the size of specific capacity
It is the key index for evaluating electrode material quality.The size of the specific capacity of electrode material directly affects its corresponding ultracapacitor
Energy density.For this point, constructing faraday's electrode material of high theoretical specific capacity becomes main research direction.It is existing
Electrode material, although fast charging and discharging, long circulation life etc. may be implemented, it might even be possible to realize flexible foldable, electrode
Active material utilization in material is still relatively low, and the requirement of many application scenarios is still not achieved in specific capacity.
Invention content
The application provides a kind of electrode material, ultracapacitor, electronic equipment and the method for preparing electrode material, Neng Gouyou
Effect improves the specific capacity of electrode material, and then improves the energy density of ultracapacitor.
In a first aspect, a kind of electrode material is provided, including charge collector film layer and graduation array bilayer film layer, institute
It includes nano-scale sheet-like array film layer and the flower-shaped array film layer of micron-scale to state graduation array bilayer film layer, wherein described
Nano-scale sheet-like array film layer is the growth in situ in the charge collector film layer, the flower-shaped array films of micron-scale
Layer is arranged in the upper layer of the nano-scale sheet-like array film layer.
The electrode material that first aspect provides growth in situ nano-scale sheet-like array film layer in charge collector film layer,
The flower-shaped array film layer of one layer of micron-scale is regenerated thereon, forms graduation array bilayer film layer, array bilayer film layer of classifying
In there is a large amount of pore structure, can greatly improve active material load quality on charge collector unit area and
The contact area of active material and electrolyte circle can effectively improve the specific capacity of electrode material.In addition, what first aspect provided
Electrode material avoids the use of conductive additive and binder, can improve the conductance of electrode material and improve active material institute
Accounting example contributes to the promotion of electrode material specific capacity.
In a kind of possible realization method of first aspect, the ingredient of the graduation array bilayer film layer can be gold
Belong to oxide, metal hydroxides or metal composite oxide, the metal oxide, metal hydroxides or composition metal oxygen
Metal in compound may include at least one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Mo.In this possible reality
In existing mode, the nano array structure of transition metal oxide, transition metal hydroxide or composite transition metal oxide has
There is higher specific surface area, is conducive to the specific capacity for improving electrode material.
In a kind of possible realization method of first aspect, the charge collector can be flexible electrical lotus collector.
It in this possible realization method, is constructed in situ on flexible charge collector using active material film layer, realizes that battery is being drawn
It the chemical property under deformations such as stretches, reverse, being bent not lose.
In a kind of possible realization method of first aspect, the charge collector can be carbon cloth, carbon fiber
Paper, carbon fiber film, graphene-based charge collector, carbon nanotube elementary charge collector, metal or alloy fiber cloth, metal or
Alloy network, metal or alloy film, one kind in foam metal are combined by least two.
In a kind of possible realization method of first aspect, the charge collector can have metal coating, alloy
Coating, carbon material coating or battery system coating layer of active substance, to be conducive to further increase the specific capacity of electrode material.
In a kind of possible realization method of first aspect, the nano-scale sheet-like array film layer may include mutual
The multiple nano-scale monolithics for the vertical arrangement that interweaves, the diameter of the nano-scale monolithic can be greater than or equal to 1nm and small
In or equal to 1000nm, the thickness of the nano-scale monolithic can be more than or equal to 1nm and less than or equal to 100nm, institute
0.5 μm can be greater than or equal to and be less than or equal to 100 μm by stating the thickness of nano-scale sheet-like array film layer.In first aspect
A kind of possible realization method in, the flower-shaped array film layer of micron-scale may include multiple micron-scale single flowers, described
The diameter of micron-scale single flower can be greater than or equal to 1 μm and be less than or equal to 10 μm, the flower-shaped array films of micron-scale
The thickness of layer can be greater than or equal to 1 μm and be less than or equal to 100 μm.In above-mentioned possible realization method, active material
The nanosizing and array of film layer are the effective means for the specific surface area active for improving electrode material, and array structure inside is a large amount of
Hole enables to active material film layer internal material to be also used effectively, to improve the specific capacity of electrode material.
In a kind of possible realization method of first aspect, the nano-scale sheet-like array film layer includes being interweaved
Multiple nano-scale monolithics of vertical arrangement, the flower-shaped array film layer of micron-scale includes multiple micron-scale single flowers, described
Micron-scale single flower is by being self-assembly of after the nano-scale monolithic diauxic growth or in-situ deposition is formed.
The good mechanical stability of the electrode material of this possible realization method.
In a kind of possible realization method of first aspect, the nano-scale sheet-like array film layer is to pass through constant current
What deposition obtained, the flower-shaped array film layer of micron-scale is to deposit to obtain by constant voltage.
Second aspect, provides a kind of ultracapacitor, and the ultracapacitor includes first aspect and corresponding reality
Electrode material described in existing mode.
The active material on electrode material charge collector unit area in the ultracapacitor that second aspect provides is negative
Mounted mass is high, and the contact area of active material and electrolyte circle is big, has high specific capacity so that ultracapacitor has high
Energy density.
In a kind of possible realization method of second aspect, the ultracapacitor is symmetrical ultracapacitor, described
The anode and cathode of symmetrical ultracapacitor are made by the electrode material.
In a kind of possible realization method of second aspect, the ultracapacitor is Asymmetric Supercapacitor, institute
The anode for stating Asymmetric Supercapacitor is made by the electrode material.The asymmetric super electricity of this possible realization method
Container uses faraday's capacitance material (electrode material of the embodiment of the present application) and double layer electrodes material to exist respectively by the two poles of the earth
Complementation on potential windows can greatly improve the operating voltage and energy density of Asymmetric Supercapacitor.
The third aspect, provides a kind of electronic equipment, and the electronic equipment includes first aspect and corresponding realization side
Electrode material described in formula.
Fourth aspect provides a kind of method preparing electrode material, including：Charge collector is purified and done
It is dry, form charge collector film layer；The charge current collector film is placed in electrolyte and carries out galvanostatic deposition, in the electricity
Growth in situ nano-scale sheet-like array film layer in lotus collector film layer；Deposition there is into the nano-scale sheet-like array film layer
The charge current collector film is placed on progress constant voltage deposition in the electrolyte, in the nano-scale sheet-like array film layer
Form the flower-shaped array film layer of micron-scale.
The method for preparing electrode material that fourth aspect provides, charge afflux is deposited on by galvanostatic deposition and constant voltage
On body, nano-scale sheet-like array film layer and the flower-shaped array film layer of micron-scale are obtained, the electrode material of height ratio capacity can be prepared
Material, preparation method is simple, can be adapted for scale of mass production.
In a kind of possible realization method of fourth aspect, the electrolyte includes source metal salt, the source metal
Salt is for generating the nano-scale sheet-like array film layer and the flower-shaped array film layer of the micron-scale, wherein the nanometer ruler
The ingredient of very little sheet-like array film layer and the flower-shaped array film layer of the micron-scale is metal oxide, metal hydroxides or compound
Metal oxide, the metal in the metal oxide, metal hydroxides or metal composite oxide include Sc, Ti, V, Cr,
At least one of Mn, Fe, Co, Ni, Cu, Zn and Mo.
Further include Na salt in the electrolyte in a kind of possible realization method of fourth aspect.
In a kind of possible realization method of fourth aspect, the electrolyte include villaumite, acetate, nitrate,
One or more of sulfate.
In a kind of possible realization method of fourth aspect, the galvanostatic deposition and constant voltage deposition pass through three
Electrode system is realized, wherein using metal platinized platinum as to electrode, using saturated calomel electrode as reference electrode, with to be deposited
Charge collector film layer is as working electrode.
In a kind of possible realization method of fourth aspect, in the electrolyte, the working electrode with it is described right
Electrode runs parallel is opposite, and the working electrode is with described to being 0.2cm at a distance from electrode.
In a kind of possible realization method of fourth aspect, the voltage range of the galvanostatic deposition is to be more than or wait
In -1V and it is less than or equal to 1V, the deposition duration of the galvanostatic deposition is greater than or equal to 10s and is less than or equal to
1000s。
In a kind of possible realization method of fourth aspect, the voltage range of the constant voltage deposition is to be more than or wait
In -1.5V and it is less than or equal to 1.5V, the deposition duration of the constant voltage deposition is greater than or equal to 10s and is less than or equal to
1000s。
In a kind of possible realization method of fourth aspect, the charge collector is carbon cloth, carbon fiber paper, carbon
Fiber membrane, graphene-based charge collector, carbon nanotube elementary charge collector, metal or alloy fiber cloth, metal or alloy
Net, metal or alloy film, one kind in foam metal are combined by least two.
In a kind of possible realization method of fourth aspect, the charge collector have metal coating, alloy coat,
Carbon material coating or battery system coating layer of active substance.
In a kind of possible realization method of fourth aspect, the nano-scale sheet-like array film layer includes being interweaved
The diameter of multiple nano-scale monolithics of vertical arrangement, the nano-scale monolithic is greater than or equal to 1nm and is less than or equal to
The thickness of 1000nm, the nano-scale monolithic are greater than or equal to 1nm and are less than or equal to 100nm, the nano-scale piece
The thickness of shape array film layer is greater than or equal to 0.5 μm and is less than or equal to 100 μm.
In a kind of possible realization method of fourth aspect, the flower-shaped array film layer of micron-scale includes multiple microns
The diameter of size single flower, the micron-scale single flower is greater than or equal to 1 μm and is less than or equal to 10 μm, the micron-scale flower
The thickness of shape array film layer is greater than or equal to 1 μm and is less than or equal to 100 μm.
In a kind of possible realization method of fourth aspect, the nano-scale sheet-like array film layer includes being interweaved
Multiple nano-scale monolithics of vertical arrangement, the flower-shaped array film layer of micron-scale includes multiple micron-scale single flowers, described
Micron-scale single flower is by being self-assembly of after the nano-scale monolithic diauxic growth or in-situ deposition is formed.
Description of the drawings
Fig. 1 is the schematic diagram of the electrode material of the application one embodiment.
Fig. 2 is the schematic diagram of the method for preparing electrode material of the application one embodiment.
Fig. 3 is the schematic flow chart of the method for preparing electrode material of the application one embodiment.
Fig. 4 is CV curve of the symmetrical ultracapacitor of the application one embodiment under different scanning speed.
Fig. 5 is that constant current charge-discharge of the symmetrical ultracapacitor of the application one embodiment under different current densities is bent
Line.
Fig. 6 is CV curve of the Asymmetric Supercapacitor of the application one embodiment under different scanning speed.
Fig. 7 is constant current charge-discharge of the Asymmetric Supercapacitor of the application one embodiment under different current densities
Curve.
Fig. 8 is the symmetrical ultracapacitor of the application one embodiment and the asymmetric super electricity of the application one embodiment
The comparison diagram of the cycle performance of container.
Specific implementation mode
Below in conjunction with attached drawing, the technical solution in the application is described.
A kind of existing scheme is to deposit Co on flexible charge collector3O4-Au-MnO2Nano-sheet array.Co3O4-
Au-MnO2It is arranged vertically to form array in nano-sheet, is a kind of three-dimensional tri compound structure.Wherein, one layer of Co3O4With one layer
MnO2As electroactive substance, middle layer Au is as conducting medium.Co3O4-Au-MnO2Nano-sheet array is as electrode
When applied to ultracapacitor, the electrochemical reaction of ultracapacitor concentrates on the active material and electrolyte interface of electrode material
Place.Co3O4-Au-MnO2The structure design of nano-sheet array is due to that with middle layer Au, can cause internal layer active material relatively low
Utilization rate, be unfavorable for the raising of the specific capacity of electrode material.
Co is deposited on flexible charge collector3O4-Au-MnO2The preparation method of nano-sheet array, including：(1) it prepares
Presoma Co3O4Nano-sheet array；(2) utilize plasma sputtering in above-mentioned Co3O4It steams on the surface of nano-sheet array
Plating obtains the Co of Au films covering3O4Nano-sheet array；(3) Co for covering above-mentioned Au films3O4Nano-sheet array in
Electrochemical deposition under 0.9V current potentials, by MnO2It is coated on the Co of Au films covering3O4The surface of nano-sheet array；(4) it has reacted
Cheng Hou, cleaning, it is dry, calcine to get.
Existing another kind scheme is that growth in situ NiAl hydrotalcite arrays, hydrotalcite are layers on flexible charge collector
One kind of shape double-metal hydroxide (Layered Double Hydroxide, LDH), then by carbon nano-particles through a level pressure
The strong poor surface for being filled into NiAl hydrotalcite arrays, forms the electrode material with NiAl-LDH@CNPs structures.NiAl-LDH@
For CNPs as application of electrode when the ultracapacitor, the interface of electrode and electrolyte contacts is carbon nano-particles.Although internal
NiAl hydrotalcites have much higher theoretical specific capacity compared to other materials, but the cladding of carbon nano-particles limits itself and electricity
The diffusion of the reaction of pole liquid and electronics, electrolyte ion inside it, and cause the lower utilization of the active material of electrode material
Rate is unfavorable for the raising of the specific capacity of electrode material.
Although fast charging and discharging, long circulation life etc. may be implemented in both the above electrode material, it might even be possible to realize flexible
It is foldable, but the active material utilization in electrode material is still relatively low, and wanting for many application scenarios is still not achieved in specific capacity
It asks.
Fig. 1 is the schematic diagram of the electrode material 100 of the application one embodiment.As shown in Figure 1, electrode material 100 includes
Charge collector film layer 110 and graduation array bilayer film layer 120, the graduation array bilayer film layer 120 include nano-scale
Sheet-like array film layer 122 and the flower-shaped array film layer of micron-scale 124, wherein the nano-scale sheet-like array film layer 122 is at this
Growth in situ in charge collector film layer 110, the flower-shaped array film layer of the micron-scale 124 are arranged in the nano-scale sheet battle array
The upper layer of row film layer 122.
The electrode material of the embodiment of the present application growth in situ nano-scale sheet-like array film layer in charge collector film layer,
The flower-shaped array film layer of one layer of micron-scale is regenerated thereon, forms graduation array bilayer film layer, array bilayer film layer of classifying
In there is a large amount of pore structure, can greatly improve active material load quality on charge collector unit area and
The contact area of active material and electrolyte circle can effectively improve the specific capacity of electrode material.
For in principle, electrode material should choose the material of high theoretical specific capacity as possible, this is because high theoretical specific capacity
(high activity specific surface area) active material film layer constructs the specific capacity that can effectively promote electrode material.Active material film layer
Nanosizing and array be the specific surface area active for improving electrode material effective means, a large amount of hole inside array structure
Active material film layer internal material is enabled to also to be used effectively, to improve the specific capacity of electrode material.The application is implemented
The electrode material of example is exactly nanosizing and array, has high specific capacity.
In addition, the electrode material of the embodiment of the present application avoids the use of conductive additive and binder, electricity can be improved
The conductance of pole material simultaneously improves active material proportion, contributes to the promotion of the specific capacity of electrode material.
Meanwhile recharge, electric discharge can be effectively relieved in a large amount of holes present in array bilayer film layer structure of classifying
The pressure born when the volume expansion of active material in the process avoids the structural collapse in film layer, improves electrode material
Cyclical stability extends the cycle life of the electrode material.
In recent years, flexible, flexible, light, wearable electronic to come into being, it advances flexible energy storage and matches
The development of part.Realize the flexibility of ultracapacitor with can be practical, in the mechanical stability and electrode material of electrode material
The chemical property of active material is equally most important.For the mechanical stability this point of electrode material, can usually utilize
Original position of the active material film layer on some flexible charge collectors is constructed, and realizes battery under the deformations such as stretching, torsion, bending
Chemical property does not lose.Meanwhile binding force between charge collector and active material film layer and interface electrical conductance all can be to super
The performance of grade capacitor impacts.
Therefore, the nano array structure of transition metal oxide or hydroxide of the design with superhigh specific surface area, and
Nano array structure is constructed in situ on flexible charge collector, is to promote flexible super capacitance to form electrode material
The useful direction of device development.
Optionally, in the embodiment of the present application, charge collector can be flexible electrical lotus collector, flexible charge collector
As substrate, with flexibility, the foldability etc. for ensureing electrode material, and then ensure to apply the electrode material of the embodiment of the present application
Flexibility, flexible, light, the wearable property of electronic equipment.For example, charge collector can be carbon cloth, carbon fiber paper,
Carbon fiber film, graphene-based charge collector, carbon nanotube elementary charge collector, metal or alloy fiber cloth, metal or conjunction
Golden net, metal or alloy film, one kind in foam metal are combined by least two, but the embodiment of the present application is not limited to
This.
Further, which can have metal coating, alloy coat, carbon material coating or battery system to live
Property matter coatings, the embodiment of the present application are not construed as limiting this.
The flexible electrode material of the embodiment of the present application and solid gel electrolyte are assembled into all-solid-state flexible super capacitor
Device can realize that flexibility, high mechanical properties and the high power capacity of ultracapacitor entirety, long circulation life and good times are forthright
Energy.
For high mechanical properties this point, the flexibility of electrode material is needed through charge collector and active material film layer
High mechanical properties and resistance to mechanical adaptability to changes realize.Using flexible charge collector, and in its surface in situ position activity
Substance film layer can realize the high degree of flexibility and mechanical strength of electrode material entirety, make its electrochemistry under various mechanical deformations
Can play is not influenced by excessive.In addition, the depositional mode of the surface roughness and active material of flexible charge collector on it
Deng the interfacial contact that both can all influence, the internal resistance to influence electrode material and its cycle performance under mechanically deform.
Optionally, in the embodiment of the present application, the ingredient of the graduation array bilayer film layer 120 is metal oxide, gold
Belong to hydroxide or metal composite oxide, the metal in the metal oxide, metal hydroxides or metal composite oxide
Including at least one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Mo.Herein, mainly with array bilayer of classifying
The ingredient of film layer 120 is Co (OH)2For be introduced, but the embodiment of the present application is without being limited thereto.
In other words, graduation array bilayer film layer is generated, needs to include source metal salt in electrolyte.That is, the metal
Source salt is for generating the nano-scale sheet-like array film layer 122 and the flower-shaped array film layer of the micron-scale 124, wherein the nanometer
The ingredient of size flakes array film layer 122 and the flower-shaped array film layer of the micron-scale 144 is metal oxide, metal hydroxides
Or metal composite oxide, the metal in the metal oxide, metal hydroxides or metal composite oxide may include Sc,
At least one of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Mo, but the embodiment of the present application is without being limited thereto.Source metal salt can be with
It is one or more of villaumite, acetate, nitrate, sulfate, but the embodiment of the present application is without being limited thereto.
Can also include other neutral salt such as Na salt in addition, in addition to source metal salt, in electrolyte, as electrolytic salt,
The environment of electro-deposition is carried out to be formed.Na salt can also include villaumite, acetate, nitrate, one kind in sulfate or
It is several, but the embodiment of the present application is without being limited thereto.
Optionally, in the embodiment of the present application, which can pass through galvanostatic deposition
It obtains, the flower-shaped array film layer of the micron-scale 124 can deposit to obtain by constant voltage.
Specifically, Fig. 2 is the schematic diagram of the method 200 for preparing electrode material of the application one embodiment.Fig. 3 is this
Apply for the schematic flow chart of the method 200 for preparing electrode material of one embodiment.As shown in Figures 2 and 3, method 200 can
To include the following steps.
S210 obtains charge collector film layer.Specifically, charge collector is purified and is dried, form charge collection
Fluid film layer.
The charge current collector film is placed in electrolyte and carries out galvanostatic deposition by S220, in the charge collector film layer
Upper growth in situ nano-scale sheet-like array film layer.
S230, will deposition have the charge current collector film of the nano-scale sheet-like array film layer be placed in the electrolyte into
Row constant voltage deposits, and the flower-shaped array film layer of micron-scale is formed in the nano-scale sheet-like array film layer.
Optionally, in the embodiment of the present application, the nano-scale sheet-like array film layer 122 that galvanostatic deposition obtains can be with
Multiple nano-scale monolithics including the vertical arrangement that is interweaved, the flower-shaped array film layer of the micron-scale that constant voltage deposits
124 include multiple micron-scale single flowers, which can be by self assembly after the nano-scale monolithic diauxic growth
It is formed, or can be that in-situ deposition is formed.In other words, a part of micro- in the flower-shaped array film layer of micron-scale 124
Meter ruler cun single flower can be by being self-assembly of after nano-scale monolithic diauxic growth, the flower-shaped array film layer of micron-scale 124
In another part micron-scale single flower can be that in-situ deposition is formed, but the embodiment of the present application is without being limited thereto.
Specifically, to prepare Co (OH)2For graduation array bilayer film layer electrode material, the preparation of the embodiment of the present application
The method of electrode material can specifically include following steps.
(1) it using charge collector as substrate, deposits nano-scale sheet-like array film layer on it and micron-scale is flower-shaped
Array film layer.Charge collector can be placed in ultrasound purifying in ethyl alcohol, and dried in air.Charge collector can be soft
Property charge collector, be specifically as follows above described in material, details are not described herein again.
(2) using certain density Co salt and Na mixed solutions as the electrolyte of entire electrodeposition process, in electrochemistry work
It stands on (such as electrochemical workstation of model CHI660D), the electrodeposition process of substep is realized with three-electrode system.That is,
The galvanostatic deposition and constant voltage deposition are realized by three-electrode system, wherein using metal platinized platinum as to electrode, to be saturated
Calomel electrode is as reference electrode, using charge collector film layer to be deposited as working electrode.In the electrolytic solution, working electrode
Can be opposite with to electrode runs parallel, the working electrode with this to that can be 0.2cm at a distance from electrode.It should be understood that the above electro-deposition
Equipment, system and running parameter etc. be citing, rather than the limitation to the embodiment of the present application.
(3) galvanostatic deposition prepares Co (OH)2Nano-scale sheet-like array film layer：Voltage range is more than or equal to -1V
And it is less than or equal to 1V, deposition duration is greater than or equal to 10s and is less than or equal to 1000s.It should be understood that the above constant current is heavy
Long-pending running parameter is only for example, rather than the limitation to the embodiment of the present application.
(4) constant voltage deposition prepares Co (OH)2The flower-shaped array film layer of micron-scale：Voltage range be more than or equal to-
1.5V and be less than or equal to 1.5V, deposition duration be greater than or equal to 10s and be less than or equal to 1000s.It should be understood that above permanent
The running parameter of voltage deposition is only for example, rather than the limitation to the embodiment of the present application.
(5) obtained electrode material after spot deposition is rinsed with deionized water repeatedly, 10~80 DEG C of vacuum is dried overnight.Most
Obtaining the growth on flexible charge current collector film layer eventually has blue Co (OH)2The electrode material for array bilayer film layer of classifying.Electricity
The active material of pole material is Co (OH)2。
In general, the electrode material prepared by the above method, which may include mutually handing over
Knit multiple nano-scale monolithics of vertical arrangement, the diameter of the nano-scale monolithic can be greater than or equal to 1nm and be less than or
Equal to 1000nm, the thickness of the nano-scale monolithic can be greater than or equal to 1nm and be less than or equal to 100nm, this nanometer of ruler
The thickness of very little sheet-like array film layer can be greater than or equal to 0.5 μm and be less than or equal to 100 μm.It should be understood that the application is implemented
The size of nano-scale sheet-like array film layer is not limited to above description in the electrode material of example.
In general, the electrode material prepared by the above method, the flower-shaped array film layer of the micron-scale may include multiple micro-
The diameter of meter ruler cun single flower, the micron-scale single flower can be greater than or equal to 1 μm and be less than or equal to 10 μm, the micron-scale
The thickness of flower-shaped array film layer can be greater than or equal to 1 μm and be less than or equal to 100 μm.It should be understood that the embodiment of the present application
The size of the flower-shaped array film layer of micron-scale is not limited to above description in electrode material.
The method for preparing electrode material of the embodiment of the present application is deposited on charge afflux by galvanostatic deposition and constant voltage
On body, nano-scale sheet-like array film layer and the flower-shaped array film layer of micron-scale are obtained, the electrode material of height ratio capacity can be prepared
Material, preparation method is simple, can be adapted for scale of mass production.
It can be by the following method to the chemical property of electrode material, for example, specific capacity is tested.For example, passing through
Three-electrode system tests the specific capacity of electrode material activity substance.Specifically, using electrode to be tested as working electrode (1 ×
1cm2), metal foil is to electrode (1 × 1cm2), saturated calomel electrode is reference electrode, and 2M LiOH aqueous solutions are electrolyte,
Using CHI660D electrochemical workstations carry out cyclic voltammetric (Cyclic Voltammetry, CV) method, constant current charge-discharge method and
AC electrochemical impedance spectrum (Electrochemical Impedance Spectroscopy, EIS) method tests electrode material
Discharge time tElectrode material.The specific capacity of electrode material passes through formula CElectrode material=IElectrode material·tElectrode material/VElectrode material·mElectrode materialIt calculates,
In, IElectrode materialFor the current density being tested used in electrode material constant current charge-discharge, VElectrode materialIt is tested electrode material discharge process
Voltage range, mElectrode materialTo be tested the quality of active material on electrode material.It should be understood that the electrification of the above test electrode material
The process for learning performance is only a specific example, and electricity can be tested or evaluate by other methods in the application other embodiment
The chemical property of pole material, is not construed as limiting herein.
The electrode material of the embodiment of the present application can be as the electrode of ultracapacitor.In one embodiment, super electricity
Container can be symmetrical ultracapacitor, and the anode and cathode of symmetrical ultracapacitor are made by the electrode material.
In a specific example, which can be all-solid-state flexible ultracapacitor, and assembling process is as follows：
By flexible electrode material (2 × 4cm of the active material film layer of deposition of the embodiment of the present application2) it is fabricated to two electrode systems
Working electrode, with LiOH- polyvinyl alcohol (PolyVinyl Alcohol, PVA) gel film (thickness be 20~40 μm) conduct
Electrode, diaphragm, electrode are superimposed in sandwich sandwich by diaphragm and solid electrolyte, and progress lug connection is simultaneously close
It is encapsulated in flexible outer packing, the external pressure for applying 10Pa forms symmetrical ultracapacitor.
Two methods can be passed through by testing the chemical property of symmetrical ultracapacitor.One is surveyed by preceding method
Examination obtains the specific capacity C of single electrodeSingle electrode=ISingle electrode·tSingle electrode/VSingle electrode·mSingle electrode, C hereSingle electrodeI.e. aforementioned CElectrode material.Due to super
Capacitor is symmetrical, can pass through formula CCapacitor=1/4CSingle electrodeObtain the specific capacity C of ultracapacitorCapacitor.Another kind is, directly
It connects to symmetrical ultracapacitor, i.e., this two electrode system is tested between all solid state electrolyte is clipped in the two poles of the earth.Using formula
CCapacitor=ICapacitor·tCapacitor/VCapacitor·mCapacitor, wherein tCapacitorFor the discharge time of ultracapacitor, ICapacitorFor ultracapacitor
Current density used in constant current charge-discharge, VCapacitorIt is the voltage range of ultracapacitor discharge process, mCapacitorFor super capacitor
On the two poles of the earth of device the quality of active material and.The energy density of ultracapacitor entirety is E=CCapacitor·V2/ 2 (Wh/kg), V are
The voltage at ultracapacitor both ends.Power density is P=E/tCapacitor(W/kg).It should be understood that the above-mentioned symmetrical ultracapacitor of test
Chemical property method it is merely illustrative, rather than the restriction to the embodiment of the present application.
In addition to the specific capacity of electrode material, another key factor for influencing the energy density of super capacitor system is super
The operating voltage range of capacitor.In addition to using nonaqueous electrolytic solution (solid electrolyte) to widen voltage width, prepare asymmetric
Electrode system be also effective approach, that is, use Asymmetric Supercapacitor.Faraday's capacitance material is used respectively by the two poles of the earth
Expect the complementation of (electrode material of the embodiment of the present application) and double layer electrodes material on potential windows, can greatly improve
The operating voltage and energy density of Asymmetric Supercapacitor.Therefore, in another embodiment, ultracapacitor can be non-
The anode of symmetrical ultracapacitor, Asymmetric Supercapacitor is made by the electrode material of the embodiment of the present application.This is non-right
It can be all-solid-state flexible ultracapacitor to claim ultracapacitor.In a specific example, Asymmetric Supercapacitor can
With using graphene paper made from freeze-drying as cathode, LiOH-PVA is as diaphragm and solid electrolyte according to above-mentioned same
Method be prepared.
It should be understood that for Asymmetric Supercapacitor, it should there is CAnode·mAnode=CCathode·mCathode.It assembles asymmetric
Ultracapacitor needs to learn the quality of the respective active material of positive and negative electrode.It then can be according to aforementioned formula CSingle electrode=ISingle electrode·
tSingle electrode/VSingle electrode·mSingle electrode, the specific capacity C of positive and negative electrode is tested respectivelyAnodeAnd CCathode, and then determine positive and negative electrode respectively active matter
The quality m of matterAnodeAnd mCathode, to configure positive and negative electrode.
The chemical property for testing Asymmetric Supercapacitor can be by the following method.Directly to asymmetric super capacitor
This two electrode system is tested between device, i.e. all solid state electrolyte are clipped in the two poles of the earth.Using formula CCapacitor=ICapacitor·tCapacitor/
VCapacitor·mCapacitor, wherein tCapacitorFor the discharge time of ultracapacitor, ICapacitorUsed in ultracapacitor constant current charge-discharge
Current density, VCapacitorIt is the voltage range of ultracapacitor discharge process, mCapacitorFor active material on the two poles of the earth of ultracapacitor
Quality and.The energy density of ultracapacitor entirety is E=CCapacitor·V2/ 2 (Wh/kg), V are the electricity at ultracapacitor both ends
Pressure.Power density is P=E/tCapacitor(W/kg).It should be understood that the method for the chemical property of the above-mentioned symmetrical ultracapacitor of test
It is merely illustrative, rather than the restriction to the embodiment of the present application.
Illustrate method that the embodiment of the present application prepares electrode material below with two specific examples.
Example 1：
(1) it using carbon cloth as flexible charge collector and deposition substrate, places it in ultrasound in ethyl alcohol and purifies, and
Air drying.
(2) with 1M Co (NO3)2With 0.1M NaNO3Electrolyte of the mixed solution as entire electrodeposition process,
On CHI660D electrochemical workstations, the electrodeposition process of substep is realized with three-electrode system.That is, using metal platinized platinum as to electricity
Pole, using saturated calomel electrode as reference electrode, using carbon cloth (2cm × 4cm) to be deposited as working electrode.It is being electrolysed
Chi Zhong, working electrode is opposite with to electrode runs parallel, and distance is 0.2cm.
(3) galvanostatic deposition prepares Co (OH)2Nano-scale sheet-like array film layer：Using -1V~1V as voltage range,
1mA/cm2Galvanostatic deposition 200s under current density.
(4) constant voltage deposition prepares Co (OH)2The flower-shaped array film layer of micron-scale：Constant voltage is heavy under the voltage of -1.2V
Product 300s.In-situ deposition is obtained in the Co (OH) on flexible charge collector by (3) and (4)2Graduation array bilayer film layer.
(5) obtained electrode material after deposition is rinsed with deionized water repeatedly, 60 DEG C of vacuum is dried overnight.It finally obtains
Growth has blue Co (OH) on flexible charge current collector film layer2The electrode material for array bilayer film layer of classifying.
It should be understood that above procedure is only a specific example, other equipment may be used in the application other embodiment
Electrode material is prepared with technological parameter etc..After obtaining electrode material, electrode material can be based on and assemble ultracapacitor.In example
It is only illustrated for assembling symmetrical ultracapacitor in son 1, the electrode material of the embodiment of the present application can also be with other materials
Material is assembled into other kinds of ultracapacitor, can also be applied to other devices or electronic equipment in addition to ultracapacitor
In, the embodiment of the present application is not construed as limiting this.
(6) assembling of symmetrical ultracapacitor：It regard above-mentioned electrode material (size can be 2cm × 4cm) as two electrodes
The working electrode of system, using LiOH-PVA gel films (thickness can be for 20~40 μm) as diaphragm and solid electrolyte.It will
Electrode, diaphragm, electrode are superimposed in sandwich sandwich, carry out lug connection and are sealed in flexible outer packing, apply
The external pressure of 10Pa is added to complete the preparation of symmetrical ultracapacitor.When the charge collector of electrode material is flexible charge collector
When, the ultracapacitor assembled can be the symmetrical ultracapacitor of all-solid-state flexible.
It should be understood that (6) are only a specific examples for assembling symmetrical ultracapacitor, the application other embodiment can be with
Symmetrical ultracapacitor is prepared using other technologies and technological parameter etc., is not limited thereto.
In the following, we specifically discuss the chemical property of the symmetrical ultracapacitor assembled in (6) with an example.
(7) test of the chemical property of symmetrical ultracapacitor：CHI660D electrochemical workstations may be used to be directed to
(6) chemical property of the symmetrical ultracapacitor assembled in carries out CV methods and the test of constant current charge-discharge method.CV methods work electricity
Ranging from 0~0.8V is pressed, the operating voltage range of constant current charge-discharge method is 0~1V.Active material on symmetrical ultracapacitor
Specific capacity pass through formula CCapacitor=ICapacitor·tCapacitor/VCapacitor·mCapacitor, wherein tCapacitorFor the discharge time of ultracapacitor,
ICapacitorFor the current density used in ultracapacitor constant current charge-discharge, VCapacitorIt is the voltage model of ultracapacitor discharge process
It encloses, mCapacitorFor active material on the two poles of the earth of ultracapacitor quality and.The energy density of ultracapacitor entirety is E=
CCapacitor·V2/ 2 (Wh/kg), V are the voltage at ultracapacitor both ends.Power density is P=E/tCapacitor(W/kg)。
Example 2：
(1) it using carbon fiber paper as flexible charge collector and deposition substrate, places it in ultrasound in ethyl alcohol and purifies, and
Air drying.
(2) with 2M Co (NO3)2With 0.5M NaNO3Electrolyte of the mixed solution as entire electrodeposition process,
On CHI660D electrochemical workstations, the electrodeposition process of substep is realized with three-electrode system.That is, using metal platinized platinum as to electricity
Pole, using saturated calomel electrode as reference electrode, using carbon cloth (2cm × 4cm) to be deposited as working electrode.It is being electrolysed
Chi Zhong, working electrode is opposite with to electrode runs parallel, and distance is 0.2cm.
(3) galvanostatic deposition prepares Co (OH)2Nano-scale sheet-like array film layer：Using -1V~1V as voltage range,
5mA/cm2Galvanostatic deposition 100s under current density.
(4) constant voltage deposition prepares Co (OH)2The flower-shaped array film layer of micron-scale：Constant voltage is heavy under the voltage of -1.2V
Product 100s.In-situ deposition is obtained in the Co (OH) on flexible charge collector by (3) and (4)2Graduation array bilayer film layer.
(5) obtained electrode material after deposition is rinsed with deionized water repeatedly, 60 DEG C of vacuum is dried overnight.It finally obtains
Growth has blue Co (OH) on flexible charge current collector film layer2The electrode material for array bilayer film layer of classifying.
It should be understood that above procedure is only a specific example, other equipment may be used in the application other embodiment
Electrode material is prepared with technological parameter etc..After obtaining electrode material, electrode material can be based on and assemble ultracapacitor.In example
It is only illustrated for assembling Asymmetric Supercapacitor in son 1, the electrode material of the embodiment of the present application can also be with other
Material is assembled into other kinds of ultracapacitor, can also be applied to other devices or electronics in addition to ultracapacitor and set
In standby, the embodiment of the present application is not construed as limiting this.
(6) negative material is made：Graphite oxide (Graphene Oxide, GO) is prepared by natural graphite, by going
The ultrasonic disperse processing of 1h in ionized water, by GO strippings at the structure of nanometer monolithic, then through high speed centrifugation 15min under 3000rpm
Remove the unstripped GO piece aggregates opened；Complete GO pieces will be removed and be scattered in deionized water, be made certain density water-dispersed
Liquid；GO dispersion liquids are placed on tablet, is removed from tablet after being freeze-dried 8h, obtains flexible GO films；Flexible GO films are placed in nitrogen
800 DEG C of heat treatment 5min, Flexible graphene GN films are reduced by GO in gas shielded.
It should be understood that it is only a specific example to prepare GN films by the method described in (6).Other implementations of the application
Other negative materials can be prepared in example by other methods, the embodiment of the present application is not construed as limiting this.
(7) assembling of Asymmetric Supercapacitor：By the electrode material prepared in (1)-(5) (size can be 2cm ×
4cm) the anode as two electrode system of ultracapacitor is thin with LiOH-PVA gels using the GN films of preparation in (6) as cathode
Film (thickness can be 20~40 μm) is used as diaphragm and solid electrolyte.Anode, diaphragm, cathode are superimposed in sandwich
Sandwich carries out lug connection and is sealed in flexible outer packing, and the external pressure for applying 10Pa completes Asymmetric Supercapacitor
Preparation.When the charge collector of the electrode material prepared in (1)-(5) is flexible charge collector, what is assembled is super
Capacitor can be all-solid-state flexible Asymmetric Supercapacitor.
It should be understood that (7) are only a specific examples for assembling Asymmetric Supercapacitor, the application other embodiment can
To prepare Asymmetric Supercapacitor using other technologies and technological parameter etc., it is not limited thereto.
In the following, we specifically discuss the chemical property of the Asymmetric Supercapacitor assembled in (7) with an example.
(8) test of the chemical property of Asymmetric Supercapacitor：CHI660D electrochemical workstations may be used to be directed to
(7) chemical property of the Asymmetric Supercapacitor assembled in carries out CV methods and the test of constant current charge-discharge method.CV methods work
Voltage range is 0~0.8V, and the operating voltage range of constant current charge-discharge method is 0~1V.The anode of Asymmetric Supercapacitor
Pass through formula C with the specific capacity of active material on the electrode material of cathodeCapacitor=ICapacitor·tCapacitor/VCapacitor·mCapacitor, wherein
tCapacitorFor the discharge time of ultracapacitor, ICapacitorFor the current density used in ultracapacitor constant current charge-discharge, VCapacitorIt is
The voltage range of ultracapacitor discharge process, mCapacitorFor active material on the two poles of the earth of ultracapacitor quality and.Super electricity
The energy density of container entirety is E=CCapacitor·V2/ 2 (Wh/kg), V are the voltage at ultracapacitor both ends.Power density is P
=E/tCapacitor(W/kg)。
The chemical property of the ultracapacitor respectively obtained below to example 1 and example 2 illustrates.
Fig. 4 is CV curve of the symmetrical ultracapacitor of example 1 under different scanning speed.Fig. 5 is the symmetrical super of example 1
Constant current charge-discharge curve of the grade capacitor under different current densities.From Fig. 4 and Fig. 5 it is known that manufactured in the present embodiment
Symmetrical ultracapacitor has preferable comprehensive electrochemical.Specifically, in Fig. 4, gradually carrying with CV sweep speeds
Excessive offset does not occur for the redox peak position of height, active material, illustrates that electrode has quick current-responsive performance.Together
When, in Figure 5, in the case where voltage is 0~1V, ultracapacitor shows cutting edge aligned, symmetrical constant current charge/discharge curve,
And coulombic efficiency is higher, illustrates Co (OH) in graduation array bilayer film layer2The electrochemical reaction process of completely reversibility occurs.It should
The surface density of active material film layer is 0.8mg/cm on electrode material in embodiment2, correspond to 1mA/cm2Charging and discharging currents it is close
Degree, capacity of super capacitor are up to 370.5F/g.The acquisition of these excellent properties is due to high in graduation array bilayer film layer
Open 3-D nano, structure is spent, it is capable of providing a large amount of electro-chemical activity site, substance is promoted to transmit, and improves active matter
The utilization rate of matter.
Fig. 6 is CV curve of the Asymmetric Supercapacitor of example 2 under different scanning speed.Fig. 7 is the non-right of example 2
Claim constant current charge-discharge curve of the ultracapacitor under different current densities.From Fig. 6 and Fig. 7 it is known that the present embodiment system
Standby symmetrical ultracapacitor has preferable comprehensive electrochemical.Specifically, the Asymmetric Supercapacitor can 0~
It works under the voltage range of 1.8V, the voltage compensation that cathode is used as by GN films acts on, the work electricity of Asymmetric Supercapacitor
Pressure is greatly widened, this is advantageous to the promotion of ultracapacitor integral energy density.In figure 6, it is scanned when CV is tested
When speed is up to 100mV/s, there is CV curves the trend of similar rectangle, relatively low sweep speed CV curves not to occur significantly
Offset；Meanwhile in the figure 7, constant current charge-discharge of the Asymmetric Supercapacitor under different current densities is tested
Capacity does not have the loss of excessive degree, illustrates the preferable high rate performance of Asymmetric Supercapacitor.
Fig. 8 is the comparison of the cycle performance of the symmetrical ultracapacitor of example 1 and the Asymmetric Supercapacitor of example 2
Figure.As can be seen from Figure 8, Asymmetric Supercapacitor selects the GN films with higher cyclical stability as cathode, helps
In the extension of Asymmetric Supercapacitor cycle life.Compared to symmetrical ultracapacitor, Asymmetric Supercapacitor has more
Excellent cyclical stability, in 100mA/cm2Current density under recycle 5000 weeks, the 67% of initial capacity can be kept.Pass through
It is calculated, corresponding 2.5mA/cm2Charging and discharging currents density, the energy density of Asymmetric Supercapacitor reaches 102.8Wh/
Kg, power density reach 55kW/kg, have a distinct increment relative to traditional ultracapacitor tool.
It should be understood that specific capacity typically refers to specific discharge capacity in this specification, naturally it is also possible to be assessed using other modes
Specific capacity, the embodiment of the present application are not construed as limiting this.
It should be understood that the terms "and/or", only a kind of incidence relation of description affiliated partner, expression can deposit
In three kinds of relationships, for example, A and/or B, can indicate：Individualism A exists simultaneously A and B, these three situations of individualism B.
In addition, character "/" herein, it is a kind of relationship of "or" to typically represent forward-backward correlation object.
It should be understood that in the various embodiments of the application, size of the sequence numbers of the above procedures is not meant to execute suitable
The execution sequence of the priority of sequence, each process should be determined by its function and internal logic, the implementation without coping with the embodiment of the present application
Process constitutes any restriction.
The above, the only specific implementation mode of the application, but the protection domain of the application is not limited thereto, it is any
Those familiar with the art can easily think of the change or the replacement in the technical scope that the application discloses, and should all contain
It covers within the protection domain of the application.Therefore, the protection domain of the application shall be subject to the protection scope of the claim.
Claims (26)
1. a kind of electrode material, which is characterized in that described to grade including charge collector film layer and graduation array bilayer film layer
Grade array bilayer film layer includes nano-scale sheet-like array film layer and the flower-shaped array film layer of micron-scale, wherein the nanometer ruler
Very little sheet-like array film layer is the growth in situ in the charge collector film layer, the flower-shaped array film layer arrangement of micron-scale
On the upper layer of the nano-scale sheet-like array film layer.
2. electrode material according to claim 1, which is characterized in that the ingredient of the graduation array bilayer film layer is gold
Belong to oxide, metal hydroxides or metal composite oxide, the metal oxide, metal hydroxides or composition metal oxygen
Metal in compound includes at least one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Mo.
3. electrode material according to claim 1 or 2, which is characterized in that the charge collector is flexible charge afflux
Body.
4. electrode material according to any one of claim 1 to 3, which is characterized in that the charge collector is carbon fiber
Wei Bu, carbon fiber paper, carbon fiber film, graphene-based charge collector, carbon nanotube elementary charge collector, metal or alloy are fine
Wei Bu, metal or alloy net, metal or alloy film, one kind in foam metal are combined by least two.
5. electrode material according to any one of claim 1 to 4, which is characterized in that the charge collector has gold
Belong to coating, alloy coat, carbon material coating or battery system coating layer of active substance.
6. electrode material according to any one of claim 1 to 5, which is characterized in that the nano-scale sheet-like array
Film layer includes the multiple nano-scale monolithics of vertical arrangement of being interweaved, and the diameter of the nano-scale monolithic is greater than or equal to
1nm and it is less than or equal to 1000nm, the thickness of the nano-scale monolithic is greater than or equal to 1nm and is less than or equal to
The thickness of 100nm, the nano-scale sheet-like array film layer are greater than or equal to 0.5 μm and are less than or equal to 100 μm.
7. electrode material according to any one of claim 1 to 6, which is characterized in that the flower-shaped array of micron-scale
Film layer includes multiple micron-scale single flowers, and the diameter of the micron-scale single flower is greater than or equal to 1 μm and is less than or equal to 10 μ
The thickness of m, the flower-shaped array film layer of micron-scale are greater than or equal to 1 μm and are less than or equal to 100 μm.
8. electrode material according to any one of claim 1 to 7, which is characterized in that the nano-scale sheet-like array
Film layer includes the multiple nano-scale monolithics of vertical arrangement of being interweaved, and the flower-shaped array film layer of micron-scale includes multiple micro-
Meter ruler cun single flower, the micron-scale single flower after the nano-scale monolithic diauxic growth by being self-assembly of, either
What in-situ deposition was formed.
9. electrode material according to any one of claim 1 to 8, which is characterized in that the nano-scale sheet-like array
Film layer is obtained by galvanostatic deposition, and the flower-shaped array film layer of micron-scale is to deposit to obtain by constant voltage.
10. a kind of ultracapacitor, which is characterized in that the ultracapacitor includes described in any one of claim 1 to 9
Electrode material.
11. ultracapacitor according to claim 10, which is characterized in that the ultracapacitor is symmetrical super capacitor
Device, the anode and cathode of the symmetrical ultracapacitor are made by the electrode material.
12. ultracapacitor according to claim 10, which is characterized in that the ultracapacitor is asymmetric super electricity
The anode of container, the Asymmetric Supercapacitor is made by the electrode material.
13. a kind of electronic equipment, which is characterized in that the electronic equipment includes the electricity described in any one of claim 1 to 9
Pole material.
14. a kind of method preparing electrode material, which is characterized in that including：
Charge collector is purified and dried, charge collector film layer is formed；
The charge current collector film is placed in electrolyte and carries out galvanostatic deposition, it is in situ in the charge collector film layer
Grow nano-scale sheet-like array film layer；
There is the charge current collector film of the nano-scale sheet-like array film layer to be placed in the electrolyte deposition to carry out
Constant voltage deposits, and the flower-shaped array film layer of micron-scale is formed in the nano-scale sheet-like array film layer.
15. according to the method for claim 14, which is characterized in that the electrolyte includes source metal salt, the metal
Source salt is for generating the nano-scale sheet-like array film layer and the flower-shaped array film layer of the micron-scale, wherein the nanometer
The ingredient of size flakes array film layer and the flower-shaped array film layer of the micron-scale is metal oxide, metal hydroxides or multiple
Close metal oxide, the metal in the metal oxide, metal hydroxides or metal composite oxide include Sc, Ti, V,
At least one of Cr, Mn, Fe, Co, Ni, Cu, Zn and Mo.
16. according to the method for claim 15, which is characterized in that further include Na salt in the electrolyte.
17. the method according to any one of claim 14 to 16, which is characterized in that the electrolyte include villaumite,
One or more of acetate, nitrate, sulfate.
18. the method according to any one of claim 14 to 17, which is characterized in that the galvanostatic deposition and the perseverance
Voltage deposition is realized by three-electrode system, wherein using metal platinized platinum as to electrode, the electricity using saturated calomel electrode as reference
Pole, using charge collector film layer to be deposited as working electrode.
19. according to the method for claim 18, which is characterized in that in the electrolyte, the working electrode with it is described
Opposite to electrode runs parallel, the working electrode is with described to being 0.2cm at a distance from electrode.
20. the method according to any one of claim 14 to 19, which is characterized in that the voltage model of the galvanostatic deposition
It encloses to be greater than or equal to -1V and being less than or equal to 1V, the deposition duration of the galvanostatic deposition is greater than or equal to 10s and small
In or equal to 1000s.
21. the method according to any one of claim 14 to 20, which is characterized in that the voltage model of the constant voltage deposition
It encloses to be greater than or equal to -1.5V and being less than or equal to 1.5V, the deposition duration of the constant voltage deposition is greater than or equal to 10s simultaneously
And it is less than or equal to 1000s.
22. the method according to any one of claim 14 to 21, which is characterized in that the charge collector is carbon fiber
Cloth, carbon fiber paper, carbon fiber film, graphene-based charge collector, carbon nanotube elementary charge collector, metal or alloy fiber
Cloth, metal or alloy net, metal or alloy film, one kind in foam metal are combined by least two.
23. the method according to any one of claim 14 to 22, which is characterized in that the charge collector has metal
Coating, alloy coat, carbon material coating or battery system coating layer of active substance.
24. the method according to any one of claim 14 to 23, which is characterized in that the nano-scale sheet-like array film
Layer includes the multiple nano-scale monolithics for the vertical arrangement that is interweaved, and the diameter of the nano-scale monolithic is greater than or equal to 1nm
And it is less than or equal to 1000nm, the thickness of the nano-scale monolithic is greater than or equal to 1nm and is less than or equal to 100nm,
The thickness of the nano-scale sheet-like array film layer is greater than or equal to 0.5 μm and is less than or equal to 100 μm.
25. the method according to any one of claim 14 to 24, which is characterized in that the flower-shaped array films of micron-scale
Layer includes multiple micron-scale single flowers, and the diameter of the micron-scale single flower is greater than or equal to 1 μm and less than or equal to 10 μm,
The thickness of the flower-shaped array film layer of micron-scale is greater than or equal to 1 μm and is less than or equal to 100 μm.
26. the method according to any one of claim 14 to 25, which is characterized in that the nano-scale sheet-like array film
Layer includes the multiple nano-scale monolithics for the vertical arrangement that is interweaved, and the flower-shaped array film layer of micron-scale includes multiple microns
Size single flower, the micron-scale single flower are or former by being self-assembly of after the nano-scale monolithic diauxic growth
Position deposition is formed.
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