CN110364682A - A kind of three-dimensional grapheme microballoon composite material - Google Patents
A kind of three-dimensional grapheme microballoon composite material Download PDFInfo
- Publication number
- CN110364682A CN110364682A CN201810336265.7A CN201810336265A CN110364682A CN 110364682 A CN110364682 A CN 110364682A CN 201810336265 A CN201810336265 A CN 201810336265A CN 110364682 A CN110364682 A CN 110364682A
- Authority
- CN
- China
- Prior art keywords
- microballoon
- thin
- film material
- core
- dimensional grapheme
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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 three-dimensional grapheme microballoon composite material including microballoon core, depends on the three-dimensional grapheme spherical shell on the microballoon core, and/or depends at least one layer of thin-film material on the three-dimensional grapheme spherical shell.The three-dimensional grapheme microballoon composite material is combined together by graphene and by the microballoon nuclear material that various heterogeneities, different size materials are constituted, the advantages of when sufficiently combining above-mentioned different materials as electrode material, mutual collaboration conduct is relied on simultaneously, overcomes defect when every kind of material is used alone.
Description
Technical field
This disclosure relates to a kind of three-dimensional grapheme microballoon 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 three-dimensional grapheme microballoon composite material, including microballoon core, depend on it is described micro-
Three-dimensional grapheme spherical shell on ball, and/or depend at least one layer of thin-film material on the three-dimensional grapheme spherical shell.
In one embodiment, for example, the three-dimensional grapheme microballoon composite material include microballoon core, depend on it is described
Three-dimensional grapheme spherical shell on microballoon core, and/or depend at least one layer of thin-film material on the three-dimensional grapheme spherical shell.
In one embodiment, for example, the three-dimensional grapheme spherical shell is on the microballoon core, three-dimensional grapheme spherical shell
Fully and partially coat the microballoon core.
In one embodiment, for example, at least one layer of thin-film material depended on the three-dimensional grapheme spherical shell is complete
Fully or partially coat the three-dimensional grapheme spherical shell or microballoon core.
In one embodiment, for example, depending at least one layer of thin-film material on the three-dimensional grapheme spherical shell
Outermost layer membrane materials coat the three-dimensional grapheme spherical shell or microballoon core and other layer membrane materials completely or partially.
In one embodiment, for example, the microballoon core can by metal material, oxide material, nonmetallic materials,
One of semiconductor material, carbon material, high-molecular organic material or the compound composition of multiple material.
In one embodiment, preferably 200nm-5 μm, excellent for example, the size of the microballoon core is 100nm-10 μm
Select 500nm-1 μm.
In one embodiment, for example, the microballoon core can have porous structure, average channel diameter is 0-
50nm, preferably 10nm-40nm, preferably 20nm-30nm.
In one embodiment, for example, the three-dimensional grapheme spherical shell include irregularly flock together it is several
Piece graphene nanometer sheet.
In one embodiment, for example, in several graphene nanometer sheets, every piece of graphite alkene nanometer sheet
With a thickness of 0.3-3nm, preferably 1-2nm.
In one embodiment, for example, the three-dimensional grapheme spherical shell has porous structure, average channel diameter is 5-
200nm, preferably 20nm-50nm.
In one embodiment, for example, the graphene nanometer sheet is having a size of 1-100nm, preferably 2-50nm, preferably
3-30nm。
In one embodiment, for example, each single thin film material thickness is 2- in at least one layer thin-film material
50nm, preferably 3-30nm, preferably 5-20nm.
In one embodiment, for example, the microballoon core include metallic microspheres core, it is oxidate microspheres core, nonmetallic micro-
Ball, semiconductor microactuator ball, carbosphere and/or polymer microballoon core, the metallic microspheres core include Sn microballoon core, Pt microballoon
Core, Au microballoon core, Ag microballoon core, Cu microballoon core, Ni microballoon core；The nonmetallic microballoon core includes S microballoon core；The oxide
Microballoon core includes SnO2Microballoon core, MnO2Microballoon core, lithium composite xoide microballoon core, Li4Ti5O12Microballoon core, nickle cobalt lithium manganate are micro-
Ball, nickel cobalt lithium aluminate microballoon core, Mn3O4Microballoon core, MnO microballoon core, NiO microballoon core, Co3O4Microballoon core, Fe2O3Microballoon core,
Fe3O4Microballoon core, V2O5Microballoon core, TiO2Microballoon core；The semiconductor microactuator ball includes Si microballoon core, ZnO microsphere core；It is described poly-
Closing object microballoon core includes polyaniline (PANI) microballoon core, poly- 3,4- hexamethylene dioxy thiophene (PEDOT) microballoon core etc..
In one embodiment, for example, the thin-film material includes metallic film material, nonmetal film material, oxygen
Compound thin-film material, sulfide film material, semiconductor film material and/or polymer thin-film material, the metal foil membrane material
Material includes Sn thin-film material, Pt thin-film material, Au thin-film material, Ag thin-film material；The nonmetal film material includes S thin
Membrane material；The oxide film material includes SnO2Thin-film material, MnO2Thin-film material, lithium composite xoide thin-film material,
LiCoO2Thin-film material, LiMnO2Thin-film material, LiMn2O4Thin-film material, LiFePO4Thin-film material, Li4Ti5O12Thin-film material,
Nickle cobalt lithium manganate thin-film material, nickel cobalt lithium aluminate thin-film material, Mn3O4Thin-film material, MnO thin-film material, NiO thin-film material,
Co3O4Thin-film material, Fe2O3Thin-film material, Fe3O4Thin-film material, V2O5Thin-film material, TiO2Thin-film material；The sulfide is thin
Membrane material includes MoS2Thin-film material；The semiconductor film material includes Si thin-film material, ZnO film material；The polymerization
Object thin-film material includes polyaniline (PANI) thin-film material, poly- 3,4- hexamethylene dioxy thiophene (PEDOT) thin-film material.
In one embodiment, for example, passing through to the three-dimensional grapheme nanometer sheet for constituting three-dimensional grapheme spherical shell
Method physically or chemically is surface modified, and the surface modification includes causing sky in the three-dimensional grapheme nanometer sheet
The defects of position, edge, foreign atom, the connection official in the three-dimensional grapheme nanometer sheet in the three-dimensional grapheme nanometer sheet
It can group, and/or connection high polymer monomer or macromolecule oligomer in the three-dimensional grapheme nanometer sheet.
The embodiment of the present invention provides a kind of negative electrode, including above-mentioned three-dimensional grapheme microballoon composite material as lithium
Ion battery cathode material.
The embodiment of the present invention provides a kind of anode electrode, is added to including above-mentioned three-dimensional grapheme microballoon composite material
In anode material for lithium-ion batteries.
The embodiment of the present invention provides a kind of lithium ion battery, including above-mentioned electrode as cathode, wherein the film
Material includes conducting polymer thin film, C film, sull, metallic film, semiconductive thin film.
The embodiment of the present invention provides a kind of lithium ion battery, including above-mentioned electrode as anode, wherein the film
Material includes conducting polymer thin film, C film, sull, metallic film, semiconductive thin film.
The embodiment of the present invention provides a kind of manufacturing method of three-dimensional grapheme microballoon composite material, comprising: using etc. from
The method that daughter enhances chemical vapor deposition (PECVD) or chemical vapor deposition, with the mixed air of carbonaceous gas and auxiliary gas
Body is as gas source, by metal material, oxide material, nonmetallic materials, semiconductor material, carbon material, high-molecular organic material
One of or the compound composition of multiple material microballoon core as substrate, prepare three-dimensional grapheme microballoon；In the three-dimensional graphite
Alkene microsphere surface deposits at least one layer of thin-film material；Wherein, the auxiliary gas includes argon gas and hydrogen.
In one embodiment, for example, depositing at least one layer of thin-film material in the three-dimensional grapheme microsphere surface
Method includes: by Directly depositing, electrochemical deposition method, wet chemistry method sedimentation, vapour deposition process etc..
In one embodiment, for example, the carbonaceous gas includes CH4, C2H2, C2H4。
In one embodiment, for example, further including activation step, by the activation step, in graphene nanometer sheet
A large amount of micropores are formed on layer, having a size of 0.5~4nm, preferably 1~2nm.
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 the schematic diagram for the three-dimensional grapheme microballoon composite material that one embodiment of the invention provides
The random graphene nanometer sheet to flock together in the graphene spherical shell that Fig. 2 provides for one embodiment of the invention
Schematic diagram；
The random graphene nanometer sheet to flock together in the graphene spherical shell that Fig. 3 provides for one embodiment of the invention
Schematic diagram；
Fig. 4 is the lithium ion battery for the three-dimensional grapheme microballoon-PANI film composite material that one embodiment of the invention provides
The capacity and multiplying power, the relational graph of cycle-index of electrode；
Fig. 5 is the lithium ion battery for the three-dimensional grapheme microballoon-PANI film composite material that one embodiment of the invention provides
The capacity of electrode and the relational graph of cycle-index；
Fig. 6 is the three-dimensional grapheme microballoon-PANI film-NCM composite material lithium-ion electric that one embodiment of the invention provides
The capacity and multiplying power, the relational graph of cycle-index of pond electrode；
Fig. 7 is the three-dimensional grapheme microballoon-PANI film-NCM composite material lithium-ion electric that one embodiment of the invention provides
The capacity of pond electrode and the relational graph of cycle-index.
Fig. 1 is the schematic diagram of the random graphene nanometer sheet to flock together in graphene spherical shell of the invention.(show
It is intended to not represent the concrete shape and dimension scale of graphene spherical shell, nanometer sheet and microballoon core, practical graphene spherical shell, nanometer
Piece coats microballoon core completely or partially, and shape and size are determined by growing specific growth parameter(s)).Fig. 2,3 are in graphene spherical shell
The schematic diagram of the random graphene nanometer sheet to flock together.The random row of graphene nanometer sheet of Fig. 2,3 visible microballoon cores
Column form 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 nanometer sheet has good electric conductivity and high-specific surface area.But also there is disadvantage, the stone of commonsense method preparation
Black alkene nanometer sheet is not three-dimensional material, need under high pressure electrode pressing with keep electrode structure stablize, be easy to happen in the process
Phenomenon is stacked, material specific surface area and ionic conductivity is caused to decline.Therefore, develop suitable preparation method, be prepared with stabilization
The porous three-dimensional material of the graphene nanometer sheet of structure, and it is surface modified, combination electrode material is formed with other materials
Material is a kind of necessary measure.Thin-film material has good conductive, thermally conductive and chemical characteristic.But thin-film material is equally also difficult to
The device architecture of macroscopic view sizing is formed, and is also easy to destroy the microstructure of thin-film material in type-approval process, causes performance
Loss even disappears.
The present inventor is by using microballoon core as structural support and substrate, with graphene nanometer sheet porous three-dimensional material
Material, thin-film material are combined together, and the three-dimensional grapheme microballoon composite material being prepared sufficiently combines above-mentioned each material
Advantage, and the shortcomings that in turn avoid each material simultaneously.The three-dimensional grapheme microballoon composite material has the advantage that
1) microballoon nuclear skeleton specific surface area is high, less between graphene nanometer sheet thereon with stable three-dimensional structure
In the presence of reuniting and stacking, be conducive to the superior electrical performance for giving full play to graphene nanometer sheet.
2) by carrying out to three-dimensional grapheme microballoon composite material, surface is modified, and the surface modification is included in the three-dimensional
Foreign atom on the defects of causing vacancy, edge on graphene spherical shell, three-dimensional grapheme spherical shell, in the three-dimensional grapheme spherical shell
Upper connection functional group, and/or connection high polymer monomer or macromolecule oligomer on the three-dimensional grapheme spherical shell, can not break
In the case where bad three-dimensional structure, the hydrophily or lipophilicity of material are substantially improved, substantially increases aqueous or non-aqueous liquid
The infiltration of body in the material, so that the chemical activity of material and physical activity all greatly increase.
3) thin-film material is prepared on three-dimensional grapheme spherical shell, thin-film material wraps up porous three-dimensional material, greatly
Increase cyclicity, the durability of three-dimensional grapheme microballoon composite material.
4) by thin-film material deposition on three-dimensional grapheme spherical shell, thin-film material (micron order) in large scale has and three
The identical three-dimensional structure of graphene spherical shell is tieed up, solves the problems, such as that nano material is difficult to shape, facilitates nano material macro
A large amount of uses in sight；In addition, the close contact of the usual three-dimensional grapheme spherical shell microballoon core of nano material, greatly improves and receives
Macroscopical conductivity of rice material.
5) three-dimensional grapheme spherical shell 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 right side, while flake structure and meso-hole structure are provided, increase the application range of material.
In conclusion the present invention perfectly combines the materials such as graphene nanometer sheet, porous microsphere substrate, thin-film material
Every advantage, and successfully overcome a variety of materials be used alone when the shortcomings that and deficiency, while keeping nanometer size effect
So that the size of composite material is reached hundreds of microns, nano-scale characteristic, effective solution have been effectively kept under macro-size
Previous nano material macro-scale using when lose nano material characteristic the problem of.The composite material can be applied to energy storage material
The fields such as material (such as secondary cell), chemical catalysis, photocatalysis and biomaterial, are a kind of a new generations for having broad prospect of application
Nanocomposite.
1 three-dimensional grapheme microballoon-PANI film composite material of embodiment
Substrate is done with silicon dioxide microsphere (1 μm), using PECVD, produces three-dimensional grapheme micro-sphere material；In three-dimensional stone
PANI thin-film material is deposited on black alkene microballoon, prepares three-dimensional grapheme microballoon-PANI film composite material, then with the composite wood
Electrode assembling lithium ion battery is made in material.
With CH4The plasma of gas is used as auxiliary gas as presoma, hydrogen and argon gas, by CH4Gas, hydrogen and
Mixed gas is formed after argon gas mixing, wherein the CH4The volume ratio of gas and the auxiliary gas is 10: 1-1: 5, by dioxy
SiClx microballoon is heated to 900 DEG C in PECVD reacting furnace.By PECVD on silicon dioxide microsphere growing three-dimensional graphene
Spherical shell, growth time control are 30 minutes, obtain the dimension graphene microballoon that radius is 10 μm.With O2Plasma bombardment 10
Minute, it is activated using chemical method.
Polyaniline (PANI) film is deposited, aniline is dissolved in 1M HCl solution, is made into the solution of concentration 0.3M, quickly stirs
It mixes and rapidly joins the 1M HCl solution with the ammonium peroxydisulfate of aniline molar ratio 1: 4, by aforementioned dimension graphene microballoon after mixing
Material is added in reaction solution and is stirred overnight at room temperature, is washed afterwards with water, ethyl alcohol and hexane.Three-dimensional graphite is obtained after drying
Alkene microballoon-PANI film composite material.
Anode is made in dimension graphene microballoon-PANI film composite material, lithium piece is cathode, LiPF6/ EC+DMC is electricity
It solves liquid and assembles lithium ion battery.It is tested at 0~3V, test result is as shown in Figure 4,5.Wherein Fig. 4 is charging and discharging currents density
With the relationship of specific capacity, it is seen that under 500mA/g current density, specific capacity can reach 500mAh/g.Fig. 5 is charge and discharge number
With the relationship of specific capacity, 500mA/g is recycled after 200mA/g activation one is enclosed, it is seen that 100 times circulating content amount is maintained at 96%.
2 microballoon core-PANI-NCM composite material of embodiment
Substrate is done with Cu microballoon (20 μm), using PECVD, produces three-dimensional grapheme microballoon-material；In Cu microballoon core
Deposited on materials PANI thin-film material prepares three-dimensional grapheme microballoon-PANI film composite material, then mixed with positive electrode NCM
It closes, obtains microballoon core-PANI-NCM composite material, electrode assembling lithium ion battery is made with the composite material.
With CH4The plasma of gas is used as auxiliary gas as presoma, hydrogen and argon gas, by CH4Gas, hydrogen and
Mixed gas is formed after argon gas mixing, wherein the CH4The volume ratio of gas and the auxiliary gas is 10: 1-1: 5, and Cu is micro-
Ball is heated to 800 DEG C in PECVD reacting furnace.By PECVD in substrate growing three-dimensional graphene spherical shell, growth time
Control is 60 minutes, obtains the three-dimensional grapheme microballoon that radius is 50 μm.With O2Plasma bombardment 10 minutes, use chemistry
Method is activated.
Polyaniline (PANI) film is deposited, aniline is dissolved in 1M HCl solution, is made into the solution of concentration 0.3M, quickly stirs
It mixes and rapidly joins the 1M HCl solution with the ammonium peroxydisulfate of aniline molar ratio 1: 4, aforementioned microsphere core is added instead after mixing
It answers in liquid and is stirred overnight at room temperature, washed afterwards with water, ethyl alcohol and hexane.It is thin that three-dimensional grapheme-PANI is obtained after drying
Film composite material.
Ball after the NCM nano particle of purchase is mixed with the aforementioned three-dimensional grapheme-PANI film composite material prepared
Mill handles (three-dimensional grapheme-PANI film composite material accounts for the 1~10% of gross mass), obtains three-dimensional grapheme-PANI film-
Electrode assembling lithium ion battery is made in the composite material by NCM composite material.
Using the composite material as anode, lithium piece is cathode, LiPF6/ EC+DMC is that electrolyte assembles lithium ion battery.?
It is tested under 0.1~5C, test result is as shown in Figure 6,7.Wherein Fig. 6 is the relationship of charging and discharging currents and specific capacity, it is seen that under 1C
Charge/discharge capacity is maintained at 120mAh/g, remains with 90mAh/g at 5C.Fig. 7 is charge and discharge number and specific capacity
Relationship, 1C is recycled after 0.1C activation for the first time, it is seen that 77% capacity is remained after 100 times.
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 (24)
1. a kind of three-dimensional grapheme microballoon composite material, including microballoon core, three-dimensional grapheme ball on the microballoon core is depended on
Shell, and/or depend at least one layer of thin-film material on the three-dimensional grapheme spherical shell.
2. three-dimensional grapheme microballoon composite material according to claim 1, which is characterized in that the three-dimensional grapheme microballoon
Composite material includes microballoon core, depends on the three-dimensional grapheme spherical shell on the microballoon core, and/or depend on the three-dimensional graphite
At least one layer of thin-film material on alkene spherical shell.
3. three-dimensional grapheme microballoon composite material according to claim 2, which is characterized in that the three-dimensional grapheme spherical shell
On the microballoon core, three-dimensional grapheme spherical shell fully and partially coats the microballoon core.
4. three-dimensional grapheme microballoon composite material according to claim 2, which is characterized in that depend on the three-dimensional graphite
At least one layer of thin-film material on alkene spherical shell coats the three-dimensional grapheme spherical shell or microballoon core completely or partially.
5. three-dimensional grapheme microballoon composite material according to claim 2, which is characterized in that depend on the three-dimensional graphite
The outermost layer membrane materials of at least one layer of thin-film material on alkene spherical shell coat completely or partially the three-dimensional grapheme spherical shell or
Microballoon core and other layer membrane materials.
6. three-dimensional grapheme microballoon composite material according to claim 2, which is characterized in that the microballoon core can be by gold
Belong to one of material, oxide material, nonmetallic materials, semiconductor material, carbon material, high-molecular organic material or a variety of materials
Expect compound composition.
7. three-dimensional grapheme microballoon composite material according to claim 2, which is characterized in that the size of the microballoon core is
100nm-10 μm, preferably 200nm-5 μm, preferably 500nm-1 μm.
8. -5 described in any item three-dimensional grapheme microballoon composite materials according to claim 1, which is characterized in that the microballoon
Core can have porous structure, and average channel diameter is 0-50nm, preferably 10nm-40nm, preferably 20nm-30nm.
9. -5 described in any item three-dimensional grapheme microballoon composite materials according to claim 1, which is characterized in that the three-dimensional
Graphene spherical shell includes several graphene nanometer sheets irregularly to flock together.
10. three-dimensional grapheme microballoon composite material according to claim 9, which is characterized in that in several graphite
In alkene nanometer sheet, every piece of graphite alkene nanometer sheet with a thickness of 0.3-3nm, preferably 1-2nm.
11. -5 described in any item three-dimensional grapheme microballoon composite materials according to claim 1, which is characterized in that described three
Tieing up graphene spherical shell has porous structure, and average channel diameter is 5-200nm, preferably 20nm-50nm.
12. -5 described in any item three-dimensional grapheme microballoon composite materials according to claim 1, which is characterized in that the stone
Black alkene nanometer sheet is having a size of 1-100nm, preferably 2-50nm, preferably 3-30nm.
13. -5 described in any item three-dimensional grapheme microballoon composite materials according to claim 1, which is characterized in that it is described extremely
Each single thin film material thickness is 2-50nm, preferably 3-30nm, preferably 5-20nm in few thin film material layer.
14. -5 described in any item three-dimensional grapheme microballoon composite materials according to claim 1, which is characterized in that described micro-
Ball includes that metallic microspheres core, oxidate microspheres core, nonmetallic microballoon core, semiconductor microactuator ball, carbosphere and/or polymer are micro-
Ball, the metallic microspheres core include Sn microballoon core, Pt microballoon core, Au microballoon core, Ag microballoon core, Cu microballoon core, Ni microballoon core；
The nonmetallic microballoon core includes S microballoon core；The oxidate microspheres core includes SnO2Microballoon core, MnO2Microballoon core, lithium composite oxygen
Compound microballoon core, Li4Ti5O12Microballoon core, nickle cobalt lithium manganate microballoon core, nickel cobalt lithium aluminate microballoon core, Mn3O4Microballoon core, MnO are micro-
Ball, NiO microballoon core, Co3O4Microballoon core, Fe2O3Microballoon core, Fe3O4Microballoon core, V2O5Microballoon core, TiO2Microballoon core；Described half
Conductor microballoon core includes Si microballoon core, ZnO microsphere core；The polymer microballoon core includes polyaniline (PANI) microballoon core, poly- 3,
4- hexamethylene dioxy thiophene (PEDOT) microballoon core etc..
15. -5 described in any item three-dimensional grapheme microballoon composite materials according to claim 1, which is characterized in that described thin
Membrane material includes metallic film material, nonmetal film material, oxide film material, sulfide film material, semiconductor film
Membrane material and/or polymer thin-film material, the metallic film material include Sn thin-film material, Pt thin-film material, Au film material
Material, Ag thin-film material；The nonmetal film material includes S thin-film material；The oxide film material includes SnO2Film
Material, MnO2Thin-film material, lithium composite xoide thin-film material, LiCoO2Thin-film material, LiMnO2Thin-film material, LiMn2O4It is thin
Membrane material, LiFePO4Thin-film material, Li4Ti5O12Thin-film material, nickle cobalt lithium manganate thin-film material, nickel cobalt lithium aluminate thin-film material,
Mn3O4Thin-film material, MnO thin-film material, NiO thin-film material, Co3O4Thin-film material, Fe2O3Thin-film material, Fe3O4Thin-film material,
V2O5Thin-film material, TiO2Thin-film material；The sulfide film material includes MoS2Thin-film material；The semiconductor film membrane material
Material includes Si thin-film material, ZnO film material；The polymer thin-film material includes polyaniline (PANI) thin-film material, poly- 3,
4- hexamethylene dioxy thiophene (PEDOT) thin-film material.
16. -5 described in any item three-dimensional grapheme microballoon composite materials according to claim 1, which is characterized in that described
The three-dimensional grapheme nanometer sheet for constituting three-dimensional grapheme spherical shell is surface modified by method physically or chemically, the surface
Modification includes the defects of causing vacancy, edge in the three-dimensional grapheme nanometer sheet, in the three-dimensional grapheme nanometer sheet
Foreign atom connects functional group in the three-dimensional grapheme nanometer sheet, and/or connects in the three-dimensional grapheme nanometer sheet
High polymer monomer or macromolecule oligomer.
17. a kind of negative electrode, described in any item three-dimensional grapheme microballoon composite material conducts including claim 1-16
Lithium ion battery negative material.
18. a kind of anode electrode, described in any item three-dimensional grapheme microballoon composite materials addition including claim 1-16
Into anode material for lithium-ion batteries.
19. a kind of lithium ion battery, including electrode as claimed in claim 17 is as cathode, wherein the thin-film material includes
Conducting polymer thin film, C film, sull, metallic film, semiconductive thin film.
20. a kind of lithium ion battery, including electrode as claimed in claim 18 are used as anode, wherein the thin-film material includes
Conducting polymer thin film, C film, sull, metallic film, semiconductive thin film.
21. a kind of manufacturing method of three-dimensional grapheme microballoon composite material, comprising: using plasma enhances chemical vapor deposition
(PECVD) or the method for chemical vapor deposition (CVD), using the mixing gas of carbonaceous gas and auxiliary gas as gas source, by gold
Belong to one of material, oxide material, nonmetallic materials, semiconductor material, carbon material, high-molecular organic material or a variety of materials
Expect that the microballoon core of compound composition as substrate, prepares three-dimensional grapheme microballoon；The three-dimensional grapheme microsphere surface deposit to
Few thin film material layer；Wherein, the auxiliary gas includes argon gas and hydrogen.
22. according to the method for claim 21, which is characterized in that deposit at least one in the three-dimensional grapheme microsphere surface
The method of layer membrane materials includes: by Directly depositing, electrochemical deposition method, wet chemistry method sedimentation, vapour deposition process etc..
23. according to the method for claim 21, which is characterized in that the carbonaceous gas includes CH4, C2H2, C2H4Deng.
24. according to described in any item methods of claim 21,22, which is characterized in that further include activation step, by described
Activation step forms a large amount of micropores on graphene nano lamella, having a size of 0.5~4nm, preferably 1~2nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810336265.7A CN110364682B (en) | 2018-04-11 | 2018-04-11 | Three-dimensional graphene microsphere composite material, and manufacturing method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810336265.7A CN110364682B (en) | 2018-04-11 | 2018-04-11 | Three-dimensional graphene microsphere composite material, and manufacturing method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110364682A true CN110364682A (en) | 2019-10-22 |
| CN110364682B CN110364682B (en) | 2022-06-24 |
Family
ID=68214703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810336265.7A Active CN110364682B (en) | 2018-04-11 | 2018-04-11 | Three-dimensional graphene microsphere composite material, and manufacturing method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110364682B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111883761A (en) * | 2020-08-05 | 2020-11-03 | 重庆信合启越科技有限公司 | Silicon graphene composite lithium battery negative electrode material and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102867650A (en) * | 2012-09-03 | 2013-01-09 | 中国科学院大连化学物理研究所 | High-magnification supercapacitor composite electrode material and preparation method thereof |
| CN103121672A (en) * | 2013-03-20 | 2013-05-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene oxide microsphere and graphene microsphere and preparation methods thereof |
| US20140322608A1 (en) * | 2011-08-15 | 2014-10-30 | Purdue Research Foundation | Modified graphitic electrodes for electrochemical energy storage enhancement |
| CN104616717A (en) * | 2015-01-13 | 2015-05-13 | 浙江大学 | Composite conductive material of graphene film and metal nanometer structure and preparation method thereof |
| CN105390682A (en) * | 2015-12-08 | 2016-03-09 | 广东石油化工学院 | Preparation method for lithium iron phosphate microsphere/three-dimensional graphene composite electrode material and application of composite electrode material |
| US20170154701A1 (en) * | 2014-07-09 | 2017-06-01 | Daegu Gyeongbuk Institute Of Science And Technology | Metal nanowire having core-shell structure coated with graphene, and manufacturing method therefor |
| CN107004518A (en) * | 2014-11-17 | 2017-08-01 | 南洋理工大学 | Composite and preparation method thereof |
| CN107579239A (en) * | 2017-09-13 | 2018-01-12 | 山东大学 | A kind of graphene/solid electrolyte compound coating silicon composite cathode and preparation method thereof |
-
2018
- 2018-04-11 CN CN201810336265.7A patent/CN110364682B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140322608A1 (en) * | 2011-08-15 | 2014-10-30 | Purdue Research Foundation | Modified graphitic electrodes for electrochemical energy storage enhancement |
| CN102867650A (en) * | 2012-09-03 | 2013-01-09 | 中国科学院大连化学物理研究所 | High-magnification supercapacitor composite electrode material and preparation method thereof |
| CN103121672A (en) * | 2013-03-20 | 2013-05-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene oxide microsphere and graphene microsphere and preparation methods thereof |
| US20170154701A1 (en) * | 2014-07-09 | 2017-06-01 | Daegu Gyeongbuk Institute Of Science And Technology | Metal nanowire having core-shell structure coated with graphene, and manufacturing method therefor |
| CN107004518A (en) * | 2014-11-17 | 2017-08-01 | 南洋理工大学 | Composite and preparation method thereof |
| CN104616717A (en) * | 2015-01-13 | 2015-05-13 | 浙江大学 | Composite conductive material of graphene film and metal nanometer structure and preparation method thereof |
| CN105390682A (en) * | 2015-12-08 | 2016-03-09 | 广东石油化工学院 | Preparation method for lithium iron phosphate microsphere/three-dimensional graphene composite electrode material and application of composite electrode material |
| CN107579239A (en) * | 2017-09-13 | 2018-01-12 | 山东大学 | A kind of graphene/solid electrolyte compound coating silicon composite cathode and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111883761A (en) * | 2020-08-05 | 2020-11-03 | 重庆信合启越科技有限公司 | Silicon graphene composite lithium battery negative electrode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110364682B (en) | 2022-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ni et al. | Designed constitution of NiO/Ni nanostructured electrode for high performance lithium ion battery | |
| Wang et al. | Excellent stability of spinel LiMn2O4-based cathode materials for lithium-ion batteries | |
| Kim et al. | Effect of carbon coating on LiNi1/3Mn1/3Co1/3O2 cathode material for lithium secondary batteries | |
| Song et al. | Enhanced electrochemical properties of Li (Ni0. 4Co0. 3Mn0. 3) O2 cathode by surface modification using Li3PO4-based materials | |
| CN102958835B (en) | Submicron sized silicon powder with low oxygen content | |
| He et al. | Self-supported mesoporous FeCo2O4 nanosheets as high capacity anode material for sodium-ion battery | |
| CN105355908B (en) | Composite cathode material for lithium ion cell and preparation method thereof, cathode and lithium ion battery using the material | |
| Ren et al. | Enhanced electrochemical performance by size-dependent SEI layer reactivation of NiCo2O4 anodes for lithium ion batteries | |
| CN104733708B (en) | A kind of preparation method of the nickle cobalt lithium manganate composite of Surface coating LiFePO4 | |
| CN107845781B (en) | Negative electrode active material for lithium ion secondary battery, method for producing same, and lithium ion secondary battery | |
| CN108807862A (en) | A kind of silicon based composite material and preparation method thereof, negative material and lithium battery | |
| CN104247105B (en) | Comprise negative active core-shell material of porous silicon oxide carbon material compound and preparation method thereof | |
| CN109065858B (en) | Surface modified ternary positive electrode material, preparation method thereof and battery prepared from surface modified ternary positive electrode material | |
| Yuan et al. | Surfactant-assisted hydrothermal synthesis of V2O5 coated LiNi1/3Co1/3Mn1/3O2 with ideal electrochemical performance | |
| WO2011009231A1 (en) | Method for preparing carbon-coated positive material of lithium ion battery | |
| CN107180949A (en) | A kind of ternary system lithium battery anode and preparation method thereof | |
| CN108346520A (en) | Three-dimensional graphene composite material, its manufacturing method and application | |
| Wu et al. | Synthesis and electrochemical performance of SnO2–Fe2O3 composite as an anode material for Na-ion and Li-ion batteries | |
| Wang et al. | Morphology control and Na+ doping toward high-performance Li-rich layered cathode materials for lithium-ion batteries | |
| Cao et al. | Sodium vanadate nanowires@ polypyrrole with synergetic core-shell structure for enhanced reversible sodium-ion storage | |
| CN110350156A (en) | Negative electrode active material and lithium rechargeable battery including it | |
| CN104716307A (en) | Negative electrode active material, method for manufacturing the same, and lithium rechargable battery including the same | |
| Wang et al. | A microstructure engineered perovskite super anode with Li-storage life of exceeding 10,000 cycles | |
| Qiao et al. | Nanoneedle-assembled hollow α-Fe2O3 microflowers as Li-ion battery anode with high capacity and good temperature tolerance | |
| Ding et al. | Enhanced electrochemical performance of silicon monoxide anode materials prompted by germanium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 510623 Room 201, building B7, No. 11, Kaiyuan Avenue, Science City, Guangzhou high tech Industrial Development Zone, Guangdong Province Applicant after: Guangzhou Xi Ink Technology Co. Ltd. Address before: No. 30 building, 510623 Guangdong Fuli Yeston Guangzhou province Tianhe District Zhujiang New City, Huaxia Road 1803 Applicant before: Guangzhou Xi Ink Technology Co. Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |