CN110247028A - A kind of nano wire/three-dimensional graphene composite material - Google Patents
A kind of nano wire/three-dimensional graphene composite material Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 89
- 239000002105 nanoparticle Substances 0.000 claims abstract description 165
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 27
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- 239000002184 metal Substances 0.000 claims description 26
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- Y02E60/10—Energy storage using batteries
Abstract
A kind of nano wire/three-dimensional graphene composite material, including nano-wire array, three-dimensional grapheme on the nano-wire array depend on multiple nano particles and/or at least one layer of nano thin-film on the three-dimensional grapheme.Nano wire (one-dimensional), grapheme material (two, three-dimensional) are combined together by the nano wire/three-dimensional graphene composite material with nano particle (zero dimension) and/or/nano thin-film (two dimension) material, it realizes compound to three-dimensional nano material by zero dimension, the advantages of sufficiently combining above-mentioned various sizes nano material, and the shortcomings that in turn avoid each material simultaneously.
Description
Technical field
This disclosure relates to nano wire/three-dimensional graphene composite material, its manufacturing method and application.
Background technique
The two dimensional crystal for only one layer of atomic thickness that graphene (Graphene) is made of carbon atom.2004, English
Stone is isolated in University of Manchester, state physicist An Deliegaimu and Constantine's Nuo Woxiao love, success from graphite
Black alkene, it was demonstrated that therefore it can also obtain jointly Nobel Prize in physics in 2010 with individualism, two people.
Currently, graphene has very promising application in all various aspects, but there is also many during functionization
Technical problem to be solved.
Summary of the invention
The embodiment of the present invention provides a kind of nano wire/three-dimensional graphene composite material, including nano-wire array, described receives
Three-dimensional grapheme on nanowire arrays depends on multiple nano particles and/or at least one layer of nanometer on the three-dimensional grapheme
Film.
In one embodiment, for example, the nano wire/three-dimensional graphene composite material includes nano-wire array, institute
It states the three-dimensional grapheme on nano-wire array, depend on the multiple nano particle on the three-dimensional grapheme and/or described
At least one layer of nano thin-film.
In one embodiment, for example, three-dimensional grapheme on the nano-wire array, the three-dimensional grapheme are complete
Or part is attached to the nano-wire array.
In one embodiment, for example, the multiple nano particle is attached on the three-dimensional grapheme, it is described extremely
Few one layer of nano thin-film coats the multiple nano particle and the three-dimensional grapheme.
In one embodiment, for example, at least part in the multiple nano particle is attached to the three-dimensional stone
On black alkene, the outermost layer nano thin-film of at least one layer nano thin-film coats the multiple nano particle, the three-dimensional stone
Black alkene and other layer of nano thin-film.
In one embodiment, for example, the nano-wire array of the attachment three-dimensional grapheme, the average length of nano wire
For 200nm~200 μm, preferably 1~100 μm, preferably 5~50 μm；Diameter 1~1000nm of average out to of nano wire, preferably 50~
200nm。
In one embodiment, for example, three-dimensional grapheme on the nano-wire array, average-size be 10nm~
1000nm, preferably 50~200nm.
In one embodiment, for example, the three-dimensional grapheme has porous structure, average channel diameter is 10nm-
200nm, preferably 20nm-50nm.
In one embodiment, if for example, the three-dimensional grapheme includes that the dry plate that irregularly flocks together is more
Layer graphene and/or single-layer graphene.
In one embodiment, if for example, in the dry plate multi-layer graphene and/or single-layer graphene, per a piece of
The carbon atom number of plies of graphene is 1-10 layers, preferably 2-7 layers, preferably 3-6 layers.
In one embodiment, for example, the nanoparticle size is 1-100nm, preferably 2-50nm, preferably 3-
30nm。
In one embodiment, for example, the nano wire for being attached with three-dimensional grapheme includes various forms and size
Monodimension nanometer material, including carbon nanotube, carbon nanocoils, metal nanometer line, oxide nano thread, polymer nanotube gather
Object nano wire, sulfide nanometer linear, semiconductor nanowires are closed, the carbon nanotube includes single-walled nanotube, many walls nanotube；Gold
Belonging to nano wire includes Cu nano wire, Au nano wire, Ag nano wire, Ni nano wire, Fe nano wire；The oxide nano thread packet
Include transition metal oxide nano line, MnO2Nano wire, Mn3O4Nano wire, MnO nano wire, NiO nanowire, Co3O4Nano wire,
Fe2O3Nano wire, Fe3O4Nano wire, V2O5Nano wire, TiO2Nano wire, lithium composite xoide nano wire, LiCoO2Nano wire,
LiMnO2Nano wire, LiMn2O4Nano wire, LiFePO4Nano wire, Li4Ti5O12Nano wire, nickle cobalt lithium manganate nano wire, nickel cobalt aluminium
Sour lithium nano wire；The semiconductor nanowires include Si nano wire, Ga nano wire, ZnO nano particle；The polymer nanocomposite
Grain includes polyaniline (PANI) nano wire, poly- 3,4- hexamethylene dioxy thiophene (PEDOT) nano wire.
In one embodiment, for example, the nano particle includes metal nanoparticle, non pinetallic nano particle, oxygen
Compound nano particle, sulfide nanoparticle, semiconductor nanoparticle and/or polymer nano granules, the metal nano
Grain includes Pt nano particle, Au nano particle, Ag nano particle；The non pinetallic nano particle includes S nano particle；The oxygen
Compound nano particle includes MnO2Nano particle, lithium composite xoide nano particle, LiCoO2Nano particle, LiMnO2Nanometer
Grain, LiMn2O4Nano particle, LiFePO4Nano particle, Li4Ti5O12Nano particle, nickle cobalt lithium manganate nano particle, nickel cobalt aluminium
Sour lithium nano particle, Mn3O4Nano particle, MnO nano particle, NiO nano particle, Co3O4Nano particle, Fe2O3Nanometer
Grain, Fe3O4Nano particle, V2O5Nano particle, TiO2Nano particle；The sulfide nanoparticle includes MoS2Nano particle；
The semiconductor nanoparticle includes Si nano particle, ZnO nano particle；The polymer nano granules include polyaniline
(PANI) nano particle, poly- 3,4- hexamethylene dioxy thiophene (PEDOT) nano particle.
In one embodiment, for example, each single-layer nano-film is in at least one layer nano thin-film with a thickness of 2-
100nm, preferably 3-50nm, preferably 5-20nm.
In one embodiment, for example, the nano thin-film includes metal nanometer thin film, non pinetallic nano film, oxygen
Compound nano thin-film, sulfide nano thin-film, semiconductor nanomembrane and/or polymer nanocomposite film, the metal nano are thin
Film includes Pt nano thin-film, Au nano thin-film, Ag nano thin-film；The non pinetallic nano film includes S nano thin-film；The oxygen
Compound nano thin-film includes MnO2Nano thin-film, lithium composite xoide nano thin-film, LiCoO2Nano thin-film, LiMnO2Nanometer thin
Film, LiMn2O4Nano thin-film, LiFePO4Nano thin-film, Li4Ti5O12Nano thin-film, nickle cobalt lithium manganate nano thin-film, nickel cobalt aluminium
Sour lithium nano thin-film, Mn3O4Nano thin-film, MnO nano thin-film, NiO nano thin-film, Co3O4Nano thin-film, Fe2O3Nanometer thin
Film, Fe3O4Nano thin-film, V2O5Nano thin-film, TiO2Nano thin-film；The sulfide nano thin-film includes MoS2Nano thin-film；
The semiconductor nanomembrane includes Si nano thin-film, ZnO nano film；The polymer nanocomposite film includes polyaniline
(PANI) nano thin-film, poly- 3,4- hexamethylene dioxy thiophene (PEDOT) nano thin-film.
In one embodiment, it is repaired for example, carrying out surface by method physically or chemically to the three-dimensional grapheme
Decorations, the surface modification are included in the defects of vacancy, edge are caused in the three-dimensional grapheme surface, in the three-dimensional grapheme table
Face foreign atom is covalently attached functional group on the three-dimensional grapheme surface, and/or covalently connects on the three-dimensional grapheme surface
Connect high polymer monomer or macromolecule oligomer.
In one embodiment, for example, the nano wire/three-dimensional graphene composite material mass specific area exists
400m2/ g or more.
The embodiment of the present invention provides a kind of electrode, including nano wire/three-dimensional graphene composite material as described above.
The embodiment of the present invention provides a kind of supercapacitor, including electrolyte, diaphragm, collector and electricity as described above
Pole.
The embodiment of the present invention provides a kind of battery, including electrode as described above.
The embodiment of the present invention provides a kind of lithium ion battery, including electrode as described above as anode, wherein described
Nano particle includes lithium composite xoide nano particle, LiCoO2Nano particle, LiMnO2Nano particle, LiMn2O4Nanometer
Grain, LiFePO4Nano particle, Li4Ti5O12Nano particle, nickle cobalt lithium manganate nano particle, nickel cobalt lithium aluminate nano particle.
The embodiment of the present invention provides a kind of lithium ion battery, including electrode as described above as cathode, wherein described
Nano particle includes Si nano particle, SiO2Nano particle, MnO2Nano particle, Mn3O4Nano particle, MnO nano particle,
Li4Ti5O12Nano particle, Fe2O3Nano particle.
The embodiment of the present invention provides a kind of manufacturing method of nano wire/three-dimensional graphene composite material, comprising: uses gas
It mutually deposits, the methods of ion sputtering, electrochemical deposition or atomic deposition grow the nano-wire array on substrate.Using etc. from
Daughter enhances chemical vapor deposition (PECVD) method, using the mixing gas of carbonaceous gas and auxiliary gas as carbon source, in nanometer
Growing three-dimensional graphene in linear array；Multiple nano particles and/or at least one layer of nanometer are prepared on the three-dimensional grapheme surface
Film；Wherein, the auxiliary gas includes argon gas and hydrogen.
In one embodiment, for example, in the above-mentioned methods, the mixing gas of the carbonaceous gas and auxiliary gas
Pressure is 0.01-500Pa, preferably 150-300Pa, further preferably 200-250Pa.
In one embodiment, described to prepare multiple receive on the three-dimensional grapheme surface for example, in the above-mentioned methods
Rice grain and/or at least one layer of nano thin-film include: by Directly depositing, electrochemical deposition method, wet chemistry method sedimentation, gas
The methods of phase sedimentation or atom deposition method prepare multiple nano particles on the three-dimensional grapheme surface and/or at least one layer is received
Rice film.
In one embodiment, for example, further including activation step in the above-mentioned methods, by the activation step,
A large amount of micropores are formed on graphene sheet layer, having a size of 0.5~5nm, preferably 1~3nm.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, the attached drawing to embodiment is simply situated between below
It continues, it should be apparent that, the accompanying drawings in the following description merely relates to some embodiments of the present invention, rather than limitation of the present invention.
Fig. 1 is nano wire of the invention/three-dimensional grapheme material schematic diagram (side view)；
Fig. 2 is nano wire of the invention/three-dimensional grapheme material schematic diagram (top view)；
Fig. 3 is showing for the three-dimensional grapheme on nano-wire array described in nano wire of the invention/three-dimensional grapheme material
It is intended to；
Fig. 4 is showing for the three-dimensional grapheme on nano-wire array described in nano wire of the invention/three-dimensional grapheme material
It is intended to；
Fig. 5 is the TEM of the three-dimensional grapheme on nano-wire array described in nano wire of the invention/three-dimensional grapheme material
Figure；
Fig. 6 be one embodiment of the invention provide based on nano wire/three-dimensional grapheme-MnO2Nano particle composite material
Electrode of super capacitor volt-ampere test result figure；
Fig. 7 be one embodiment of the invention provide based on nano wire/three-dimensional grapheme-MnO2- PANI nanometers of nano particle
Film composite material electrode of super capacitor volt-ampere test result figure；
Fig. 8 is that the same electrode material of Fig. 2 carries out the result after 200,000 volt-ampere tests；
Fig. 9 is three-dimensional grapheme-nano particle composite material structural schematic diagram that one embodiment of the invention provides；
Figure 10 is three-dimensional grapheme-nano thin-film composite structure schematic diagram that one embodiment of the invention provides；
Figure 11 is that three-dimensional grapheme-nano particle-nano thin-film composite structure that one embodiment of the invention provides shows
It is intended to；
Figure 12 is the compound based on nano wire/three-dimensional grapheme material-PANI nano thin-film of one embodiment of the invention offer
The lithium ion battery charging/discharging voltage of material and the relationship of capacity；
Figure 13 is the compound based on nano wire/three-dimensional grapheme material-PANI nano thin-film of one embodiment of the invention offer
The lithium ion battery charge and discharge number and multiplying power of material and the relationship of capacity；
Figure 14 is nano wire/three-dimensional grapheme material-Ni/Pt nano particle composite material that one embodiment of the invention provides
Catalytic performance test result.
Fig. 1,2 are nano wire of the invention/three-dimensional grapheme material schematic diagrames, and wherein Fig. 1 is side view, and Fig. 2 is top
View.In Fig. 1,1 is nano-wire array, and 2 for the three-dimensional grapheme on nano-wire array, (schematic diagram does not represent three-dimensional graphite
The concrete shape of alkene, practical three-dimensional grapheme are attached on nano-wire array completely or partially).In Fig. 2 in visible situation and Fig. 1
Similar, graphene is attached on nano-wire array that (actual ratio can be by change nano wire or three-dimensional grapheme completely or partially
Growth time regulation).Fig. 3,4 be three-dimensional grapheme material on nano-wire array schematic diagram, Fig. 5 is on nano-wire array
The TEM of three-dimensional grapheme material schemes.The random arrangement of graphene nanometer sheet in the visible three-dimensional grapheme material in Fig. 3,4,5, shape
At porous three-dimensional mechanism.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be to the embodiment of the present invention
Technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiments of the present invention, rather than
Whole embodiments.Based on described the embodiment of the present invention, those of ordinary skill in the art are without creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
Unless otherwise defined, technical term or scientific term used in the disclosure are should be in fields of the present invention
The ordinary meaning that personage with general technical ability is understood.
Graphene (Graphene) has the closely packed monoatomic layer structure of carbon atom, has good electric conductivity and Gao Bi
Surface area.By development in recent years, graphene has comparable research and application in terms of electronic device, photoelectricity, the energy,
It is ideal supercapacitor carbon-based material.But graphene also has disadvantage, and the graphene of commonsense method preparation is similar with active carbon,
Need under high pressure electrode pressing with keep electrode structure stablize, be easy to happen stacking phenomenon in the process, lead to material specific surface
The decline of long-pending and ionic conductivity.Therefore, develop suitable preparation method, be prepared with the graphene of rock-steady structure, and to graphene
It is surface modified, forming combination electrode material with other materials is a kind of necessary measure.Nano particle and nano thin-film tool
There is good conductive, thermally conductive and chemical characteristic.But nano particle nature is in bulky powder, is purchased into the device of macroscopic view
Part, component, molding are a very big problems, and furthermore nano particle is easy to happen reunion, and many nano particles is excellent after reunion
Heterogeneity will receive adverse effect；Nano thin-film is equally also difficult to form the device architecture of macroscopic view sizing, and in type-approval process
It is also easy to destroy the microstructure of nano thin-film, the loss of performance is caused even to disappear.
The present inventor by by nano wire/three-dimensional graphene composite material by nano wire (one-dimensional), graphene material
Material (two dimension, three-dimensional) is combined together, the nanometer being prepared with nano particle (zero dimension) and/or/nano thin-film (two dimension) material
Line/three-dimensional graphene composite material realizes and is combined by zero dimension to three-dimensional nano material, given full play to above-mentioned various sizes
The advantages of nano material, and the shortcomings that in turn avoid each material simultaneously.Nano wire/the three-dimensional graphene composite material has following
Advantage:
1) it is provided as nano wire/three-dimensional graphene composite material skeleton structure nano-wire array and is conducive to three-dimensional stone
The bigger serface of black alkene growth.Its mechanical strength facilitates the maintenance macroscopic three dimensional of the three-dimensional grapheme on nano-wire array simultaneously
Structure.Furthermore nano-wire array can increase three-dimensional grapheme and nano particle/leading between nano thin-film and substrate thereon
Electrically.
2) three-dimensional grapheme further increases the specific surface area height of material, has stable three-dimensional structure, internal stone
It is less between black alkene layer to there is reunion and stack, be conducive to the superior electrical performance for giving full play to graphene, and not in application
Need additionally to add conductive agent and binder, with the increase of total amount of material in practical application, effective ratio area will not be reduced.
3) it is modified by carrying out surface to three-dimensional grapheme material or nano wire/three-dimensional graphene composite material, the table
Face modification is included in the defects of vacancy, edge are caused in the three-dimensional grapheme surface, in the three-dimensional grapheme surface doping original
Son is covalently attached functional group on the three-dimensional grapheme surface, and/or is covalently attached macromolecule on the three-dimensional grapheme surface
Monomer or macromolecule oligomer can substantially improve the hydrophily and oleophylic of graphene in the case where not destroying three-dimensional structure
Property, aqueous or non-aqueous liquid is substantially increased in three-dimensional grapheme material or nano wire/three-dimensional graphene composite material
Infiltration so that three-dimensional grapheme material or nano wire/three-dimensional graphene composite material chemical activity and physical activity all pole
Big increase.
4) nano particle being loaded on three-dimensional grapheme material, nano particle is dispersed by grapheme material, keeps apart,
So as to avoid the reunion between nano particle, be conducive to the excellent properties for keeping nano particle；In nano particle and three-dimensional stone
Nano film material is prepared on black alkene material, nano film material wraps up nano particle and three-dimensional grapheme material,
It can prevent nano particle in application process from falling off from three-dimensional grapheme material, nano wire/three-dimensional grapheme has been significantly greatly increased
Cyclicity, the durability of composite material.
5) by nano particle and Nanometer thin film deposition on three-dimensional grapheme material, nano particle and nano thin-film are in big ruler
Very little upper (micron order) has three-dimensional structure identical with three-dimensional grapheme material, and efficiently solve that nano material is difficult to shape asks
Topic, facilitates nano material in a large amount of uses macroscopically；In addition, the usual poorly conductive of nano material, especially non pinetallic nano
The electric conductivity of material is very poor, and the close contact with the good three-dimensional grapheme material of electric conductivity greatly improves a nanometer material
Macroscopical conductivity of material.
6) three-dimensional grapheme material has a porous structure, and internal have a large amount of mesoporous, and it is left that average pore size is less than 20nm
The advantages of right side, this effectively combines graphene and porous carbon materials, while flake structure and meso-hole structure are provided, increase stone
The application range of black alkene.
In conclusion the present invention perfectly combines the materials such as nano wire, graphene, porous carbon, nano particle, nano thin-film
Every advantage of material, and the shortcomings that successfully overcome when a variety of materials are used alone and deficiency, keeping nanometer size effect
So that the size of composite material is reached hundreds of microns simultaneously, nano-scale characteristic has been effectively kept under macro-size, effectively
Solve the problems, such as previous nano wire, graphene and other nano materials macro-scale using when lose nano material characteristic.
The composite material can be applied to the fields such as energy storage material (such as secondary cell), chemical catalysis, photocatalysis and biomaterial, be one
Kind has the nanocomposite of new generation of broad prospect of application.
1 carbon nanocoils of embodiment/three-dimensional grapheme-nano particle composite material
Using copper sheet as substrate, using chemical vapour deposition technique (Chemical Vapor Deposition, abbreviation CVD method)
Produce carbon nanocoils array；Using plasma enhances chemical vapour deposition technique (Plasma Enhanced Chemical
Vapor Deposition, abbreviation PECVD), three-dimensional grapheme is produced on carbon nanocoils array；It is former on three-dimensional grapheme
Position deposition MnO2Nano particle prepares carbon nanocoils/three-dimensional grapheme-MnO2Nano particle composite material, then it is based on carbon nanometer
Line/three-dimensional grapheme-MnO2Nano particle composite material prepares electrode of super capacitor.
With CH4Gas is heated to 850 DEG C as presoma, Cu in CVD reacting furnace, by CH4Gas introduces CVD reacting furnace
In, carbon nanocoils array is grown on Cu by CVD method, growth time 5h obtains the carbon nanocoils array that height is 10 μm.
Then with CH4The plasma of gas is used as auxiliary gas as presoma, hydrogen and argon gas, by CH4Gas, hydrogen and argon gas
Mixed gas is formed after mixing, wherein the CH4The volume ratio of gas and the auxiliary gas is 1: 2, obtained carbon nanometer
Array is heated to 850 DEG C in PECVD reacting furnace.Foregoing mixed gas is introduced into PECVD reactor, is existed by PECVD
Growing three-dimensional graphene on carbon nano-array, growth time control are 1 minute, obtain carbon nanocoils/three-dimensional grapheme composite wood
Material.With O210 minutes progress surfaces of plasma bombardment it is modified, activated using chemical method.By the activation step,
A large amount of micropores are formed on graphene sheet layer, having a size of 0.5~5nm, preferably 1~3nm.Certainly, the activation is not limited to
It states and uses O2Plasma bombardment, can also include other activation methods.For example, can be by the nano wire/three-dimensional grapheme
Composite material is soaked in KOH solution, is sufficiently dried after infiltration, is heat-treated in N2 atmosphere；Or by the carbon nanocoils/
Three-dimensional graphene composite material is under the vacuum of < 100Pa in H2O (g), CO2Middle heat treatment.No matter with which kind of activation method, only
Want can be formed the micropore of a large amount of Nano grades on graphene sheet layer.
Deposit MnO2Nano particle: with MnSO4For presoma, MnO is deposited on graphene using electrochemical oxidation process2It receives
Rice grain.Configure the MnSO of 0.5M4Aqueous solution, carbon nanocoils/three-dimensional graphene composite material do anode, and platinized platinum is cooked cathode, with
1mA/cm2Current deposits 10s, then -0.5mA/cm2Electric current reversely continue 5s, repeat 60 times, obtain being deposited on three-dimensional stone
MnO on black alkene2Nanoparticle size is about 20nm.
In 100 DEG C of dry 1h after cleaning, carbon nanocoils/three-dimensional grapheme-MnO is obtained2Nano particle super capacitor electrode
Pole.By electrochemical workstation, using linear voltammetry (50mV/s), use platinum electrode of the same area as to electrode, with
6M KOH aqueous solution makees electrolyte, carries out electrochemical property test, test results are shown in figure 6.As seen from Figure 6, it is based on this reality
Apply carbon nanocoils/three-dimensional grapheme-MnO of example2The electrode of super capacitor of nano particle composite material has good linear
Volt-ampere performance.
Fig. 9 illustrates the present invention-embodiment three-dimensional grapheme-nano particle composite material possibility structure, nanometer
Grain is attached on the graphene film of three-dimensional grapheme material, and is formed and directly contacted.
2 metal nanometer lines of embodiment/three-dimensional grapheme-MnO2Nano particle-PANI nano thin-film composite material
Nano wire is deposited using electrochemical process, to be coated with the alumina formwork of Ag film as substrate, AgNO3、CuSO4Or
HAuO4, mixed solution produce the nano wire of Ag, Cu or Au, then alumina formwork is removed using NaOH solution, obtains gold
Belong to the nano-wire array of Ag, Cu or Au.
Three-dimensional grapheme material using PECVD, in preparing nano linear array；It sinks in situ on three-dimensional grapheme material
Product MnO2Nano particle and polyaniline (PANI) nano thin-film, prepare metal nanometer line three-dimensional grapheme-MnO2Nano particle-
PANI nano thin-film composite material, then it is based on the metal nanometer line/three-dimensional grapheme-MnO2Nano particle-PANI nano thin-film
Composite material prepares electrode of super capacitor.
With CH4The plasma of gas is used as auxiliary gas as presoma, hydrogen and argon gas, by CH4Gas, hydrogen, nitrogen
Mixed gas is formed after gas and argon gas mixing, wherein the CH4The volume ratio of gas and the auxiliary gas is 1: 4, has been obtained
Metal nanometer line 850 DEG C are heated in PECVD reacting furnace.Foregoing mixed gas is introduced into PECVD reactor, is passed through
PECVD growing three-dimensional graphene on metal nanometer line array, growth time control are 1 minute, obtain metal nanometer line/tri-
Tie up graphene composite material.With O210 minutes progress surfaces of plasma bombardment it is modified, activated using chemical method.
Deposit MnO2Nano particle: with MnSO4For presoma, MnO is deposited on graphene using electrochemical oxidation process2It receives
Rice grain.Configure the MnSO of 0.5M4Aqueous solution, three-dimensional grapheme do anode, and platinized platinum is cooked cathode, with 1mA/cm2Current deposits
10s, then -0.5mA/cm2Electric current reversely continue 5s, repeat 60 times, obtain being deposited on the MnO on three-dimensional grapheme2Nanometer
Particle size is about 20nm.
In 100 DEG C of dry 1h after cleaning, metal nanometer line/three-dimensional grapheme-MnO is obtained2Nano particle composite material.It
Afterwards using electrochemical oxidation process in above-mentioned metal nanometer line/three-dimensional grapheme-MnO2Continue to deposit on nano particle composite material
PANI film, with metal nanometer line/three-dimensional grapheme-MnO2Nano particle composite material preparation work electrode, platinum electrode are pair
Electrode, Ag/AgCl electrode are auxiliary electrode, and electrolyte is 0.1M aniline, 0.1M LiClO4It is molten in propene carbonate (PC)
Liquid polymerize PANI by cyclic voltammetry with the rate of 50mV/s on the surface of graphene, polymerize after 50 circulations and complete, use PC
Then electrolyte solvent cleaning sample surface uses ethyl alcohol cleaning sample surface, metal nanometer line/three-dimensional can be obtained after dry
Graphene-MnO2Nano particle-PANI nano thin-film composite supercapacitor electrode.Electrode is prepared with the composite material,
By electrochemical workstation, using linear voltammetry (50mV/s), platinum electrode of the same area is used as to electrode, with 6M
KOH aqueous solution makees electrolyte, carries out electrochemical property test, and test result is as shown in Figure 7,8.
Fig. 7 is provided in this embodiment based on nano wire/three-dimensional grapheme-MnO2Nano particle-PANI nano thin-film is multiple
The electrode of super capacitor volt-ampere test result figure of condensation material preparation；Fig. 8 is that same electrode material carries out 200,000 volt-ampere tests
Result afterwards.Fig. 8's the result shows that, the present embodiment be based on three-dimensional grapheme-MnO2Nano particle-PANI nano thin-film composite wood
After the electrode of material carries out the test of 200,000 volt-ampere, still remain initially be more than 95% capacitance, this is very outstanding follows
Ring performance, this will be attributed to the PANI nano thin-film of package to internal MnO2Nano particle and three-dimensional grapheme material play
Protective effect.
Figure 10 illustrates three-dimensional grapheme-nano thin-film composite material possibility structure, and nano thin-film attachment is wrapped in three
On the graphene film for tieing up grapheme material；Figure 11 illustrates three-dimensional grapheme-nano particle-nano thin-film composite material
Possible structure, nano particle are attached on the graphene film of three-dimensional grapheme material, and are formed and directly contacted, nano thin-film
Further Encapsulation nanoparticle and three-dimensional grapheme form protection to nano particle and three-dimensional grapheme.
3 carbon nanocoils of embodiment/three-dimensional grapheme-PANI nano thin-film composite material
Using copper sheet as substrate, using chemical vapour deposition technique (Chemical Vapor Deposition, abbreviation CVD method)
Produce carbon nanocoils array；Using plasma enhances chemical vapour deposition technique (Plasma Enhanced Chemical
Vapor Deposition, abbreviation PECVD), three-dimensional grapheme material is produced on carbon nanocoils array；In three-dimensional grapheme
Upper in-situ deposition MnO2Nano particle prepares carbon nanocoils/three-dimensional grapheme-MnO2Nano particle composite material, then received based on carbon
Rice noodles/three-dimensional grapheme-MnO2Nano particle composite material prepares electrode of super capacitor.
With CH4Gas is as presoma, the CH4The flow of gas is 10~1000sccm, and Cu adds in CVD reacting furnace
Aforementioned CH4 gas is introduced into CVD reacting furnace by heat to 850 DEG C, and carbon nanocoils array is grown in Cu substrate by CVD method,
Growth time is 5h, obtains the carbon nanocoils array that height is 10 μm.Then with CH4The plasma of gas as presoma,
Hydrogen and argon gas are as auxiliary gas, by CH4Mixed gas is formed after gas, hydrogen and argon gas mixing, wherein the CH4Gas
Volume ratio with the auxiliary gas is 1: 2, and the carbon nano-array of obtained Cu on piece is heated in PECVD reacting furnace
850℃.Foregoing mixed gas is introduced into PECVD reactor, growing three-dimensional graphene, life in Cu substrate by PECVD
Control for a long time is 1 minute, obtains carbon nanocoils/three-dimensional graphene composite material.With O2Plasma bombardment 10 minutes into
Row surface is modified, is activated using chemical method.
It is thin to continue deposition PANI on above-mentioned carbon nanocoils/three-dimensional graphene composite material using electrochemical oxidation process later
Film, using carbon nanocoils/three-dimensional graphene composite material as working electrode, platinum electrode is to electrode, and Ag/AgCl electrode is auxiliary
Electrode, electrolyte are 0.1M aniline, 0.1M LiClO4Solution in propene carbonate (PC), by cyclic voltammetry with
The rate of 50mV/s polymerize PANI on the surface of graphene, polymerize after 50 circulations and completes, uses PC electrolyte solvent cleaning sample
Then surface uses ethyl alcohol cleaning sample surface, carbon nanocoils/three-dimensional grapheme-PANI nano thin-film can be obtained after dry
Composite supercapacitor electrode.
Using the carbon nanocoils/three-dimensional grapheme-PANI nano thin-film as anode, lithium piece is cathode, LiPF6/EC+DMC
Lithium ion battery is assembled for electrolyte.It is tested at 0.1C~5C, test result is as shown in Figure 12,13.Wherein Figure 12 is charge and discharge
The relationship of piezoelectric voltage and capacity, it is seen that first charge-discharge capacity has been more than 600mAh/g, is also approached after 100 circulations
500mAh/g.Figure 13 is the relationship of charge and discharge number and electric current and capacity, it is seen that recycles, still retains close under 1A electric current
The capacity of 300mAh/g.
4 metal nanometer lines of embodiment/three-dimensional grapheme-Ni/Pt nano particle composite material
Nano wire is deposited using electrochemical process, to be coated with the alumina formwork of Ag film as substrate, AgNO3、CuSO4Or
HAuO4, mixed solution produce the nano wire of Ag, Cu or Au, then alumina formwork is removed using NaOH solution, obtains gold
Belong to the nano-wire array of Ag, Cu or Au.
Three-dimensional grapheme material using PECVD, in preparing nano linear array；It sinks in situ on three-dimensional grapheme material
Product Ni/Pt nano particle prepares metal nanometer line/three-dimensional grapheme-Ni/Pt nano particle composite material, then is based on the metal
Nano wire/three-dimensional grapheme-Ni/Pt nano particle composite material prepares electrode of super capacitor.
With CH4The plasma of gas is used as auxiliary gas as presoma, hydrogen and argon gas, by CH4Gas, hydrogen, nitrogen
Mixed gas is formed after gas and argon gas mixing, wherein the CH4The volume ratio of gas and the auxiliary gas is 1: 4, has been obtained
Metal nanometer line array 850 DEG C are heated in PECVD reacting furnace.Foregoing mixed gas is introduced into PECVD reactor, is led to
Cross PECVD growing three-dimensional graphene on metal nanometer line array, growth time control is 1 minute, obtain metal nanometer line/
Three-dimensional graphene composite material.With O210 minutes progress surfaces of plasma bombardment it is modified, activated using chemical method.
Ni/Pt nano particle is prepared using solvent-thermal method, 600mg nickel acetylacetonate is added in 60mL benzyl ether, after dissolution
8mL oleyl amine and 2.5mL tributyl phosphate is added, vacuumizes 1h at 100 DEG C after being sufficiently mixed, is passed through nitrogen later, with 10 DEG C/
The heating rate of min is warming up to 230 DEG C, is down to room temperature after reacting 15min, obtains Ni nano particle, and cleaning is dispersed in n-hexane
In it is spare, using the Ni nano particle as nucleus, prepare Ni/Pt nano particle, 120mg acetylacetone,2,4-pentanedione foil is dissolved in 20mL 1-
In octadecylene, 4mL oleyl amine and 2mL oleic acid is added, is heated to 100 DEG C, vacuumizes 1h, then pass to nitrogen, iron pentacarbonyl is added,
3 DEG C/min is warming up to 180 DEG C, reacts half an hour, is cooled to room temperature, obtains Ni/Pt nano particle, be dispersed in n-hexane after cleaning
In it is spare.
Using the aforementioned metal nanometer line/three-dimensional graphene composite material being prepared as working electrode, platinum electrode is pair
Electrode, Ni/Pt nanoparticulate dispersion are electrolyte, 10mA/cm2Current density electrophoretic deposition Ni/Pt nano particle to three
Graphene surface is tieed up, obtains metal nanometer line/three-dimensional grapheme-Ni/Pt nano particle composite material after electrophoresis 10min.Pass through
Electrochemical workstation, using above-mentioned composite material as working electrode, in O2-saturated 0.1M HClO4In with linear voltammetry
Test ORR polarization curve.Test result is as shown in figure 14.From the point of view of the result of Figure 14, three-dimensional grapheme-Ni/Pt nano particle
The curve of composite material is located at the right of commercialization Pt electrode, shows three-dimensional grapheme-Ni/Pt nano-particles reinforcement of the invention
Material catalytic performance is more preferable.Wherein, the three-dimensional grapheme-Ni/Pt nano particle composite material catalytic performance used for the first time is optimal,
With the increase of number of use, its catalytic performance gradually weakens, but using after 100,000 times, catalytic performance is still better than being commercialized
Pt electrode.
The above is only exemplary embodiment of the invention, protection scope and is not intended to limit the present invention, this hair
Bright protection scope is determined by the attached claims.
Claims (25)
1. a kind of nano wire/three-dimensional graphene composite material, including the three-dimensional graphite on nano-wire array, the nano-wire array
Alkene depends on multiple nano particles on the three-dimensional grapheme and/or at least one layer of nano thin-film.
2. nano wire/three-dimensional graphene composite material according to claim 1, which is characterized in that the nano wire/three-dimensional
Graphene composite material includes nano-wire array, the three-dimensional grapheme on the nano-wire array, depends on the three-dimensional graphite
The multiple nano particle and/or at least one layer of nano thin-film on alkene.
3. nano wire/three-dimensional graphene composite material according to claim 2, which is characterized in that the three-dimensional grapheme
It is attached to the nano-wire array completely or partially, the average length of nano wire is 100nm~200 μm, preferably 1~100 μm, excellent
Select 5~50 μm；Diameter average out to 1nm~1 μm of nano wire, preferably 10~100nm.
4. nano wire/three-dimensional graphene composite material according to claim 2, which is characterized in that the three-dimensional grapheme
It is attached to the nano-wire array completely or partially, the average-size of three-dimensional grapheme is 10nm~1000nm, preferably 50~
200nm。
5. nano wire/three-dimensional graphene composite material according to claim 2, which is characterized in that the multiple nanometer
Grain is attached on the three-dimensional grapheme, and at least one layer nano thin-film coats the multiple nano particle and the three-dimensional
Graphene.
6. nano wire/three-dimensional graphene composite material according to claim 2, which is characterized in that the multiple nanometer
At least part in grain is attached on the three-dimensional grapheme, the outermost layer nano thin-film of at least one layer nano thin-film
Coat the multiple nano particle, the three-dimensional grapheme and other layers of nano thin-film.
7. -6 described in any item nano wire/three-dimensional graphene composite materials according to claim 1, which is characterized in that described
Three-dimensional grapheme has porous structure, and average channel diameter is 10nm-200nm, preferably 20nm-100nm.
8. -6 described in any item nano wire/three-dimensional graphene composite materials according to claim 1, which is characterized in that described
If three-dimensional grapheme includes the dry plate multi-layer graphene and/or single-layer graphene irregularly to flock together.
9. nano wire/three-dimensional graphene composite material according to claim 8, which is characterized in that if more in the dry plate
In layer graphene and/or single-layer graphene, the carbon atom number of plies of every piece of graphite alkene is 1-10 layers, preferably 2-7 layers, preferably 3-6
Layer.
10. -6 described in any item nano wire/three-dimensional graphene composite materials according to claim 1, which is characterized in that described
Nanoparticle size is 1-100nm, preferably 2-50nm, preferably 3-30nm.
11. -6 described in any item nano wire/three-dimensional graphene composite materials according to claim 1, which is characterized in that described
The nano wire for being attached with three-dimensional grapheme includes the monodimension nanometer material of various forms and size, including carbon nanotube, carbon nanometer
Line, metal nanometer line, oxide nano thread, polymer nano rice noodles, sulfide nanometer linear, semiconductor nanowires, the carbon nanometer
Pipe includes single-walled nanotube, many walls nanotube；The metal nanometer line includes that Cu nano wire, Au nano wire, Ag nano wire, Ni receive
Rice noodles, Fe nano wire；The oxide nano thread includes transition metal oxide nano line, MnO2Nano wire, Mn3O4Nano wire,
MnO nano wire, NiO nanowire, Co3O4Nano wire, Fe2O3Nano wire, Fe3O4Nano wire, V2O5Nano wire, TiO2Nano wire, lithium
Oxide composite oxide nanowire, LiCoO2Nano wire, LiMnO2Nano wire, LiMn2O4Nano wire, LiFePO4Nano wire, Li4Ti5O12
Nano wire, nickle cobalt lithium manganate nano wire, nickel cobalt lithium aluminate nano wire；The semiconductor nanowires include Si nano wire, Ga nanometers
Line, ZnO nano particle；The polymer nano granules include polyaniline (PANI) nano wire, poly- 3,4- hexamethylene dioxy thiophene
(PEDOT) nano wire etc..
12. -6 described in any item nano wire/three-dimensional graphene composite materials according to claim 1, which is characterized in that described
Nano particle includes metal nanoparticle, non pinetallic nano particle, oxide nano particles, sulfide nanoparticle, semiconductor
Nano particle and/or polymer nano granules, the metal nanoparticle include Pt nano particle, Au nano particle, Ag nanometers
Particle；The non pinetallic nano particle includes S nano particle；The oxide nano particles include MnO2Nano particle, lithium are multiple
Close oxide nano particles, LiCoO2Nano particle, LiMnO2Nano particle, LiMn2O4Nano particle, LiFePO4Nano particle,
Li4Ti5O12Nano particle, nickle cobalt lithium manganate nano particle, nickel cobalt lithium aluminate nano particle, Mn3O4Nano particle, MnO nanometers
Grain, NiO nano particle, Co3O4Nano particle, Fe2O3Nano particle, Fe3O4Nano particle, V2O5Nano particle, TiO2Nanometer
Grain；The sulfide nanoparticle includes MoS2Nano particle；The semiconductor nanoparticle includes that Si nano particle, ZnO receive
Rice grain；The polymer nano granules include that polyaniline (PANI) nano particle, poly- 3,4- hexamethylene dioxy thiophene (PEDOT) are received
Rice grain.
13. -4 described in any item nano wire/three-dimensional graphene composite materials according to claim 1, which is characterized in that described
Each single-layer nano-film is at least one layer of nano thin-film with a thickness of 2-100nm, preferably 3-50nm, preferably 5-20nm.
14. -4 described in any item nano wire/three-dimensional graphene composite materials according to claim 1, which is characterized in that described
Nano thin-film includes metal nanometer thin film, non pinetallic nano film, oxide nano-film, sulfide nano thin-film, semiconductor
Nano thin-film and/or polymer nanocomposite film, the metal nanometer thin film include Pt nano thin-film, Au nano thin-film, Ag nanometers
Film；The non pinetallic nano film includes S nano thin-film；The oxide nano-film includes MnO2Nano thin-film, lithium are multiple
Close oxide nano-film, LiCoO2Nano thin-film, LiMnO2Nano thin-film, LiMn2O4Nano thin-film, LiFePO4Nano thin-film,
Li4Ti5O12Nano thin-film, nickle cobalt lithium manganate nano thin-film, nickel cobalt lithium aluminate nano thin-film, Mn3O4Nano thin-film, MnO nanometer thin
Film, NiO nano thin-film, Co3O4Nano thin-film, Fe2O3Nano thin-film, Fe3O4Nano thin-film, V2O5Nano thin-film, TiO2Nanometer thin
Film；The sulfide nano thin-film includes MoS2Nano thin-film；The semiconductor nanomembrane includes that Si nano thin-film, ZnO receive
Rice film；The polymer nanocomposite film includes that polyaniline (PANI) nano thin-film, poly- 3,4- hexamethylene dioxy thiophene (PEDOT) are received
Rice film.
15. -4 described in any item nano wire/three-dimensional graphene composite materials according to claim 1, which is characterized in that institute
It states three-dimensional grapheme to be surface modified by method physically or chemically, the surface modification is included in the three-dimensional grapheme
Cause the defects of vacancy, edge, in the three-dimensional grapheme surface doping atom, covalent on the three-dimensional grapheme surface in surface
It connects functional group, and/or is covalently attached high polymer monomer or macromolecule oligomer on the three-dimensional grapheme surface.
16. -6 described in any item nano wire/three-dimensional graphene composite materials according to claim 1, which is characterized in that described
Nano wire/three-dimensional graphene composite material mass specific area is in 400m2/ g or more.
17. a kind of electrode, described in any item nano wire/three-dimensional graphene composite materials including claim 1-16.
18. a kind of supercapacitor, including electrolyte, diaphragm, collector and electrode as claimed in claim 17.
19. a kind of battery, including electrode as claimed in claim 17.
20. a kind of lithium ion battery, including electrode as claimed in claim 17 are used as anode, wherein the nano particle includes
Lithium composite xoide nano particle, LiCoO2Nano particle, LiMnO2Nano particle, LiMn2O4Nano particle, LiFePO4Nanometer
Particle, Li4Ti5O12Nano particle, nickle cobalt lithium manganate nano particle, nickel cobalt lithium aluminate nano particle.
21. a kind of lithium ion battery, including electrode as claimed in claim 17 is as cathode, wherein the nano particle includes
Si nano particle, SiO2Nano particle, MnO2Nano particle, Mn3O4Nano particle, MnO nano particle, Li4Ti5O12Nanometer
Grain, Fe2O3Nano particle.
22. a kind of manufacturing method of nano wire/three-dimensional graphene composite material, comprising: using vapor deposition, ion sputtering, electricity
The methods of chemical deposition or atomic deposition grow the nano-wire array on substrate.Using plasma enhances chemical vapor deposition
Product (PECVD) method, using the mixing gas of carbonaceous gas and auxiliary gas as carbon source, the growing three-dimensional stone on nano-wire array
Black alkene；Multiple nano particles and/or at least one layer of nano thin-film are prepared on the three-dimensional grapheme surface；Wherein, the auxiliary
Gas includes argon gas and hydrogen.
23. according to described in any item methods of claim 22-23, which is characterized in that the carbonaceous gas and auxiliary gas
Mixing gas pressure be 0.01-500Pa, preferably 150-300Pa, further preferably 200-250Pa.
24. according to method described in claim 21-23, which is characterized in that prepare multiple receive on the three-dimensional grapheme surface
Rice grain and/or at least one layer of nano thin-film include: by Directly depositing, electrochemical deposition method, wet chemistry method sedimentation, gas
The methods of phase sedimentation or atom deposition method prepare multiple nano particles on the three-dimensional grapheme surface and/or at least one layer is received
Rice film.
25. according to described in any item methods of claim 22-24, which is characterized in that further include activation step, by described
Activation step forms a large amount of micropores on graphene sheet layer, having a size of 0.5~5nm, preferably 1~3nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110482519A (en) * | 2019-09-19 | 2019-11-22 | 西南交通大学 | A kind of material with carbon superstructure, preparation method and application |
| CN112516927A (en) * | 2020-11-09 | 2021-03-19 | 安徽宇航派蒙健康科技股份有限公司 | Preparation method of three-dimensional graphene-nanowire hybrid aerogel |
| CN112928346A (en) * | 2021-01-22 | 2021-06-08 | 佛山仙湖实验室 | Preparation method and application of polymer-containing nanowire composite film material |
| CN113253534A (en) * | 2021-05-13 | 2021-08-13 | 吉林大学 | Electrochromic device and manufacturing method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811690A (en) * | 2009-02-24 | 2010-08-25 | 国家纳米科学中心 | Method for forming carbon composite structure by using carbon nano tube and graphene |
| CN102765713A (en) * | 2012-08-16 | 2012-11-07 | 西南石油大学 | Fast preparation method for carbon nano tube/ graphene sandwich structure mateirals |
| CN103153843A (en) * | 2010-12-30 | 2013-06-12 | 海洋王照明科技股份有限公司 | Graphene ramification-carbon nanotube composite material and preparation method thereof |
| TWI452012B (en) * | 2011-03-29 | 2014-09-11 | Hon Hai Prec Ind Co Ltd | Graphene-carbon nanotube film structure |
| TWI469411B (en) * | 2012-07-13 | 2015-01-11 | Hon Hai Prec Ind Co Ltd | Method for making thin film lithium ion battery |
| CN104577077A (en) * | 2013-10-16 | 2015-04-29 | 国家纳米科学中心 | Silicon-carbon nanocomposite film, preparation method and application thereof and lithium ion battery |
| CN105174268A (en) * | 2015-09-21 | 2015-12-23 | 中国科学院上海微***与信息技术研究所 | Nanowire and graphene composite material and preparation method thereof |
| CN105405682A (en) * | 2015-12-24 | 2016-03-16 | 广州墨储新材料科技有限公司 | Fabrication method of PEDOT:PSS-coated nano MnO<2>-based graphene nano wall electrode |
| CN106548876A (en) * | 2015-09-22 | 2017-03-29 | 南京绿索电子科技有限公司 | The carbon nano pipe array of superficial oxidation/graphene/manganese dioxide composite material electrode and its preparation method and application |
| CN106953098A (en) * | 2017-04-06 | 2017-07-14 | 重庆大学 | A kind of high-capacity and long-life lead carbon battery negative pole and preparation method |
| CN107134504A (en) * | 2017-04-01 | 2017-09-05 | 昆明理工大学 | A kind of preparation method of nano silicon-based graphene solar cell |
-
2018
- 2018-03-09 CN CN201810256899.1A patent/CN110247028A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811690A (en) * | 2009-02-24 | 2010-08-25 | 国家纳米科学中心 | Method for forming carbon composite structure by using carbon nano tube and graphene |
| CN103153843A (en) * | 2010-12-30 | 2013-06-12 | 海洋王照明科技股份有限公司 | Graphene ramification-carbon nanotube composite material and preparation method thereof |
| TWI452012B (en) * | 2011-03-29 | 2014-09-11 | Hon Hai Prec Ind Co Ltd | Graphene-carbon nanotube film structure |
| TWI469411B (en) * | 2012-07-13 | 2015-01-11 | Hon Hai Prec Ind Co Ltd | Method for making thin film lithium ion battery |
| CN102765713A (en) * | 2012-08-16 | 2012-11-07 | 西南石油大学 | Fast preparation method for carbon nano tube/ graphene sandwich structure mateirals |
| CN104577077A (en) * | 2013-10-16 | 2015-04-29 | 国家纳米科学中心 | Silicon-carbon nanocomposite film, preparation method and application thereof and lithium ion battery |
| CN105174268A (en) * | 2015-09-21 | 2015-12-23 | 中国科学院上海微***与信息技术研究所 | Nanowire and graphene composite material and preparation method thereof |
| CN106548876A (en) * | 2015-09-22 | 2017-03-29 | 南京绿索电子科技有限公司 | The carbon nano pipe array of superficial oxidation/graphene/manganese dioxide composite material electrode and its preparation method and application |
| CN105405682A (en) * | 2015-12-24 | 2016-03-16 | 广州墨储新材料科技有限公司 | Fabrication method of PEDOT:PSS-coated nano MnO<2>-based graphene nano wall electrode |
| CN107134504A (en) * | 2017-04-01 | 2017-09-05 | 昆明理工大学 | A kind of preparation method of nano silicon-based graphene solar cell |
| CN106953098A (en) * | 2017-04-06 | 2017-07-14 | 重庆大学 | A kind of high-capacity and long-life lead carbon battery negative pole and preparation method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110482519A (en) * | 2019-09-19 | 2019-11-22 | 西南交通大学 | A kind of material with carbon superstructure, preparation method and application |
| CN112516927A (en) * | 2020-11-09 | 2021-03-19 | 安徽宇航派蒙健康科技股份有限公司 | Preparation method of three-dimensional graphene-nanowire hybrid aerogel |
| CN112516927B (en) * | 2020-11-09 | 2022-06-28 | 安徽宇航派蒙健康科技股份有限公司 | Preparation method of three-dimensional graphene-nanowire hybrid aerogel |
| CN112928346A (en) * | 2021-01-22 | 2021-06-08 | 佛山仙湖实验室 | Preparation method and application of polymer-containing nanowire composite film material |
| CN113253534A (en) * | 2021-05-13 | 2021-08-13 | 吉林大学 | Electrochromic device and manufacturing method thereof |
| CN113253534B (en) * | 2021-05-13 | 2022-07-26 | 吉林大学 | Electrochromic device and manufacturing method thereof |
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