CN108328611A - A kind of self-supporting redox graphene volume network material and preparation method thereof - Google Patents
A kind of self-supporting redox graphene volume network material and preparation method thereof Download PDFInfo
- Publication number
- CN108328611A CN108328611A CN201710302040.5A CN201710302040A CN108328611A CN 108328611 A CN108328611 A CN 108328611A CN 201710302040 A CN201710302040 A CN 201710302040A CN 108328611 A CN108328611 A CN 108328611A
- Authority
- CN
- China
- Prior art keywords
- self
- graphene
- supporting
- volume
- network material
- 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
- 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
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
- 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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
The present invention provides a kind of self-supporting redox graphenes to roll up network material and preparation method thereof, belongs to nano materials research field.Preparation method：Configure the mixed solution of graphene oxide dispersion and additive；Mixed solution is freeze-dried, unreduced graphene oxide volume network material is obtained；Unreduced graphene oxide volume network material is placed in protective gas atmosphere, the predetermined time is handled with predetermined temperature, the graphene oxide volume network material for obtaining the partial reduction of self-supporting or restoring completely；After the repeated washing that the partial reduction of self-supporting or the graphene oxide restored completely volume network material are carried out to predetermined extent, freeze-drying process is carried out；Obtain the self-supporting redox graphene volume network material containing low additive level.Its method have many advantages, such as it is simple and practicable, at low cost, can heavy industrialization prepare.The graphene roll material of preparation with complete self supporting structure, and has different coil diameters, has wide range of applications.
Description
Technical field
The present invention relates to technical field of nano material, more particularly to a kind of self-supporting redox graphene rolls up network material
And preparation method thereof.
Background technology
Graphene roll is the one-dimentional structure for being similar to radial unclosed carbon nanotube curled by graphene.It is this
Not only there are high electron mobility and high mechanical properties between graphene and the material of carbon nanotube, also have different from the two
Unique excellent electricity and mechanical property.This structure not only avoids graphene sheet layer and is easy to stack the problem of reuniting, and protects
Its larger specific surface area is held, and relative to the carbon nanotube with enclosed construction, the coiled structure of its lamella of graphene roll
Filled composite other materials is made it easier to, energy aspect has a wide range of applications valence in terms of ultracapacitor, lithium battery etc.
Value.Prepared by previous graphene roll, including arc discharge, high-energy ball milling, chemical method；First two contains due to being difficult to control in product
There are a large amount of graphite and agraphitic carbon so that graphene roll is difficult to detach.By using partial reduction graphite oxide in chemical method
Then alkene carries out freeze-drying and is allowed to form coil structure.The sample that above method obtains is usually the graphene roll powder disperseed
End cannot form the structure of self-supporting, while the above method cannot prepare graphene oxide volume, the volume of the graphene roll of preparation
Diameter leverages its application field generally in 1000nm hereinafter, its ingredient, structure, range scale are all restricted.
Therefore, a kind of simple and practicable, at low cost graphene roll network material of the preparation with self supporting structure how is designed
Expect significant.
Invention content
It is an object of the present invention to provide a kind of self-supporting redox graphene roll up network material preparation method, with
Solve the graphene roll prepared at present can only be reducing condition, be of limited application, and graphene roll is in powdered, graphite
The problems such as alkene coil diameter size is limited.It has many advantages, such as it is simple and practicable, at low cost, can heavy industrialization prepare.The present invention
Another purpose be to provide a kind of self-supporting redox graphene volume network material, with complete self supporting structure, and
With different coil diameters, have wide range of applications.
Particularly, a kind of self-supporting redox graphene provided by the invention rolls up network material, by the preceding preparation
Method is made, and self-supporting redox graphene rolls up network material, and by single layer, as dried layer redox graphene piece is connected with each other
And it is wound into redox graphene volume, it is mutually overlapping between redox graphene volume that be overlapped to form self-supporting three-dimensional porous
Network structure；The self-supporting redox graphene volume network material contains additive, has certain shape and flexibility, energy
It is enough to be processed or cut into arbitrary shape.
Further, the redox graphene volume can have different reducing degrees, the redox graphene
The constitution element of volume is carbon, hydrogen and oxygen, and the mass ratio of carbon and oxygen can regulate and control；
Optionally, the redox graphene volume can be unreduced graphene oxide volume；
Optionally, the redox graphene volume can be the redox graphene volume of partial reduction；
Optionally, the redox graphene volume can be the redox graphene volume restored completely, oxygen element
Content≤1%.
Further, the adjustable porosity of the redox graphene volume network material, preferably 10-99%.
Further, the density of the self-supporting redox graphene volume network material is adjustable, it is therefore preferable to be less than
10mg/cm3.The diameter of the redox graphene volume network material is adjustable, preferably 1nm-10 μm.
Further, the draw ratio of the redox graphene volume network materialIt is adjustable；
Preferably, the draw ratioMore than 5；
Wherein, the length of volumes of the L between two node of graphene roll network, d are the diameter of graphene roll.
The present invention also provides the preparation methods that a kind of self-supporting redox graphene rolls up network material, including following step
Suddenly：
S1, configure certain mass ratio graphene oxide dispersion and additive mixed uniformly mixed solution；
S2, the mixed solution is freeze-dried, obtains unreduced graphene oxide volume network material；
S3, the unreduced graphene oxide volume network material is placed in protective gas atmosphere handled with predetermined temperature it is pre-
It fixes time, the graphene oxide volume network material for obtaining the partial reduction of self-supporting or restoring completely；
S4, the repeated washing that the graphene oxide volume network material of the partial reduction of the self-supporting is carried out to predetermined extent
Afterwards, freeze-drying process is carried out；Obtain the self-supporting part redox graphene volume network material containing low additive level.
Further, in S1 steps, the mass ratio of the graphene oxide dispersion and additive is adjustable；
Preferably, the mass ratio is 1:10-10:1.
Further, in S1 steps, the additive can be one or more of monosaccharide and disaccharide or polysaccharide；
Preferably, the monosaccharide is one or more of glucose, fructose and galactolipin；
Preferably, the disaccharide is one or more of sucrose, lactose and maltose；
Preferably, the polysaccharide is one or more of glycogen and starch.
Further, in S3 steps, the protective gas is the mixed gas of inert gas, reducibility gas or both；
Preferably, the inert gas is nitrogen, argon gas or its mixed gas；
Preferably, the reducibility gas is hydrogen.
Further, in S3 steps, the predetermined time is more than 0.1h；The predetermined temperature is not less than 50 DEG C；
Preferably, the predetermined temperature is 50-1000 DEG C；
Preferably, the predetermined time is 1-30h.
Further, in S4 steps, the organic solvent that the repeated washing uses is unlimited, it is therefore preferable to ethyl alcohol, methanol and
One or more of acetone.
Redox graphene volume network structure material of a kind of self-supporting provided by the invention and preparation method thereof, has
Following advantageous effect：
(1) the redox graphene volume network structure material of the self-supporting can have different ingredients, i.e., completely not
The graphene oxide of reduction, partial reduction and the graphene oxide restored completely so that graphene oxide is in different also original states
The heap between graphene sheet layer caused by avoiding the modes such as tradition suction filtration using its larger specific surface area can be played under state
It is folded.It has wide range of applications, and can be applied to gas detector, such as sulfur dioxide gas bulk detector；It applies in energy storage, including
Lithium-sulfur cell, lithium silion cell and ultracapacitor etc..
(2) by the mass fraction of control additive, the material shows different graphene roll diameters, network aperture
Etc. structures, further expanded the application range of graphene roll；
A kind of preparation method of the redox graphene volume network structure material of self-supporting provided by the invention has behaviour
Make simple, at low cost, controllability is strong, can a large amount of preparations of industrialization the advantages that.
The preparation method of the redox graphene volume network structure material of a kind of self-supporting provided by the invention, using adding
Add the mixed solution of agent and graphene oxide dispersion, the oxidation of different reducing degrees is directly prepared by Freeze Drying Technique
Graphene roll self supporting structure.This configuration avoids the stackings of graphene, using the specific surface area that graphene is larger, while between volume
Mutual connection is good, and has certain flexibility, and different reducing degrees can be applied to no field.
According to the following detailed description of specific embodiments of the present invention in conjunction with the accompanying drawings, those skilled in the art will be brighter
The above and other objects, advantages and features of the present invention.
Description of the drawings
Some specific embodiments that the invention will be described in detail by way of example and not limitation with reference to the accompanying drawings hereinafter.
Identical reference numeral denotes same or similar component or part in attached drawing.It should be appreciated by those skilled in the art that these
What attached drawing was not necessarily drawn to scale.In attached drawing：
Fig. 1 is a kind of scanning of the redox graphene volume network structure material of self-supporting of one embodiment of the invention
The surface topography map (SEM figures) of electron microscope；
Fig. 2 is a kind of scanning of the redox graphene volume network structure material of self-supporting of one embodiment of the invention
The surface topography map (SEM figures) of electron microscope；
Fig. 3 is the surface topography map (SEM of the scanning electron microscope of self-supporting graphene roll prepared by non-doping
Figure)；
Fig. 4 is the preparation method of the redox graphene volume network structure material of the self-supporting of one embodiment of the invention
Flow diagram.
Specific implementation mode
The present invention is specifically described by embodiment, the present embodiment is served only for doing further the present invention
It is bright, it should not be understood as limiting the scope of the invention, other people make some non-intrinsically safes according to the content of foregoing invention
Change and adjustment, all belong to the scope of protection of the present invention.
Fig. 1 is a kind of scanning of the redox graphene volume network structure material of self-supporting of one embodiment of the invention
The surface topography map (SEM figures) of electron microscope；
Fig. 2 is a kind of scanning of the redox graphene volume network structure material of self-supporting of one embodiment of the invention
The surface topography map (SEM figures) of electron microscope.
As depicted in figs. 1 and 2, the present invention provides a kind of self-supporting redox graphenes to roll up network material.
Self-supporting redox graphene provided by the invention rolls up network material, by single layer as dried layer reduction-oxidation graphite
Alkene piece is connected with each other and is wound into redox graphene volume, mutually overlaps and is overlapped to form certainly between the redox graphene volume
Support three-dimensional porous network structure；The self-supporting redox graphene volume network material contains additive, has centainly
Shape and flexibility can be processed or cut into arbitrary shape.
Specifically, the redox graphene volume of self-supporting redox graphene volume network material can have different go back
Former degree.The constitution element of redox graphene volume is carbon, hydrogen and oxygen.The mass ratio of its carbon and oxygen can be added by controlling
The predetermined time and predetermined temperature of agent and mass fraction and heat treatment are regulated and controled.
In a specific embodiment, redox graphene volume can be unreduced graphene oxide volume.Not
The appearance for the self-supporting redox graphene volume network material that the graphene oxide volume of reduction is constituted is non-black, including pale brown
Color, brown.Its constitution element is carbon, hydrogen and oxygen.
In another particular embodiment of the invention, redox graphene volume can be the reduction-oxidation graphite of partial reduction
Alkene is rolled up；The appearance for the self-supporting redox graphene volume network material that the redox graphene volume of partial reduction is constituted is black
Color.Its constitution element is carbon, hydrogen and oxygen.The mass ratio of its carbon and oxygen element can regulate and control, preferably between 2-100.
In another particular embodiment of the invention, redox graphene volume can be the reduction-oxidation graphite restored completely
Alkene is rolled up.Its constitution element is carbon, hydrogen and oxygen, content≤1% of oxygen element.What the redox graphene volume restored completely was constituted
The appearance that self-supporting redox graphene rolls up network material is black.The mass ratio of its carbon and oxygen can regulate and control.Preferably, carbon
Oxygen mass ratio is 100 or more.
Self-supporting redox graphene rolls up the adjustable porosity of network material, preferably 10-99%.Optionally, described
Redox graphene rolls up network structure material porosity in 10-50%.Optionally, the redox graphene reel wire network knot
Structure material porosity is in 50-99%.
Further, the density of the self-supporting redox graphene volume network material is adjustable, it is therefore preferable to be less than
10mg/cm3。
Optionally, the density of the self-supporting redox graphene volume network material is adjustable, to be less than 0.5 mg/cm3。
Optionally, the density of the self-supporting redox graphene volume network material is adjustable, is 0.5-1 mg/cm3。
Optionally, the density of the self-supporting redox graphene volume network material is adjustable, is 1-5mg/cm3。
Optionally, the density of the self-supporting redox graphene volume network material is adjustable, is 5-10 mg/cm3.It can
The density of selection of land, the self-supporting redox graphene volume network material is adjustable, to be more than 10mg/cm3。
Further, the diameter of the redox graphene volume of self-supporting redox graphene volume network material is adjustable,
Preferably between 1nm-10 μm.
Optionally, the diameter of the redox graphene volume is between 1nm-200nm.
Optionally, the diameter of the redox graphene volume can be at 0.2-0.4 μm.
Optionally, the diameter of the redox graphene volume can be at 0.4-0.6 μm.
Optionally, the diameter of the redox graphene volume is at 0.6-0.8 μm.
Optionally, the diameter of the redox graphene volume is at 0.8-1 μm.
Optionally, the diameter of the redox graphene volume is at 1-5 μm.
Optionally, the diameter of the redox graphene volume is at 5-10 μm.
Further, the draw ratio of self-supporting redox graphene volume network material provided by the inventionIt is adjustable.It is preferred that
Ground, self-supporting redox graphene roll up the draw ratio of network materialMore than 5.Wherein, L be two node of graphene roll network it
Between volume length, d be graphene roll diameter.
Optionally, the draw ratio of self-supporting redox graphene volume network material is less than or equal to 20.
Optionally, the draw ratio of self-supporting redox graphene volume network material is in 20-500.
Optionally, the draw ratio of self-supporting redox graphene volume network material is more than 500.
Fig. 4 is the preparation method of the redox graphene volume network structure material of the self-supporting of one embodiment of the invention
Flow diagram.As shown in figure 4, a kind of redox graphene volume network structure material of self-supporting provided by the invention
Preparation method may comprise steps of in general manner：
S1, configure certain mass ratio graphene oxide dispersion and additive mixed uniformly mixed solution；
S2, the mixed solution is freeze-dried, obtains unreduced graphene oxide volume network material；
S3, the unreduced graphene oxide volume network material is placed in protective gas atmosphere handled with predetermined temperature it is pre-
It fixes time, the graphene oxide volume network material for obtaining the partial reduction of self-supporting or restoring completely；
S4, the repeated washing that the graphene oxide volume network material of the partial reduction of the self-supporting is carried out to predetermined extent
Afterwards, freeze-drying process is carried out；Obtain the self-supporting part redox graphene volume network material containing low additive level.
Specifically, in step sl, graphene oxide dispersion, which can lead to, is aoxidized through strong acid and is obtained, preparation side by graphite
Method can be Brodie methods, any one in Staudenmaier methods and Hummers methods.The preparation process of Hummers methods
Timeliness is relatively preferably and also relatively safer in preparation process, is current most common one kind.Hummers methods use the concentrated sulfuric acid
In potassium permanganate with powdered graphite is oxidized react after, obtain brown has derivative carboxylic acid group at edge and leads in the plane
To be the graphite flake of phenolic hydroxyl group and epoxy group, it is oxygen that this graphene layers can be vigorously stirred stripping through ultrasound or high shear
Graphite alkene, and formed stablize in water, the single-layer graphene oxide suspension of sundown.Preferably, oxidation of the invention
Graphene dispersing solution is prepared using Hummers methods.In step sl, additive is carbohydrate organic compound.Additive can
Think one or more of monosaccharide and disaccharide or polysaccharide.Optionally, the monosaccharide that additive uses can for glucose, fructose and
One or more of galactolipin.Optionally, the disaccharide that additive uses is one kind in sucrose, lactose and maltose or several
Kind.Optionally, the polysaccharide that additive uses is one or more of glycogen and starch.Of course, the carbohydrate that additive uses
Organic compound is not limited only to the above-mentioned several specific carbohydrates referred to, can also be other carbohydrate organic compounds
Or other large biological molecules being made of tri- kinds of elements of C, H, O.
In step s3, protective gas is the mixed gas of inert gas, reducibility gas or both.It is specific at one
In embodiment, inert gas be nitrogen, argon gas or its mixed gas, can also be other not with graphene oxide dispersion with
And the gas that additive chemically reacts.In a specific embodiment, reducibility gas is hydrogen.Reducibility gas
Graphene oxide is partly or completely restored when for heat treatment in step s3.
In step s 4, the organic solvent that repeated washing uses is unlimited, it is therefore preferable to one kind in ethyl alcohol, methanol and acetone
Or it is several.Of course, other organic solvents can also be used, it is only necessary to disclosure satisfy that and wash self-supporting reduction-oxidation graphite
Alkene rolls up the additive in network material.
Further, in S1 steps, the mass ratio of graphene oxide dispersion and additive is adjustable.Preferably at one
Embodiment in, the mass ratio of graphene oxide dispersion and additive is 1:10-10:1.Preparing self-supporting oxygen reduction
During graphite alkene rolls up network material, by adjusting the mass ratio of graphene oxide dispersion and additive, it can control
The microstructure for the self-supporting redox graphene volume network material prepared, makes it show different graphene rolls straight
Diameter, network aperture etc., to further expand the application range of self-supporting redox graphene volume network material.
Further, in S3 steps, predetermined time not restriction, optionally, predetermined time are not less than 0.1h, in advance
Constant temperature degree is not less than 50 DEG C.Preferably, predetermined time 1-30h.Preferably, predetermined temperature is 50-1000 DEG C.By controlling heat
The predetermined time of processing and predetermined temperature can control the reduction for the self-supporting redox graphene volume network material prepared
Degree.
For example, in a specific embodiment, in S3 steps, after solution freeze-drying at 50-500 DEG C at heat
It manages 1-30h and rolls up network structure up to the redox graphene of the partial reduction of self-supporting.
In another particular embodiment of the invention, it in S3 steps, is heat-treated at 50-300 DEG C after solution freeze-drying
1-10h rolls up network structure up to the redox graphene of the partial reduction of self-supporting.
In another particular embodiment of the invention, it in S3 steps, is heat-treated at 300-500 DEG C after solution freeze-drying
10-20h rolls up network structure up to the redox graphene of the partial reduction of self-supporting.
In another particular embodiment of the invention, in S3 steps, after solution freeze-drying at 300-1000 DEG C at heat
Reason 1-30h is to obtain the redox graphene volume network structure of self-supporting restored completely.
In another particular embodiment of the invention, it in S3 steps, is heat-treated at 300-700 DEG C after solution freeze-drying
1-100h is to obtain the redox graphene volume network structure of self-supporting restored completely.
In another particular embodiment of the invention, in S3 steps, after solution freeze-drying at 700-1000 DEG C at heat
Reason 20-30h is to obtain the redox graphene volume network structure of self-supporting restored completely.
The redox graphene rolls up the principle with above structure and property：Additive is added in step S1
Afterwards, solution still keeps homogeneously dispersed state, but the solidification point of whole solution reduces at this time；Simultaneously because the weak reduction of additive
It acting on, the reaction force attenuation between graphene sheet layer is used as template so in step S2 freezing dry process by ice crystal,
Ultimately form mutually overlapping winding overlapped graphene coil structure；After this step S2, shape of the additive as similar " mud "
State coats or part is coated on the surface of graphene oxide layer, while being attached between graphene oxide layer and lamella
At gap, graphene roll can be made to keep network structure without loosely or in powdered.After step S3 heat treatments, as class
Become the graphene oxide being partially reduced or the graphene being completely reduced like the graphene oxide of " brick "；And additive is by portion
Point pyrolysis is amorphous carbon by carbonization, and is coated on reduction or partial reduction completely as " mud " cladding or part
Graphene oxide layer (being usually also referred to simply as graphene sheet layer) surface, while filling or being partially fill in reduction or partial reduction
Graphene oxide layer and lamella between gap at, formed " brick mud structure " so that nanometer roll can keep self-supporting three
Tie up network structure；In step s 4, after the graphene oxide to partial reduction rolls up cleaning, the graphene oxide volume of partial reduction
The additive heat-treated products on surface are largely cleaned out, and are conducive to the density for reducing nanometer roll；And it is filled in as " mud "
Portions additive heat-treated products at gap between graphene sheet layer and lamella be still in graphene sheet layer and lamella it
Between, it is not removed, this may be due to the key between additive heat-treated products and graphene sheet layer caused by reduction process
Connection or bridge linking effect, so that graphene roll can keep self-supporting three-dimensional net structure without loosely or in powdered.And
Coil structure cannot be formed by additive is not added also passing through the graphenes of step S2 processing procedures, and sample does not have certain soft
Property, it is loosely organized or in powdered but in frangible, stable macrostructure state cannot be formed.
A kind of preparation method of the redox graphene volume network structure material of self-supporting provided by the invention, specifically
Embodiment is as follows：
Specific embodiment 1
The unreduced graphene oxide of the self-supporting containing additive is prepared using glucose and graphene oxide to roll up：
1) a certain amount of dense H is taken2SO4, graphite powder, NaNO3It is stirred in ice-water bath；Then KMnO is added4And deionized water
Continuation is stirred in ice-water bath, is eventually adding H2O2Multiple eccentric cleaning afterwards, obtains graphene oxide dispersion.
2) graphene oxide dispersion of certain mass and glucose is taken to be dissolved in deionized water ultrasonic, wherein graphite oxide
The concentration of alkene and glucose is 0.5mg/mL.
3) above-mentioned solution is injected in the mold of polytetrafluoroethylene material, a bottom part for mold is then immersed in liquid
In nitrogen, formation temperature gradient is poor, and material is prepared using ice crystal mould plate technique, after solution all solidification, is put into freeze drier
It is taken out after middle dry 36h, that is, produces the self-supporting graphene oxide volume containing glucose.
In method provided in this embodiment, certain density graphene oxide is with additive ultrasonic mixing (in the present embodiment
Additive is glucose, and the concentration of graphene oxide and glucose is similarly 0.5mg/mL), the condensation point of solution is relatively not added at this time
Solidification point when additive reduces, and graphene oxide dispersion is easy to form three-dimensional grapheme web-like in follow-up ice crystal template
Structure；Simultaneously because additive solution is non-electrolytic solution, therefore the reunion of graphene oxide dispersion will not be caused, this makes
The graphene oxide sheet for obtaining mixed solution keeps good dispersity；Then by solution inject container in (container can be glass,
Stainless steel, the material preparation not soluble in water such as plastics, the present embodiment is polytetrafluoroethylene (PTFE)) and container part is immersed into liquid nitrogen, shape
At temperature difference, graphene coil structure is prepared using ice crystal as template, then utilizes Refrigeration Technique removal ice crystal (freezing
Drying time is indefinite, and 36h is dried using freeze drier in the present embodiment), obtain three-dimensional unreduced graphene oxide volume.
According to the above method prepare graphene oxide volume can self-supporting, there is certain macroscopic property and be cleavable
Three-dimensional net structure；The sample is in brown color, the diameter about 500nm of the graphene roll, density about 1mg/ under macrostate
cm3(concentration of additive and graphene dispersing solution is adjusted by adjusting, can obtain color similar in macrostate and brown color with
The density of graphene roll diameter unlike and and three-dimensional redox graphene volume).The unreduced oxidation stone of the self-supporting
Black alkene volume network structure material remains the larger specific surface area of graphene, and can be applied to gas sensor, (such as sulfur dioxide passes
Sensor) in, while the concentration by adjusting graphene oxide dispersion and additive, the graphene oxide of different size can be prepared
Volume structure, such as different voidages, the sample of different coil diameters expand the application range of material.
Specific embodiment 2
Fructose is done unlike the present embodiment and specific implementation mode example 1 and does additive, and its concentration is 0.25mg/
ML finally produces out the self-supporting graphene oxide volume containing fructose, the diameter about 300nm of the graphene roll.Other and tool
Body embodiment example 1 is identical.
Specific embodiment 3
The present embodiment contains additive unlike specific implementation mode example 1 using sucrose and graphene oxide preparation
Self-supporting graphene oxide is rolled up, a concentration of 0.5mg/mL of sucrose, produces out the self-supporting graphene oxide volume containing sucrose, institute
State the diameter about 500nm of graphene roll.Other are identical as specific implementation mode example 1.
Specific embodiment 4
Maltose is done unlike the present embodiment and specific implementation mode example 1 and does additive, and its concentration is 1 mg/
ML finally produces out the self-supporting graphene oxide volume containing maltose, the diameter about 1000nm of the graphene roll.Other with
Specific implementation mode example 1 is identical.
Specific embodiment 5
The complete redox graphene of the self-supporting containing additive is prepared using glucose and graphene oxide to roll up：
1) graphene oxide dispersion of certain mass and glucose is taken to be dissolved in deionized water ultrasonic, wherein graphite oxide
The concentration of alkene and glucose is respectively 0.5mg/mL and 1mg/mL.
2) above-mentioned solution is injected in the mold of polytetrafluoroethylene material, is solidified by liquid nitrogen frozen, is put into freezing therewith
It is taken out after dry 36h in drying machine.
3) material that above-mentioned freeze-drying is produced is put into tube furnace at 800 DEG C, 8h is heat-treated in argon atmosphere, with
Cooled to room temperature is to get to the complete redox graphene volume structure of self-supporting afterwards, described at this time to restore completely
Graphene oxide is rolled up it is characterized in that being in black under macrostate, as shown in attached drawing 2；The diameter of graphene roll is about at this time
500nm。
In method provided in this embodiment, certain density graphene oxide is with additive ultrasonic mixing (in the present embodiment
Additive is glucose, and the concentration of graphene oxide and glucose is respectively 0.5mg/mL and 1 mg/mL), solution is cold at this time
Condensation point less doping when solidification point reduce, graphene oxide dispersion is easy to be formed in follow-up ice crystal template three-dimensional
Graphene coil structure；Simultaneously because additive solution is non-electrolytic solution, therefore graphene oxide dispersion will not be caused
Reunion, this makes the graphene oxide sheet of mixed solution keep good dispersity；Then solution is injected in container and (is held
Device can be glass, and stainless steel, the material preparation not soluble in water such as plastics, the present embodiment is polytetrafluoroethylene (PTFE)) and by container part
Liquid nitrogen is immersed, temperature difference is formed, graphene coil structure is prepared using ice crystal as template, then Refrigeration Technique is utilized to remove
Ice crystal (sublimation drying is indefinite, and 36h is dried using freeze drier in the present embodiment), obtains three-dimensional unreduced oxidation stone
Black alkene volume.Then by the above-mentioned material isolation air high-temperature process produced, (the present embodiment is in tube furnace to postcooling for a period of time
In 800 DEG C heat treatment 8h after natural cooling), the additive that material contains at this time is carbonized, and graphene oxide is completely reduced；Profit
The graphene oxide volume restored completely prepared in aforementioned manners can self-supporting, there is certain macroshape and be cleavable
Three-dimensional net structure；The sample macrostate is in black, and the diameter of graphene roll and density etc. can be according to initial oxidation graphite
The concentration of alkene and additive is adjustable (diameter of graphene roll is about 1000nm in the present embodiment, and density is about 0.5 mg/mL).It should
The graphite oxide volume of self-supporting maintains graphene large specific surface area, and also has certain flexibility, and its density is smaller,
It is a kind of preferable conductive network structural material, can be used as ultracapacitor, lithium silion cell, the host materials such as lithium-sulfur cell.
Specific embodiment 6
The present embodiment does additive unlike specific implementation mode 5 with galactolipin, and concentration is 0.25 mg/mL, most
The complete redox graphene volume of the self-supporting containing galactolipin, the diameter about 300nm of the graphene roll are produced out afterwards；It is other
It is identical as specific implementation mode example 5.
Specific embodiment 7
The present embodiment does additive unlike specific implementation mode example 5 using sucrose, and concentration is 1 mg/mL, most
The complete redox graphene volume of the self-supporting containing sucrose, the diameter about 1000nm of the graphene roll are produced out afterwards；It is other
It is identical as specific implementation mode example 5.
Fig. 3 is the surface topography map (SEM of the scanning electron microscope of self-supporting graphene roll prepared by non-doping
Figure).As shown in figure 3, the present invention also utilizes graphene oxide dispersion, using additivated preparation method is not added, to attempt
Directly prepare self-supporting graphene roll.The grapheme material prepared is subjected to electron microscope observation, discovery is passing through this hair
When bright preparation method does not add additive, the grapheme material prepared is stripped, there is no winding-structure, specific mistake
Journey is as follows：
Specific embodiment 8
Using graphene oxide dispersion, not doping is attempted directly to prepare self-supporting graphene roll process：
1) it takes the graphite oxide graphene dispersing solution of certain mass ultrasonic in deionized water, prepares graphene oxide concentration
For the solution of 0.5mg/mL.
2) above-mentioned solution is injected in the mold of polytetrafluoroethylene material, is solidified by liquid nitrogen frozen, is put into freezing therewith
It is taken out after dry 36h in drying machine.
3) by SEM figures in attached drawing 4 as can be seen that graphene is stripped at this time, there is no winding-structures.
Specific embodiment 9
It prepares self-supporting part redox graphene and rolls up network structure material, and use it for lithium-sulfur cell.
1) graphene oxide dispersion of certain mass and glucose is taken to be dissolved in deionized water ultrasonic, wherein graphite oxide
The concentration of alkene and glucose is respectively 1mg/mL and 0.5mg/mL.
2) above-mentioned solution is injected in the mold of polytetrafluoroethylene material, is solidified by liquid nitrogen frozen, is put into freezing therewith
It is taken out after dry 36h in drying machine.
3) material for producing above-mentioned freeze-drying is heat-treated 12h in 180 DEG C, argon atmosphere, then naturally cools to
Room temperature.
4) material of above-mentioned preparation is placed in the mixed solution of deionized water and ethyl alcohol at 60 DEG C of water-bath and heats 2 h,
The volume ratio of middle water and ethyl alcohol is 1:1, it then replaces mixed solution and handles under the same conditions；This process is spent after being repeated 5 times
Sample is cleaned multiple times in ionized water, removes the glucose heat-treated products in graphene roll.
In method provided in this embodiment, certain density graphene oxide is with additive ultrasonic mixing (in the present embodiment
Additive is glucose, and the concentration of graphene oxide and glucose is respectively 1mg/mL and 0.5 mg/mL), solution is cold at this time
Condensation point less doping when solidification point reduce, graphene oxide dispersion is easy to be formed in follow-up ice crystal template three-dimensional
Graphene coil structure；Simultaneously because additive solution is non-electrolytic solution, therefore graphene oxide dispersion will not be caused
Reunion, this makes the graphene oxide sheet of mixed solution keep good dispersity；Then solution is injected in container and (is held
Device can be glass, and stainless steel, the material preparation not soluble in water such as plastics, the present embodiment is polytetrafluoroethylene (PTFE)) and by container part
Liquid nitrogen is immersed, temperature difference is formed, graphene coil structure is prepared using ice crystal as template, then Refrigeration Technique is utilized to remove
Ice crystal (sublimation drying is indefinite, and 36h is dried using freeze drier in the present embodiment), obtains three-dimensional unreduced oxidation stone
Black alkene volume.By unreduced graphene oxide volume, (the present embodiment is handled natural cooling at 180 DEG C after lower temperature thermal reduction
12h), the partial reduction graphene oxide volume containing additive is obtained.(use is originally implemented by further removing additive
The 60 DEG C of processing 2h cleaning removal glucose heat treatments of mixed solution water-bath for reusing isometric deionized water and ethyl alcohol are produced
Object), it obtains the partial reduction graphene oxide without additive and rolls up.The partial reduction graphene roll can be further in higher temperature
Lower heat treatment a period of time (such as 500 DEG C or more, processing time is more than 5h), that is, obtain the additive reaction that is free of restored completely and produce
The graphene oxide of object is rolled up.
Using the above method prepare partial reduction graphene oxide volume can self-supporting, have certain macroshape simultaneously
And it is cleavable three-dimensional net structure；The sample macrostate is in black, and the diameter of graphene roll and density etc. can be according to first
The concentration of beginning graphene oxide and additive is adjustable, and (diameter of graphene roll is about 1000nm in the present embodiment, and density is about
0.8mg/mL), and the graphene roll without or with minimal amount of additive heat-treated products (in the present embodiment additive heat
Handle mass fraction of product<1%).The graphite oxide volume of the self-supporting maintains graphene large specific surface area, and also has one
Fixed flexibility, and its density is smaller, is a kind of preferable conductive network structural material, while its surface has oxygen-containing functional group
(such as carboxyl, epoxy group etc.) can effectively hold onto when being applied to lithium-sulfur cell and generate more sulphur productions in battery discharge procedure
Object avoids it from being dissolved in electrolyte and causes " shuttle effect "；The graphene oxide volume of partial reduction further expands oxygen reduction
The application range of graphite alkene volume.
So far, although those skilled in the art will appreciate that present invention has been shown and described in detail herein multiple shows
Example property embodiment still without departing from the spirit and scope of the present invention, still can according to the present disclosure directly
Determine or derive many other variations or modifications consistent with the principles of the invention.Therefore, the scope of the present invention is understood that and recognizes
It is set to and covers other all these variations or modifications.
Claims (10)
1. a kind of self-supporting redox graphene rolls up network material, which is characterized in that self-supporting redox graphene reel wire
By single layer, as dried layer redox graphene piece is connected with each other and is wound into redox graphene volume, the reduction network material
It is mutually overlapping between graphene oxide volume to be overlapped to form self-supporting three-dimensional porous network structure；The self-supporting redox graphene
Volume network material contains additive, has certain shape and flexibility, can be processed or cut into arbitrary shape.
2. self-supporting redox graphene according to claim 1 rolls up network material, which is characterized in that the oxygen reduction
Graphite alkene volume can have a different reducing degrees, and the constitution element of redox graphene volume is carbon, hydrogen and oxygen, carbon with
The mass ratio of oxygen can regulate and control；
Optionally, the redox graphene volume can be unreduced graphene oxide volume；
Optionally, the redox graphene volume can be the redox graphene volume of partial reduction；
Optionally, the redox graphene volume can be the redox graphene volume restored completely, the content of oxygen element
≤ 1%.
3. self-supporting redox graphene according to claim 1 rolls up network material, which is characterized in that the oxygen reduction
Graphite alkene rolls up the adjustable porosity of network material, preferably 10-99%；
The density of the redox graphene volume network material is adjustable, it is therefore preferable to be less than 10mg/cm3；
The diameter of the redox graphene volume network material is adjustable, preferably 1nm-10 μm.
4. self-supporting redox graphene according to claim 1 rolls up network material, which is characterized in that the oxygen reduction
Graphite alkene rolls up the draw ratio of network materialIt is adjustable；
Preferably, the draw ratioMore than 5；
Wherein, the length of volumes of the L between two node of graphene roll network, d are the diameter of graphene roll.
5. a kind of preparation method of self-supporting redox graphene volume network material, which is characterized in that include the following steps：
S1, configure certain mass ratio graphene oxide dispersion and additive mixed uniformly mixed solution；
S2, the mixed solution is freeze-dried, obtains unreduced graphene oxide volume network material；
S3, the unreduced graphene oxide volume network material is placed in protective gas atmosphere with the pre- timing of predetermined temperature processing
Between, the graphene oxide for obtaining the partial reduction of self-supporting or restoring completely rolls up network material；
S4, after the graphene oxide of the partial reduction of self-supporting volume network material to be carried out to the repeated washing of predetermined extent,
Carry out freeze-drying process；Obtain the self-supporting part redox graphene volume network material containing low additive level.
6. the preparation method of self-supporting redox graphene volume network material according to claim 5, which is characterized in that S1
In step, the mass ratio of the graphene oxide dispersion and additive is adjustable；
Preferably, the mass ratio is 1:10-10:1.
7. the preparation method of self-supporting redox graphene volume network material according to claim 5, which is characterized in that
In S1 steps, the additive can be one or more of monosaccharide and disaccharide or polysaccharide；
Preferably, the monosaccharide is one or more of glucose, fructose and galactolipin；
Preferably, the disaccharide is one or more of sucrose, lactose and maltose；
Preferably, the polysaccharide is one or more of glycogen and starch.
8. the preparation method of self-supporting redox graphene volume network material according to claim 5, which is characterized in that
In S3 steps, the protective gas is the mixed gas of inert gas, reducibility gas or both；
Preferably, the inert gas is nitrogen, argon gas or its mixed gas；
Preferably, the reducibility gas is hydrogen.
9. the preparation method of self-supporting redox graphene volume network material according to claim 5, which is characterized in that
In S3 steps, the predetermined temperature is not less than 50 DEG C；The predetermined time is no less than 0.1h；
Preferably, the predetermined temperature is 50-1000 DEG C；
Preferably, the predetermined time is 1-30h.
10. the preparation method of self-supporting redox graphene volume network material according to claim 5, feature exist
In in S4 steps, the organic solvent that the repeated washing uses is unlimited, it is therefore preferable to one kind in ethyl alcohol, methanol and acetone or
It is several.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2017100418425 | 2017-01-20 | ||
| CN201710041842 | 2017-01-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108328611A true CN108328611A (en) | 2018-07-27 |
| CN108328611B CN108328611B (en) | 2021-03-16 |
Family
ID=62922877
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710302040.5A Active CN108328611B (en) | 2017-01-20 | 2017-05-02 | Self-supporting reduced graphene oxide roll network material and preparation method thereof |
| CN201710302310.2A Active CN108336310B (en) | 2017-01-20 | 2017-05-02 | Composite material based on self-supporting reduced graphene oxide roll and preparation method |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710302310.2A Active CN108336310B (en) | 2017-01-20 | 2017-05-02 | Composite material based on self-supporting reduced graphene oxide roll and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN108328611B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110391419A (en) * | 2019-07-26 | 2019-10-29 | 广东工业大学 | A kind of porous carbon and its application in lithium-sulphur cell positive electrode |
| CN113880079A (en) * | 2021-11-12 | 2022-01-04 | 四川大学 | Graphene nano-roll and preparation method thereof |
| CN115663166A (en) * | 2022-12-08 | 2023-01-31 | 北京石墨烯技术研究院有限公司 | Metal lithium composite material and preparation method thereof, negative electrode plate, lithium battery and electric device |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113903888B (en) * | 2021-09-02 | 2023-04-18 | 青岛科技大学 | Cross-linked reduced graphene oxide-based flexible self-supporting membrane electrode and rapid preparation method thereof |
| CN113921778B (en) * | 2021-09-02 | 2023-04-18 | 青岛科技大学 | Reduced graphene oxide-based hollow Co-MOF composite flexible electrode material and preparation method thereof |
| CN113877614B (en) * | 2021-10-27 | 2023-04-21 | 北京石墨烯技术研究院有限公司 | Modified graphene roll and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105948029A (en) * | 2016-05-09 | 2016-09-21 | 东华大学 | Graphene roll/carbon nanotube composite aerogel material, preparation and application thereof |
| CN106024424A (en) * | 2016-07-01 | 2016-10-12 | 东华大学 | Nickel hydroxide/graphene roll-carbon nano-tube composite carbon aerogel, preparation thereof and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496719A (en) * | 2011-12-15 | 2012-06-13 | 中国科学院化学研究所 | Silicon/graphene composite material, and preparation method and application of the same |
| CN103723716B (en) * | 2013-12-23 | 2016-06-08 | 北京化工大学 | Nitrogen-doped carbon cladding graphene oxide two-dimensional is composite porous and preparation method thereof |
| CN106299309A (en) * | 2016-09-30 | 2017-01-04 | 上海交通大学 | Graphene half cladding tin oxide nano particles cluster composite material and preparation method thereof |
-
2017
- 2017-05-02 CN CN201710302040.5A patent/CN108328611B/en active Active
- 2017-05-02 CN CN201710302310.2A patent/CN108336310B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105948029A (en) * | 2016-05-09 | 2016-09-21 | 东华大学 | Graphene roll/carbon nanotube composite aerogel material, preparation and application thereof |
| CN106024424A (en) * | 2016-07-01 | 2016-10-12 | 东华大学 | Nickel hydroxide/graphene roll-carbon nano-tube composite carbon aerogel, preparation thereof and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| JU-HASING CHENG ET AL.: "Enhancement of Electrochemical Properties by Freeze-dried Graphene Oxide via Glucose-assisted Reduction", 《ELECTROCHIMICA ACTA》 * |
| 郑鑫垚: "石墨烯基气凝胶的制备及其CO2吸附", 《万方数据》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110391419A (en) * | 2019-07-26 | 2019-10-29 | 广东工业大学 | A kind of porous carbon and its application in lithium-sulphur cell positive electrode |
| CN110391419B (en) * | 2019-07-26 | 2022-07-05 | 广东工业大学 | Porous carbon and application thereof in lithium-sulfur battery anode |
| CN113880079A (en) * | 2021-11-12 | 2022-01-04 | 四川大学 | Graphene nano-roll and preparation method thereof |
| CN115663166A (en) * | 2022-12-08 | 2023-01-31 | 北京石墨烯技术研究院有限公司 | Metal lithium composite material and preparation method thereof, negative electrode plate, lithium battery and electric device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108336310A (en) | 2018-07-27 |
| CN108328611B (en) | 2021-03-16 |
| CN108336310B (en) | 2021-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108328611A (en) | A kind of self-supporting redox graphene volume network material and preparation method thereof | |
| Zhou et al. | Synthesis of fish skin-derived 3D carbon foams with broadened bandwidth and excellent electromagnetic wave absorption performance | |
| Hao et al. | Hierarchical three-dimensional Fe3O4@ porous carbon matrix/graphene anodes for high performance lithium ion batteries | |
| CN104495780B (en) | Hydrophilic graphene-carbon nano-tube composite super-light elastic aerogel and preparation method thereof | |
| JP6019228B2 (en) | Method for producing high density and high hardness graphene porous carbon material | |
| JP5864687B2 (en) | Method for producing graphene-based composite negative electrode material, and manufactured negative electrode material and lithium ion secondary battery | |
| CN105540573B (en) | A kind of more fold dry state graphene oxide microballoons of highly dissoluble and preparation method thereof | |
| Li et al. | Terminal hollowed Fe2O3@ SnO2 heterojunction nanorods anode materials with enhanced performance for lithium-ion battery | |
| CN105948029A (en) | Graphene roll/carbon nanotube composite aerogel material, preparation and application thereof | |
| CN105731428B (en) | A kind of graphene of sulfur doping and its preparation method of derivative and purposes | |
| CN108530073A (en) | A kind of preparation method of the three-dimensional porous graphene film of flexible self-supporting | |
| CN109437202A (en) | A kind of two dimension magnesium-yttrium-transition metal carbon (nitrogen) compound aeroge and its preparation method and application | |
| Wang et al. | Poplar branch bio-template synthesis of mesoporous hollow Co3O4 hierarchical architecture as an anode for long-life lithium ion batteries | |
| Su et al. | Three-dimensional mesoporous γ-Fe2O3@ carbon nanofiber network as high performance anode material for lithium-and sodium-ion batteries | |
| KR102590821B1 (en) | Porous carbon microball including surface-treated carbon material, method of manufacturing the porous carbon microball, and composite including the porous carbon microball | |
| CN104445153A (en) | Method for macroscopic quantity preparation of carbon nano coil from graphene | |
| KR20130083128A (en) | Method for producing graphene dispersed solution and powder thereof | |
| CN107456928B (en) | Graphene/sodium alginate/carbon nanotube composite elastic aerogel for strain sensor and preparation method thereof | |
| Gu et al. | Synthesis of hierarchical α-Fe2O3 nanotubes for high-performance lithium-ion batteries | |
| CN107393622B (en) | Graphene-titanium suboxide composite conductive agent and preparation method thereof | |
| Liu et al. | Biotemplate-assisted hydrothermal synthesis of tubular porous Co3O4 with excellent charge-discharge cycle stability for supercapacitive electrodes | |
| CN106024424A (en) | Nickel hydroxide/graphene roll-carbon nano-tube composite carbon aerogel, preparation thereof and application thereof | |
| CN109942029B (en) | Universal method for assembling ultrathin porous nanosheets by using metal oxide quantum dots | |
| Wang et al. | Preparation of novel porous carbon spheres from corn starch | |
| Shao et al. | Yolk-shell Si@ void@ C composite with Chito-oligosaccharide as a C–N precursor for high capacity anode in lithium-ion batteries |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |