CN107610937A - Electrode structure and preparation method thereof, graphene ultracapacitor and preparation method thereof - Google Patents
Electrode structure and preparation method thereof, graphene ultracapacitor and preparation method thereof Download PDFInfo
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides a kind of electrode structure and preparation method thereof, graphene ultracapacitor and preparation method thereof, the electrode structure includes：Graphene film；The first semiconductor layer being made up of nanosphere positioned at graphene film surface；The second semiconductor layer on the first semiconductor layer, the second semiconductor layer are made up of nano wire, and at least nano wire contact normal thereto on each nanosphere；The 3rd semiconductor layer on the second semiconductor layer, the 3rd semiconductor layer are made up of nano flower, and at least a nano flower contacts on every nano wire；Solid electrolyte is set on whole graphene film surface, solid electrolyte is permeated in the gap of the first semiconductor layer, the second semiconductor layer and the 3rd semiconductor layer, and the first semiconductor layer, the second semiconductor layer and the 3rd semiconductor layer are wrapped, the top of solid electrolyte is higher than the top of the 3rd semiconductor layer, and the present invention improves the capacitance, energy density and stability of ultracapacitor.
Description
Technical field
The present invention relates to technical field of semiconductors, and in particular to a kind of electrode structure and preparation method thereof, graphene are super
Capacitor and preparation method thereof.
Background technology
Ultracapacitor is by polarized dielectric come energy storage.It is a kind of electrochemical element, but its energy storage process simultaneously
Do not chemically react, be reversible.The capacitance density of ultracapacitor is high, influences its use without having to worry about overcharging or putting excessively
The problem of life-span, it is a kind of green energy resource.However, compared with existing lithium ion battery, the energy density of ultracapacitor compared with
It is low.
Graphene is considered as omnipotent material, and graphene is applied to the super electricity of graphene that ultracapacitor is prepared
Container, energy density greatly improve, and cyclical stability is preferable, up time length, are expected to turn into the energy of new generation.It is but existing
Also there are many bottlenecks, for example, energy density is not met by people couple in the structure design of some graphene ultracapacitors
Demand, graphene ultracapacitor can not be mutually compatible with existing patterned semiconductor technique, how framework graphene surpasses
The structure of level capacitor, further improves its energy stores amount and energy density, and make it be more beneficial for realizing large-scale
Production, is the problem of current people generally explore.
The content of the invention
In order to overcome problem above, the present invention is intended to provide a kind of electrode structure and graphene ultracapacitor, using more
Layer electrode structure improves the energy density of capacitor, and the graphene ultracapacitor is more suitable for large-scale production.
In order to achieve the above object, the invention provides a kind of electrode structure of ultracapacitor, including：
Graphene film；
The first semiconductor layer being made up of nanosphere positioned at graphene film surface；
The second semiconductor layer on the first semiconductor layer, the second semiconductor layer are made up of nano wire, and each nanometer
At least nano wire contact normal thereto on ball；
The 3rd semiconductor layer on the second semiconductor layer, the 3rd semiconductor layer are made up of nano flower, and every nanometer
At least a nano flower contacts on line；
Solid electrolyte is set on whole graphene film surface, and solid electrolyte is permeated in the first semiconductor layer,
In the gap of two semiconductor layers and the 3rd semiconductor layer, and by the first semiconductor layer, the second semiconductor layer and the 3rd semiconductor layer
Wrap, the top of solid electrolyte is higher than the top of the 3rd semiconductor layer.
Preferably, the nanosphere of first semiconductor layer is hollow ball.
Preferably, the hollow ball is bulbus cordis in midair, and the diametral plane of bulbus cordis is located at graphene film surface, semi-hollow in midair
The sphere of ball is set upward so that forms closed cavity between bulbus cordis and graphene film in midair.
Preferably, the internal diameter of hollow ball is
Preferably, summit of the nano wire vertical-growth of second semiconductor layer at the top of the hollow ball.
Preferably, the height of the nano wire is 1~10nm.
Preferably, the nano flower is nanometer bar construction from root to external radiation that opened from, the root growth of the nano flower
In the top of the nano wire.
Preferably, the width of the nano flower is 5~10nm, highly no more than 10nm.
Preferably, be additionally provided with current collector layers in the bottom of the graphene film, the pattern of the graphene film with
The pattern of current collector layers is identical.
Preferably, the material of first semiconductor layer is transition group metallic oxide.
Preferably, the height of the nanosphere is less than or equal to the height of the nano wire, and the height of the nano flower is small
In or equal to the nano wire height, the width of the nano flower is less than or equal to the diameter of nano wire, the nano flower
Width is less than or equal to the diameter of nanosphere.
Preferably, there are multiple projections at the top of the solid electrolyte.
In order to achieve the above object, present invention also offers a kind of preparation method of above-mentioned electrode structure, it includes：
Step 01：Prepare the graphene film with substrate；
Step 02：Nanosphere is synthesized on graphene film surface, so as to form the first semiconductor layer；
Step 03：The first fluid electrolyte is filled in the first semiconductor layer, and the first solid electrolyte is formed through solidification；
Wherein, the top of the first solid electrolyte is less than the top of nanosphere so that is exposed at the top of nanosphere；
Step 04：The epitaxial growth nanowire at the top of the nanosphere exposed, so as to form the second semiconductor layer；
Step 05：The second fluid electrolyte is filled in nano wire, and the second solid electrolyte is formed through solidification；Wherein,
The top of second solid electrolyte is less than the top of nano wire so that is exposed at the top of nano wire；
Step 06：Go out nano flower in the top epitaxial growth of the nano wire exposed, so as to form the 3rd semiconductor layer；
Step 07：The 3rd fluid electrolyte is filled in nano flower, and the 3rd solid electrolyte is formed through solidification；Wherein,
The top of 3rd solid electrolyte is higher than the top of nano flower.
Preferably, in the step 02, nanosphere is synthesized using hydro-thermal method, solvent-thermal method, inorganic template method.
Preferably, the step 03 specifically includes：
Step 031：Under the first rotating speed, the first fluid electrolyte is filled by spin coating mode in the first semiconductor layer；
Step 032：First rotating speed is promoted to the second rotating speed so that the first semiconductor layer and its first electricity of top
Solution mass flow body is thrown out of, then, near 3rd rotating speed of the second rotating speed, so that the first electrolysis in the first semiconductor layer
The top of mass flow body is less than the top of the first semiconductor layer；
Step 033：The first fluid electrolyte is set to solidify to form the first solid electrolyte；
The step 05 specifically includes：
Step 051：Under the 3rd rotating speed, the second fluid electrolyte is filled by spin coating mode in the second semiconductor layer；
Step 052：3rd rotating speed is promoted to the 4th rotating speed so that the second semiconductor layer and its second electricity of top
Solution mass flow body is thrown out of, so that the top of the second fluid electrolyte in the second semiconductor layer is less than the second semiconductor layer
Top；
Step 053：The second fluid electrolyte is set to solidify to form the second solid electrolyte；
The step 07 specifically includes：Under the 5th rotating speed, the 3rd is filled by spin coating mode in the 3rd semiconductor layer
Fluid electrolyte, rotating speed is then gradually reduced until static, makes the top of the 3rd fluid electrolyte being located in the 3rd semiconductor layer
Portion is higher than the top of the 3rd semiconductor layer, finally, makes the 3rd fluid electrolyte solidify to form the 3rd solid electrolyte.
Preferably, first rotating speed, the 3rd rotating speed and the 5th rotating speed are identical, second rotating speed and the 4th rotating speed
It is identical.
Preferably, second rotating speed is 2~6 times of the first rotating speed, and the 4th rotating speed is 2~6 times of the 3rd rotating speed.
Preferably, in the step 04, the nano wire is using chemical vapour deposition technique, aqua-solution method, electrochemical plating
To prepare；In the step 06, the nano flower is prepared using aqua-solution method, template.
Preferably, before the step 01, in addition to：
Step a：One high temperature-resistant liner bottom is provided, also, current collector layers are deposited on substrate；
Step b：Current collector layers are etched, so as to form the pattern of current collector layers；
Step c：Not by the top of the substrate surface of the exposure of the pattern covers of current collector layers and the pattern of current collector layers
Dielectric layer, and planarized dielectric layer are formed with side wall, is made at the top of dielectric layer with being flushed at the top of the pattern of current collector layers；
Step d：Using chemical vapour deposition technique, whole high temperature-resistant liner bottom is placed in chemical vapor deposition process chamber,
The superficial growth of the pattern exposure of current collector layers goes out graphene film；
After step 07, in addition to：Remove high temperature-resistant liner bottom.
Preferably, before the step 01, in addition to：
Step I：One high temperature-resistant liner bottom, also, the deposition of sacrificial layer on high temperature-resistant liner bottom are provided；
Step II：Etched in sacrifice layer for filling the groove of current collector layers, and fill collector in the trench
Layer；
Step III：Using chemical vapour deposition technique, whole high temperature-resistant liner bottom is placed in chemical vapor deposition process chamber,
Go out graphene film in the superficial growth of collector exposure；
Step IV：Using release process, sacrifice layer is removed, so as to leave current collector layers on high temperature-resistant liner bottom；
After step 07, in addition to：Remove the high temperature-resistant liner bottom.
In order to achieve the above object, present invention also offers a kind of graphene ultracapacitor, it includes：Two above-mentioned
Electrode structure is oppositely arranged, and the separation layer between the electrode structure.
Preferably, the separation layer is organic barrier film, is had at the top of the solid electrolyte of the electrode structure multiple convex
Rise；Two surfaces of organic barrier film have multiple depressions respectively, and depression is engaged with projection, make raised embedded depression
In.
Preferably, the distance between bottom of two depressions in the surface of organic barrier film is not more than 2nm.
Preferably, the separation layer is graphene oxide film.
In order to achieve the above object, present invention also offers a kind of preparation method of above-mentioned graphene ultracapacitor,
It includes：
First, there is provided two electrode structures；
Secondly, wherein the solid electrolyte of an electrode structure have raised surface deposit one layer it is organic every
From film colloid, and the solid electrolyte of another electrode structure had into raised surface from organic barrier film glue simultaneously
In the organic isolating film colloid of overlying contact of body and embedded organic isolating film colloid, so that organic isolating film colloid is filled in this
In the raised gap of the solid electrolyte of two electrode structures；
Then, solidify organic isolating film colloid, so as to complete the preparation of graphene ultracapacitor.
In order to achieve the above object, present invention also offers a kind of preparation method of above-mentioned graphene ultracapacitor,
It includes：
First, organic barrier film glue is deposited on surface of the solid electrolyte of an electrode structure with projection wherein
Body；
Then, solidify organic isolating film colloid；
Then, the solid electrolyte with another electrode structure is etched in organic isolating film colloid using etching technics
The depression that is engaged of projection；
Finally, the raised alignment of another electrode structure is fitted together in depression, so as to complete graphene ultracapacitor
Preparation.
Present invention utilizes the semiconductor layer of three layers of different-shape to be used as Ion transfer and transmission channel, three-layer semiconductor
Layer intermediate ion passes speed and density and differed, so as to improve the capacitance of graphene ultracapacitor, energy density and steady
It is qualitative.Also, the thickness of the graphene ultracapacitor of the present invention can realize nanoscale, such as hundreds of nanometers, width can
Arbitrarily to set, multiple supercapacitor structures units of big density can be realized in the area of per square centimeter, by this
Individual multiple ultracapacitor serial or parallel connections can realize big voltage or high current demand, so as to improve making for ultracapacitor
Use flexibility.
Brief description of the drawings
Fig. 1 is a kind of cross section structure schematic diagram of electrode structure of the preferred embodiment of the present invention
Fig. 2 is the structural representation of the graphene ultracapacitor of the preferred embodiment of the present invention
Fig. 3 is the raised structural representation of the solid electrolyte of another preferred embodiment of the present invention
Fig. 4 is the structural representation of the separation layer of another preferred embodiment of the present invention
Fig. 5 is the raised recessed with separation layer of the solid electrolyte of the electrode structure of another preferred embodiment of the present invention
Sunken fit structure schematic diagram
Fig. 6 is the schematic flow sheet of the preparation method of the electrode structure of the preferred embodiment of the present invention
Fig. 7~21 are each preparation process schematic diagram of the preparation method of Fig. 6 electrode structure
Embodiment
To make present disclosure more clear understandable, below in conjunction with Figure of description, present disclosure is made into one
Walk explanation.Certainly the invention is not limited in the specific embodiment, the general replacement known to those skilled in the art
Cover within the scope of the present invention.
The electrode for super capacitor structure of the present invention, has a graphene film, and first positioned at graphene film surface
Semiconductor layer, the second semiconductor layer on the first semiconductor layer, the 3rd semiconductor layer on the second semiconductor layer, with
And the solid electrolyte on graphene film surface is arranged at, solid electrolyte is permeated in the first semiconductor layer, the second semiconductor
In the gap of layer and the 3rd semiconductor layer, the first semiconductor layer, the second semiconductor layer and the 3rd semiconductor layer are wrapped.Solid-state
Electrolyte can not only play a part of electrolyte herein, can also play and fix the first semiconductor layer, the second semiconductor layer
With the effect of the 3rd semiconductor layer.
It should be noted that in order to which electrode structure will not only have to the transfer ability and adsorption capacity of ion, electrode structure
There is big surface area and to have to provide passage, therefore, in the present invention, the first semiconductor layer is using nanosphere, the
Two semiconductor layers use nano wire, and the 3rd semiconductor layer uses nano flower, and nanosphere directly contacts with graphene film, due to stone
There are dangling bonds on black alkene film, promote on nanosphere absorption graphite film, the ion of electrolyte dissociation by the use of nano wire as
Channel transfer is on nano flower, and nano flower is due to more radial nanometer rods, having higher specific surface area and electrolyte
Contact, and a plurality of flyway can be provided for ion, cause ion largely to be produced in nano flower and moment occur and gather
And diffusion, layer occurs as new leafing, more ions are generated for electrode structure, it is achieved thereby that multilayer ion
Migration, the capacitance and energy density of ultracapacitor are further increased, and the 3rd semiconductor layer of nano flower is also in wink
Between relaxed the migration rate of ion, the charge and discharge process of capacitor can be played a protective role.Further, positioned at stone
(electrolyte is thin in graphene due to that can also be considered as one layer of effective ion generation layer with larger specific surface area for black alkene film
Film surface dissociation), the nanosphere positioned at bottom occurs because that can also be considered as one layer of effective ion with larger specific surface area
Layer (electrolyte is in nanosphere surface dissociation), so, in single electrode structure just there is three leafing layer occurs：Graphene
Film, nanosphere and nano flower, this three leafing occur layer in the vertical direction and are intervally arranged, and realize the multilayer release of ion,
The capacitance and energy density of ultracapacitor are improved, furthermore, nano wire causes graphene film, nanosphere as transmission channel
The ion that film occurs migration or make it that ion caused by nano flower migrates downward into all more regular, efficiently and quickly upwards.
In addition, the material of the first semiconductor layer of the present invention, the second semiconductor layer and the 3rd semiconductor layer can be identical
With difference, in order to preferably realize the effect above, the material of the first semiconductor layer, the second semiconductor layer and the 3rd semiconductor layer is excellent
Selection of land is half transition group metallic oxide, also, transition group metallic oxide has characteristic of semiconductor mostly, is more suitably applied to
In electrode structure, the migration of ion can be promoted to a certain extent, and be unlikely to make short circuit between electrode structure.
The present invention is described in further detail below in conjunction with accompanying drawing 1~21 and specific embodiment.It should be noted that accompanying drawing
Using very simplified form, using non-accurately ratio, and only to it is convenient, clearly reach aid illustration the present embodiment
Purpose.
In the present embodiment, using the material of the first semiconductor layer, the second semiconductor layer and the 3rd semiconductor layer as TiO2Exemplified by
To illustrate, so this, which is not used in, limits the scope of the invention.A kind of referring to Fig. 1, ultracapacitor of the present embodiment
Electrode structure include：Graphene film 01, the first TiO2The 11, the 2nd TiO of layer2The 12, the 3rd TiO of layer2Layer 13 and solid electrolyte
02.In addition, in order to improve the efficiency of transmission of electrode structure, current collector layers 03 are additionally provided with the lower surface of graphene film 01.
Here the thickness of graphene film 01 can be monoatomic layer thickness or multiple atomic layer level thickness, preferably 1
~3 layers of atomic layer level thickness.
The first TiO positioned at graphene film surface2Layer 11 is by TiO2Nanosphere is formed, and forms nanometer ball array here；For
Increase comparison surface and bending resistance, the first TiO here2The TiO of layer2Nanosphere is arranged to hollow ball, preferably, empty
Bulbus cordis is bulbus cordis in midair, and the diametral plane of bulbus cordis is located at graphene film surface in midair, and the sphere of bulbus cordis is set upward in midair so that
Closed cavity is formed between bulbus cordis and graphene film in midair.Preferably, the internal diameter of hollow ball isHollow ball
The difference of internal diameter and external diameter that is to say that the thickness of hollow ball is not more than 10nm.
Positioned at the first TiO2The 2nd TiO on layer2Layer is by TiO2Nano wire is formed, and each TiO2On nanosphere at least
There is a TiO2Nano wire contact normal thereto, form vertical nanowires linear array；In the present embodiment, in order to improve nanosphere pair
TiO2The enabling capabilities of nano wire, the 2nd TiO2The TiO of layer2Summit of the nano wire vertical-growth at the top of hollow ball.Preferably,
The height of nano wire is 1~10nm.
Positioned at the 2nd TiO2The 3rd TiO on layer2Layer is by TiO2Nano flower is formed, and forms nano flower array here；And every
TiO2At least TiO on nano wire2Nano flower contacts.Here TiO2Nano flower is to be opened from root to external radiation
Nanometer bar construction, the TiO2The root growth of nano flower is in the TiO2The top of nano wire.Preferably, the width of nano flower
Spend for 5~10nm, highly no more than 10nm.
In order to realize that electrode structure produces more ion and fast ionic migrates, in the present embodiment, TiO2Nanosphere
Highly it is less than or equal to TiO2The length of nano wire, TiO2The height of nano flower is less than or equal to TiO2The height of nano wire, TiO2
The width of nano flower is less than or equal to TiO2The diameter of nano wire, in addition, TiO2The width of nano flower might be less that or be equal to
TiO2The diameter of nanosphere.Preferably, the diameter of nanosphere is not more than 50nm, the height of nano wire is not more than 50nm, nano flower
Width be not more than 50nm, highly no more than 50nm, that is to say the first semiconductor layer, the second semiconductor layer and the 3rd semiconductor layer
Height, so as to be advantageous to the filming of the graphene ultracapacitor of the present invention, miniaturization, realizes ultra-thin stone no more than 50nm
Black alkene ultracapacitor.
The solid electrolyte of the present embodiment is formed on whole graphene film surface, and solid electrolyte is permeated in
One TiO2Layer, the 2nd TiO2Layer and the 3rd TiO2In the gap of layer, by the first TiO2Layer, the 2nd TiO2Layer and the 3rd TiO2Layer parcel
Firmly, while the top of solid electrolyte is caused to be higher than the 3rd TiO2The top of layer, this first TiO2Layer, the 2nd TiO2Layer and the 3rd
TiO2Sealed by solid electrolyte.
The electrode structure of the present embodiment could be arranged to arbitrary shape, in order to improve capacitor due to showing film-form
Energy density, preferably, set graphene film pattern it is identical with the pattern of current collector layers.
Referring to Fig. 2, the graphene ultracapacitor that the above-mentioned electrode structure of the present embodiment is formed, two electrode structure phases
To setting, separation layer 04 is between two electrode structures.The material of separation layer 04 is insulating materials, for insulating electron in electricity
Migration between the structure of pole, two electrode structure short circuits are avoided, while the material of separation layer 04 also needs to have good ion
Penetration capacity, in the present embodiment, separation layer 04 can be graphene oxide film, because graphene oxide film is non-conductive, and
And graphene oxide film has network structure, be advantageous to penetrating for ion.In addition, in other embodiments of the invention, every
Absciss layer 04 can also be organic barrier film, and in order to improve the close contact between separation layer 04 and solid electrolyte 02, avoid
Interface loss ion and cause capacitor charge and discharge ability to decline, there are multiple projections at the top of the solid electrolyte of electrode structure；Have
Two surfaces of machine barrier film have multiple depressions, and depression is engaged with projection, make in raised embedded depression.Refer to Fig. 3~
5, Fig. 3 be the raised structural representation of the solid electrolyte of another preferred embodiment of the present invention, and Fig. 4 is the another of the present invention
The structural representation of the separation layer of one preferred embodiment, Fig. 5 are the recessed of top bump T and the separation layer 04 of solid electrolyte 02
A fit structure schematic diagram is fallen into, the raised T and separation layer 04 at the top of solid electrolyte 02 depression A are mutual cooperation relation, are made
Obtain solid electrolyte 02 and separation layer 04 can be nested against one another, meanwhile, the He of solid electrolyte 02 shown in Fig. 5 of the present embodiment
In the matching relationship of separation layer 04, the both ends of separation layer 04 also show raised structures relative to depression A, and solid electrolyte 02
Both ends show groove structure relative to raised T so that the raised structures at the both ends of separation layer 04 are by solid electrolyte 02
Raised T withstand so that solid electrolyte 02 can not horizontally slip relative to separation layer 04, so as to the depression A in separation layer 04
And not only separation layer 04 enables between the solid electrolyte 02 of upper and lower two electrode structures the raised T in solid electrolyte 02
Even closer contact, additionally it is possible to avoid two electrode structures are relative up and down from sliding, add the electrochemically stable of ultracapacitor
Property and mechanical stability.
The preparation method of above-mentioned electrode structure is further described below in conjunction with accompanying drawing 6~15.
Referring to Fig. 6, the preparation method of the electrode structure of the present embodiment, including：
Step 01：Referring to Fig. 7, prepare the graphene film 01 with substrate 00；
Specifically, it can be, but not limited to use chemical gas on the resistant to elevated temperatures substrate 00 such as gallium nitride, sapphire, copper
Phase depositing operation prepares graphene film 01.Graphene film 01 is preferably the graphene film of monoatomic layer.
In addition, in order to strengthen the charging and discharging capabilities of electrode structure, also first layer afflux is formed in the bottom of graphene film 04
Body layer 03, isolated using dielectric layer 05 between current collector layers 03；Can be after electrode structure prepares, by the stone of electrode structure
Black that side of alkene film 01 upward, then by current collector layers 03 is deposited on the surface of graphene film 01；It is it is of course also possible to use other
Mode prepares the graphene film 01 with substrate, and this will subsequently describe in detail.
It should be noted that if backing material directly uses current collector material, substrate need not be subsequently removed, without
Increase the preparation process of current collector layers 03.
Step 02：Referring to Fig. 8, nanosphere is synthesized on the surface of graphene film 01, so as to form the first semiconductor layer 11；
Specifically, the preparation of nanosphere can use hydro-thermal method, solvent-thermal method, inorganic template method, absorption method, sonochemistry
Method.On the preparation that nanosphere is nano-hollow ball, using hydro-thermal method and template can be combined to prepare (for example, function material
Material, the 3rd phase volume 37 in 2006, the Advances in preparation of inorganic hollow nanospheres；Chemical research, volume 24 the 4th
Phase, mesoporous silicon dioxide nano hollow ball is prepared as template using chiral amphiphilic small molecule；Chem Mater,2001,13(2):
400-409,Multilayered Titania,Silica,and Laponite Nanoparticle Coatings on
Polystyrene Colloidal Templates and Resulting Inorganic Hollow Spheres), on
The synthesis of nanosphere has a variety of prior arts to prepare, and this is that those skilled in the art could be aware that, is repeated no more here.Due to
Nanosphere prepared by hydro-thermal method is transferred on graphene film after filtering, and drying, due to having very on graphene film
More dangling bonds, in drying course, nanometer ball surface can be bonded with graphene film and realize firm combination；In addition, on
Nano-hollow ball is the preparation of nano-hollow hemisphere, using galvanoplastic and can combine template to prepare.Detailed process is as follows：
First, one layer of mould material is deposited on a substrate, and is etched through photoetching and etching technics on mould material
The core prints of nano-hollow hemisphere, graphene film surface is exposed between core prints；Here mould material can be adopted
With the expendable material of routine.
Then, using the core prints on mould material as template, using electroplating technology in the exposed table of graphene film 01
The material of the first semiconductor layer 11 is deposited on face and core prints, nano-hollow hemisphere pattern is formed so as to depend on core prints,
The first semiconductor layer 11 between nano-hollow hemisphere is etched into removal again；It is of course also possible to not by between nano-hollow hemisphere
The first semiconductor layer 11 etching remove, now, the first semiconductor layer 11 is directly covered on graphene film 01.Here, by
The technique that semiconductor material layer is prepared in electroplating technology deposition has been existing process, and those skilled in the art could be aware that here
, repeat no more here.
Then, using release process, mould material is discharged, so as to form nano-hollow hemisphere.On nano-hollow
The size of hemisphere can be controlled by controlling the size of core prints.
Step 03：Referring to Fig. 9, fill the first fluid electrolyte in the first semiconductor layer 11, and the is formed through solidification
One solid electrolyte 021；
Specifically, the top of the first solid electrolyte 021 is less than the top of nanosphere so that is exposed at the top of nanosphere
Come；This step 03 can specifically include：
Step 031：Under the first rotating speed, first electrolysis mass flow is filled by spin coating mode in the first semiconductor layer 11
Body；The time that the first fluid electrolyte spin coating now enters the surface of graphene film 01 is extremely short, such as 1 millisecond to 1 second of model
It is likely in enclosing.The graphene film 01 with substrate 00 can be first set to be rotated with the first rotating speed, then by the first electrolyte
On fluid injection graphene film 01, preferably, the first rotating speed is 50~90r/min.
Step 032：First rotating speed is promoted to the second rotating speed so that the first of at the top of the first semiconductor layer 11 and its top
Fluid electrolyte is thrown out of, then, near 3rd rotating speed of the second rotating speed, so that first in the first semiconductor layer 11
The top of fluid electrolyte is less than the top of the first semiconductor layer 11；
Specifically, the first rotating speed is promoted into the process of the second rotating speed also quickly, scope is between 1 millisecond to 1 second, preferably
, the second rotating speed is 2~6 times of the first rotating speed, and in the present embodiment, the second rotating speed is 150~300r/min.Here, control is passed through
Rotating speed processed will be exposed at the top of nano-hollow hemisphere.Detection method can be seen by SEM
Examine, if do not spilt, can also further second rotating speed the first fluid electrolyte is further thrown out of part so that nanometer
It is exposed at the top of hollow hemisphere
Step 033：The first fluid electrolyte is set to solidify to form the first solid electrolyte；
Specifically, due to the second rotating speed in step 032 be present, rotating speed can be gradually reduced to make the graphite with substrate 00
Alkene film 01 is stood, and in order to avoid being moved and changed in for the first fluid electrolyte, slowing down for rotating speed should relax, and rotating speed successively decreases
Value can be 3~5s/min.Here, the solidification of electrolyte is realized according to the property of used electrolyte, can with but it is unlimited
In realizing the solidification of the first fluid electrolyte by way of drying.
Step 04：Referring to Fig. 10, the epitaxial growth nanowire at the top of the nanosphere exposed, so as to form the second half
Conductor layer 12；
Specifically, here because the top of nano-hollow hemisphere has been exposed, the initial stage of nanowire growth, Ke Yi
The top forming core of nano-hollow hemisphere exposure simultaneously grows.The growth of nano wire can use existing process, such as chemical vapor deposition
Area method, aqua-solution method, galvanoplastic etc., because hydro-thermal method is one kind of aqua-solution method, its growth temperature is very low, can be less than 100
DEG C, the solid electrolyte 021 of graphene film 01 and first will not be had an impact, be synthesized here using hydrothermal reaction at low temperature, on
The prior art of nanowire growth is that those skilled in the art could be aware that, is repeated no more here.
Step 05：Figure 11 is referred to, the second fluid electrolyte is filled in nano wire, and the second solid-state electricity is formed through solidification
Solve matter 022；
Specifically, the top of the second solid electrolyte 022 is less than the top of nano wire so that is exposed at the top of nano wire
Come；The preparation process of second solid electrolyte 022 of this step 05 and the preparation process of the first solid electrolyte 021 of step 03
Similarly, including：
Step 051：Under the 3rd rotating speed, second electrolysis mass flow is filled by spin coating mode in the second semiconductor layer 12
Body；
Specifically, the 3rd rotating speed and the first rotating speed here can may be referred to the process description of step 031 with identical, this
In repeat no more.
Step 052：3rd rotating speed is promoted to the 4th rotating speed so that the second of at the top of the second semiconductor layer 12 and its top
Fluid electrolyte is thrown out of, so that the top of the second fluid electrolyte in the second semiconductor layer 12 is led less than the second half
The top of body layer；
Specifically, the 4th rotating speed and the second rotating speed here can with identical, the 4th rotating speed can also be the 3rd rotating speed 2~
6 times, the process description of step 032 is may be referred to, is repeated no more here.
Step 053：The second fluid electrolyte is set to solidify to form the second solid electrolyte 022；
Specifically, the solidification of the second fluid electrolyte is identical with the process of the solidification of the first fluid electrolyte, may be referred to
The process description of step 033, is repeated no more here.
Step 06：Figure 12 is referred to, goes out nano flower in the top epitaxial growth of the nano wire exposed, so as to form the 3rd
Semiconductor layer 13；
Specifically, because the top of nano wire has been exposed, the early growth period of nano flower can expose in nano wire
Top forming core and grow up.Preparation on nano flower can use existing process, such as aqua-solution method, template etc.,
Because hydro-thermal method belongs to one kind of aqua-solution method, its growth temperature is very low, can be less than 100 DEG C, will not be to graphene film 01
Have an impact, synthesized here using hydrothermal reaction at low temperature, on nanometer with the first solid electrolyte 021, the second solid electrolyte 022
The prior art of flower growth is that those skilled in the art could be aware that, is repeated no more here.
Step 07：Figure 13 is referred to, the 3rd fluid electrolyte is filled in nano flower, and the 3rd solid-state electricity is formed through solidification
Solve matter 023；Wherein, the top of the 3rd solid electrolyte 023 is higher than the top of nano flower.
Specifically, the 5th rotating speed and the first rotating speed here can also be slightly larger than the first rotating speed with identical, this is to consider
To the 3rd fluid electrolyte completed under a rotating speed, if rotating speed is too low, can influenceed flat at the top of the 3rd fluid electrolyte
Smooth degree.On the premise of top of the top of 3rd solid electrolyte 023 higher than nano flower, according to the need of actual ultracapacitor
Will, to be related to the height of the 3rd solid electrolyte, reach the target thickness of virtual electrode structure.
It should be noted that the first fluid electrolyte, the second fluid electrolyte and the 3rd fluid electrolyte are identical material
Material, so that the first solid electrolyte 021 ultimately formed, the second solid electrolyte 022 and the structure of the 3rd solid electrolyte 023
Into the solid electrolyte 02 of whole electrode structure, graphene film 01 that above-mentioned electrode structure includes, the first semiconductor layer 11,
Second semiconductor layer 12, the 3rd semiconductor layer 13 determine the base altitude of electrode structure, on this basis, adjust solid state electrolysis
The height of matter 02 reaches target thickness.
In addition, in order to strengthen the charging and discharging capabilities of electrode structure, also first layer afflux is formed in the bottom of graphene film 01
Body layer 03, as it was previously stated, as do not prepared current collector layers 03 first, graphene film 01 is only deposited on substrate 00, Ke Yi
After electrode structure prepares, substrate 00 is removed, that side that the graphene film 01 of electrode structure is exposed upward, then will
Current collector layers 03 are deposited on the surface of graphene film 01；Further, it is also possible to first prepare current collector layers 03, then electrode structure is prepared,
Specifically step 01 comes to prepare current collector layers, and its process can include：
Step a：Refer to Figure 14, there is provided a resistant to elevated temperatures substrate 00, also, deposit afflux on resistant to elevated temperatures substrate 00
Body layer 03；
Specifically, resistant to elevated temperatures substrate 00 can use flexible organic polymer layer, it is easy using flexible organic polymer layer
In stripping, convenient follow-up removal.It can be, but not limited to deposit current collector layers using physical gas-phase deposition.
Step b：Figure 15 is referred to, current collector layers 03 are etched, so as to form the pattern of current collector layers 03；
Specifically, can be, but not limited to etch the pattern of current collector layers 03 using photoetching and etching technics, here, collecting
The groove of hollow out is formed between the pattern of fluid layer 03.
Step c：Figure 16 and 17 are referred to, not by the surface of substrate 00 of the exposure of the pattern covers of current collector layers 03 and collection
The top of the pattern of fluid layer 03 and side wall form dielectric layer 05, and planarized dielectric layer 05, make the top of dielectric layer 05 and collection
Flushed at the top of the pattern of fluid layer 03；
Specifically, Figure 16 is referred to, the groove formed between the pattern of the full current collector layers 03 of the filling of dielectric layer 05, and cover
In the patterned surfaces of current collector layers 03, Figure 17 is referred to, can be, but not limited to remove to grind using CMP process
The dielectric layer 05 on the surface of current collector layers 03；The material of dielectric layer 03 can also be different from the material at high temperature-resistant liner bottom 00, after avoiding
Also it is removed together during continuous removal high temperature-resistant liner bottom 00.Due to foring the pattern of current collector layers 03, the figure of current collector layers 03
Equivalent to being filled with dielectric layer 05 between case；Dielectric layer 05 without removing, when can be used as subsequent deposition graphene film 01 with
Protecting the side wall of current collector layers 03 not grow when preparing the first to the 3rd semiconductor layer 11,12,13 of electrode structure has graphite
The semiconductor layer 11,12,13 of alkene film the 01 and first to the 3rd, in addition, the pattern of current collector layers 03 is essentially follow-up multiple
The current collector layers 03 of electrode structure, can by by the electrode structure prepared from the gap between the pattern of current collector layers 01
Dielectric layer 05 in cut open come so as to obtain single electrode structure, the pattern that two current collector layers 03 are shown in Figure 16 is
Example.
Step d：Figure 18 is referred to, using chemical vapour deposition technique, whole resistant to elevated temperatures substrate 00 is placed in chemical gaseous phase
In depositing operation chamber, go out graphene film 01 in the superficial growth that the pattern of current collector layers 03 exposes；
Specifically, the particularity of the chemical vapor deposition method due to graphene film 01, that is to say in chemical vapor deposition
Under product process conditions, graphene film 01 is only in the surface epitaxial growth of current collector layers 03, without in the surface extension of dielectric layer 05
Growth, therefore, the pattern of graphene film 01 is identical with the pattern of current collector layers 03.
In addition, after using step a~d processes, and after experience step 01~07, in addition to：Remove resistant to elevated temperatures
Substrate 00, the removing of resistant to elevated temperatures substrate 00 can use chemical corrosion method or be selected for different backing material different normal
The release process of rule.
, then can be it should be noted that if the above-mentioned resistant to elevated temperatures substrate 00 used is current collector material, such as copper
Substrate 00 is not removed after step 07, directly as collector, no longer can also additionally increase above-mentioned preparation current collector layers
Process.
On the preparation of current collector layers 03, such as lower section can also be used in other embodiments of the invention before step 01
Method：
Step I：Refer to Figure 19, there is provided a resistant to elevated temperatures substrate 00, also, the deposition medium on resistant to elevated temperatures substrate 00
Layer 05；
Specifically, resistant to elevated temperatures substrate 00 can still select flexible organic polymer layer, the material of dielectric layer 05 wants area
Not in the material of organic polymer layer, avoid removing flexible organic polymer layer and also got rid of together.
Step II：Figure 20 is referred to, the groove for filling current collector layers 03 is etched in dielectric layer 05, also, please
Refering to Figure 21, current collector layers 03 are filled in the trench；
Specifically, it can be, but not limited to etch groove using photoetching and etching technics, it is then possible to but be not limited to use
Electroplating technology deposits current collector layers 03 in the trench.It should be noted that using afflux deposited by physical vapour deposition (PVD)
Body layer 03 is also possible to be deposited on the surface of dielectric layer 05 outside groove, now needs outside groove using grinding or etching technics
The current collector layers 05 on the surface of dielectric layer 05 remove because current collector layers 03 use metal, such as copper, aluminium etc., using grinding or
Etching technics is not easy to remove, and therefore, preferably uses electroplating technology in the present embodiment, electroplating technology need to be in trench wall and bottom
Portion first prepares Seed Layer, so as to which accurately deposition current collector layers avoid current collector layers from being grown in outside groove in the trench.
Step III：Using chemical vapour deposition technique, whole resistant to elevated temperatures substrate 00 is placed in chemical vapor deposition process chamber
In, go out graphene film 01 in the superficial growth that current collector layers 00 expose；
Specifically, it is identical with step d, Figure 18 can be referred to, is repeated no more here.
In the present embodiment, after above-mentioned electrode structure is prepared, it is from the dielectric layer 05 between the pattern of current collector layers 03
Boundary cuts each electrode structure open to come, such as in Figure 18 shown in the position of dotted line, it is possible to continue to prepare this implementation
The graphene ultracapacitor of example.After multiple graphene ultracapacitors can also be prepared on substrate 00, cut, made
It is separated to obtain each graphene ultracapacitor, or, do not cut, but each graphene ultracapacitor is connected
Or it is in parallel, for example, by the previously prepared one layer of interconnection layer in the surface of substrate 00 of the bottom of current collector layers 03, for each collection that is electrically connected
Fluid layer 03.
In addition, surpassed in the said one embodiment of the present invention using graphene oxide film as the graphene of separation layer 04
,, can be by the way that graphene oxide film be transferred to without projection to be flat at the top of solid electrolyte 02 in level capacitor
The surface of solid electrolyte 02 of one of electrode structure, then by the surface of solid electrolyte 02 of another electrode structure and oxygen
Graphite alkene film is oppositely arranged, so as to graphene oxide film is located between two electrode structures to complete super capacitor
The preparation of device.
In addition, referring to Fig. 3~5, organic barrier film is used in the above-mentioned graphene ultracapacitor of the present embodiment
The top of solid electrolyte 02 as separation layer 04, and electrode structure has multiple raised T, two surfaces of organic barrier film
There is multiple depression A, depression A to coordinate with raised T-phase respectively, here, make the graphene super capacitor in raised T insertions depression A
The preparation method of device can include：
First, there is provided two above-mentioned electrode structures；
Secondly, wherein the solid electrolyte 02 of an electrode structure with raised T surface deposition one layer it is organic every
From film colloid, and simultaneously by the surface with raised T of the solid electrolyte 02 of another electrode structure from organic barrier film glue
In the organic isolating film colloid of overlying contact of body and embedded organic isolating film colloid, so that organic isolating film colloid is filled in this
In the raised T of the solid electrolyte 02 of two electrode structures gap；Here, on there is raised T in solid electrolyte 02
Surface deposit the method for organic isolating film colloid can be by the way of spin coating, further, since here using two electricity
The mode of pole structure opposing compression fitting, extruding can be produced to organic isolating film colloid when two electrode structures are bonded to each other
Power so that organic isolating film colloid is in close contact in two organic isolating film colloids, it is achieved thereby that organic isolating film colloid exists
Good filling between two electrode structures, therefore, the thickness of organic barrier film should be greater than twice of raised T height d.Such as figure
Shown in 3, raised T height d is the height on the surface of the solid electrolyte 02 of raised T top to raised T bottoms.
Then, solidify organic isolation membrane fluid, so as to complete the preparation of graphene ultracapacitor.
Please join again for the preparation method for making the graphene ultracapacitor in raised T insertions depression A of the present embodiment
Fig. 3~5 are read, following process can also be used：
First, organic barrier film is deposited on surface of the solid electrolyte 02 of an electrode structure with raised T wherein
Colloid；
Then, solidify organic isolating film colloid；
Then, the solid electrolyte with another electrode structure is etched in organic isolating film colloid using etching technics
The depression A that 02 raised T-phase coordinates；
Finally, the raised T alignments of another electrode structure are fitted together in depression A, so as to complete graphene super capacitor
The preparation of device.
Although the present invention is disclosed as above with preferred embodiment, the right embodiment illustrated only for the purposes of explanation and
, the present invention is not limited to, if those skilled in the art can make without departing from the spirit and scope of the present invention
Dry change and retouching, the protection domain that the present invention is advocated should be to be defined described in claims.
Claims (26)
- A kind of 1. electrode structure of ultracapacitor, it is characterised in that including：Graphene film；The first semiconductor layer being made up of nanosphere positioned at graphene film surface；The second semiconductor layer on the first semiconductor layer, the second semiconductor layer are made up of nano wire, and on each nanosphere At least nano wire contact normal thereto；The 3rd semiconductor layer on the second semiconductor layer, the 3rd semiconductor layer are made up of nano flower, and on every nano wire At least a nano flower contacts；Solid electrolyte is set on whole graphene film surface, and solid electrolyte is permeated in the first semiconductor layer, the second half In the gap of conductor layer and the 3rd semiconductor layer, and the first semiconductor layer, the second semiconductor layer and the 3rd semiconductor layer are wrapped up Firmly, the top of solid electrolyte is higher than the top of the 3rd semiconductor layer.
- 2. electrode structure according to claim 1, it is characterised in that the nanosphere of first semiconductor layer is hollow Ball.
- 3. electrode structure according to claim 2, it is characterised in that the hollow ball is bulbus cordis in midair, in midair bulbus cordis Diametral plane is located at graphene film surface, and the sphere of bulbus cordis is set upward in midair so that in midair between bulbus cordis and graphene film Form closed cavity.
- 4. electrode structure according to claim 2, it is characterised in that the internal diameter of hollow ball is
- 5. electrode structure according to claim 2, it is characterised in that the nano wire vertical-growth of second semiconductor layer Summit at the top of the hollow ball.
- 6. electrode structure according to claim 5, it is characterised in that the height of the nano wire is 1~10nm.
- 7. electrode structure according to claim 1, it is characterised in that the nano flower is received for what is opened from root to external radiation Rice bar construction, the root growth of the nano flower is in the top of the nano wire.
- 8. electrode structure according to claim 7, it is characterised in that the width of the nano flower is 5~10nm, and height is not More than 10nm.
- 9. electrode structure according to claim 1, it is characterised in that be additionally provided with collection in the bottom of the graphene film Fluid layer, the pattern of the graphene film are identical with the pattern of current collector layers.
- 10. electrode structure according to claim 1, it is characterised in that the material of first semiconductor layer is transition group Metal oxide.
- 11. electrode structure according to claim 1, it is characterised in that the height of the nanosphere is less than or equal to described The height of nano wire, the height of the nano flower are less than or equal to the height of the nano wire, and the width of the nano flower is less than Or the diameter equal to nano wire, the width of the nano flower are less than or equal to the diameter of nanosphere.
- 12. electrode structure according to claim 1, it is characterised in that there are multiple projections at the top of the solid electrolyte.
- A kind of 13. preparation method of the electrode structure described in claim 1, it is characterised in that including：Step 01：Prepare the graphene film with substrate；Step 02：Nanosphere is synthesized on graphene film surface, so as to form the first semiconductor layer；Step 03：The first fluid electrolyte is filled in the first semiconductor layer, and the first solid electrolyte is formed through solidification；Its In, the top of the first solid electrolyte is less than the top of nanosphere so that is exposed at the top of nanosphere；Step 04：The epitaxial growth nanowire at the top of the nanosphere exposed, so as to form the second semiconductor layer；Step 05：The second fluid electrolyte is filled in nano wire, and the second solid electrolyte is formed through solidification；Wherein, second The top of solid electrolyte is less than the top of nano wire so that is exposed at the top of nano wire；Step 06：Go out nano flower in the top epitaxial growth of the nano wire exposed, so as to form the 3rd semiconductor layer；Step 07：The 3rd fluid electrolyte is filled in nano flower, and the 3rd solid electrolyte is formed through solidification；Wherein, the 3rd The top of solid electrolyte is higher than the top of nano flower.
- 14. the preparation method of electrode structure according to claim 13, it is characterised in that in the step 02, using water Hot method, solvent-thermal method, inorganic template method synthesize nanosphere.
- 15. the preparation method of electrode structure according to claim 13, it is characterised in that the step 03 specifically includes：Step 031：Under the first rotating speed, the first fluid electrolyte is filled by spin coating mode in the first semiconductor layer；Step 032：First rotating speed is promoted to the second rotating speed so that the first semiconductor layer and its first electrolyte of top Fluid is thrown out of, then, near 3rd rotating speed of the second rotating speed, so that the first electrolysis mass flow in the first semiconductor layer The top of body is less than the top of the first semiconductor layer；Step 033：The first fluid electrolyte is set to solidify to form the first solid electrolyte；The step 05 specifically includes：Step 051：Under the 3rd rotating speed, the second fluid electrolyte is filled by spin coating mode in the second semiconductor layer；Step 052：3rd rotating speed is promoted to the 4th rotating speed so that the second semiconductor layer and its second electrolyte of top Fluid is thrown out of, so that the top of the second fluid electrolyte in the second semiconductor layer is less than the top of the second semiconductor layer Portion；Step 053：The second fluid electrolyte is set to solidify to form the second solid electrolyte；The step 07 specifically includes：Under the 5th rotating speed, the 3rd electrolysis is filled by spin coating mode in the 3rd semiconductor layer Mass flow body, rotating speed is then gradually reduced until static, make the top of the 3rd fluid electrolyte that is located in the 3rd semiconductor layer high In the top of the 3rd semiconductor layer, finally, the 3rd fluid electrolyte is set to solidify to form the 3rd solid electrolyte.
- 16. the preparation method of electrode structure according to claim 15, it is characterised in that first rotating speed, the 3rd turn Speed is identical with the 5th rotating speed, and second rotating speed is identical with the 4th rotating speed.
- 17. the preparation method of electrode structure according to claim 16, it is characterised in that second rotating speed is first turn 2~6 times of speed, the 4th rotating speed are 2~6 times of the 3rd rotating speed.
- 18. the preparation method of electrode structure according to claim 13, it is characterised in that described to receive in the step 04 Rice noodles are prepared using chemical vapour deposition technique, aqua-solution method, electrochemical plating；In the step 06, the nano flower uses It is prepared by aqua-solution method, template.
- 19. the preparation method of electrode structure according to claim 13, it is characterised in that before the step 01, also wrap Include：Step a：One high temperature-resistant liner bottom is provided, also, current collector layers are deposited on substrate；Step b：Current collector layers are etched, so as to form the pattern of current collector layers；Step c：Not by the top and side of the substrate surface of the exposure of the pattern covers of current collector layers and the pattern of current collector layers Wall forms dielectric layer, and planarized dielectric layer, makes at the top of dielectric layer with being flushed at the top of the pattern of current collector layers；Step d：Using chemical vapour deposition technique, whole high temperature-resistant liner bottom is placed in chemical vapor deposition process chamber, in afflux The superficial growth of the pattern exposure of body layer goes out graphene film；After step 07, in addition to：Remove high temperature-resistant liner bottom.
- 20. the preparation method of electrode structure according to claim 13, it is characterised in that before the step 01, also wrap Include：Step I：One high temperature-resistant liner bottom, also, the deposition of sacrificial layer on high temperature-resistant liner bottom are provided；Step II：Etched in sacrifice layer for filling the groove of current collector layers, and fill current collector layers in the trench；Step III：Using chemical vapour deposition technique, whole high temperature-resistant liner bottom is placed in chemical vapor deposition process chamber, collected The superficial growth of fluid exposure goes out graphene film；Step IV：Using release process, sacrifice layer is removed, so as to leave current collector layers on high temperature-resistant liner bottom；After step 07, in addition to：Remove the high temperature-resistant liner bottom.
- A kind of 21. graphene ultracapacitor, it is characterised in that including：Electrode structure described in two claims 1 is set relatively Put, and the separation layer between the electrode structure.
- 22. graphene ultracapacitor according to claim 21, it is characterised in that the separation layer is organic isolation Film, the solid electrolyte top of the electrode structure have multiple projections；Two surfaces of organic barrier film have respectively Multiple depressions, depression are engaged with projection, are made in raised embedded depression.
- 23. graphene ultracapacitor according to claim 22, it is characterised in that two tables of organic barrier film The distance between the bottom of depression in face is not more than 2nm.
- 24. graphene ultracapacitor according to claim 21, it is characterised in that the separation layer is graphene oxide Film.
- A kind of 25. preparation method of the graphene ultracapacitor described in claim 22, it is characterised in that including：First, there is provided two electrode structures；Secondly, the surface with projection of the solid electrolyte of an electrode structure deposits one layer of organic barrier film wherein Colloid, and the solid electrolyte of another electrode structure is had into raised surface from organic isolating film colloid simultaneously In the organic isolating film colloid of overlying contact and embedded organic isolating film colloid, so that organic isolating film colloid is filled in the two In the raised gap of the solid electrolyte of electrode structure；Then, solidify organic isolating film colloid, so as to complete the preparation of graphene ultracapacitor.
- A kind of 26. preparation method of the graphene ultracapacitor described in claim 22, it is characterised in that including：First, organic isolating film colloid is deposited on surface of the solid electrolyte of an electrode structure with projection wherein；Then, solidify organic isolating film colloid；Then, etched using etching technics in organic isolating film colloid convex with the solid electrolyte of another electrode structure Act the depression being engaged；Finally, the raised alignment of another electrode structure is fitted together in depression, so as to complete the system of graphene ultracapacitor It is standby.
Priority Applications (1)
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100216026A1 (en) * | 2009-02-25 | 2010-08-26 | Applied Materials, Inc. | Thin film electrochemical energy storage device with three-dimensional anodic structure |
| US20130153860A1 (en) * | 2011-12-16 | 2013-06-20 | Samsung Electronics Co., Ltd. | Method of forming hybrid nanostructure on graphene, hybrid nanostructure, and device including the hybrid nanostructure |
| CN104201006A (en) * | 2014-08-15 | 2014-12-10 | 国家纳米科学中心 | Preparation method of carbon nanotube/manganese dioxide hybridization supercapacitor electrode material |
| CN104701030A (en) * | 2015-03-24 | 2015-06-10 | 武汉理工大学 | All-solid-state symmetrical three-dimensional micro super capacitor and preparation method thereof |
| CN105845447A (en) * | 2015-01-13 | 2016-08-10 | 苏州复纳电子科技有限公司 | Nanorod-shaped electrode, nano structure supercapacitor, and preparation method for nano structure supercapacitor |
| CN106409518A (en) * | 2016-10-09 | 2017-02-15 | 全普光电科技(上海)有限公司 | Graphene-based composite thin film, self-cleaning solar thin film cell and preparation method |
| CN106449133A (en) * | 2016-10-08 | 2017-02-22 | 全普光电科技(上海)有限公司 | Single-layer graphene thin film-based composite structure, preparation method and semiconductor device |
| CN206976175U (en) * | 2017-08-01 | 2018-02-06 | 全普光电科技(上海)有限公司 | Electrode structure, graphene ultracapacitor |
-
2017
- 2017-08-01 CN CN201710645370.4A patent/CN107610937A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100216026A1 (en) * | 2009-02-25 | 2010-08-26 | Applied Materials, Inc. | Thin film electrochemical energy storage device with three-dimensional anodic structure |
| US20130153860A1 (en) * | 2011-12-16 | 2013-06-20 | Samsung Electronics Co., Ltd. | Method of forming hybrid nanostructure on graphene, hybrid nanostructure, and device including the hybrid nanostructure |
| CN104201006A (en) * | 2014-08-15 | 2014-12-10 | 国家纳米科学中心 | Preparation method of carbon nanotube/manganese dioxide hybridization supercapacitor electrode material |
| CN105845447A (en) * | 2015-01-13 | 2016-08-10 | 苏州复纳电子科技有限公司 | Nanorod-shaped electrode, nano structure supercapacitor, and preparation method for nano structure supercapacitor |
| CN104701030A (en) * | 2015-03-24 | 2015-06-10 | 武汉理工大学 | All-solid-state symmetrical three-dimensional micro super capacitor and preparation method thereof |
| CN106449133A (en) * | 2016-10-08 | 2017-02-22 | 全普光电科技(上海)有限公司 | Single-layer graphene thin film-based composite structure, preparation method and semiconductor device |
| CN106409518A (en) * | 2016-10-09 | 2017-02-15 | 全普光电科技(上海)有限公司 | Graphene-based composite thin film, self-cleaning solar thin film cell and preparation method |
| CN206976175U (en) * | 2017-08-01 | 2018-02-06 | 全普光电科技(上海)有限公司 | Electrode structure, graphene ultracapacitor |
Non-Patent Citations (1)
| Title |
|---|
| 吴红英;王欢文;: "钴酸镍纳米花/活性炭纤维复合物的制备和表征及其超级电容器性能", 物理化学学报 * |
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