CN106241784B - A kind of preparation method of the grapheme material of multilevel structure - Google Patents
A kind of preparation method of the grapheme material of multilevel structure Download PDFInfo
- Publication number
- CN106241784B CN106241784B CN201610611560.XA CN201610611560A CN106241784B CN 106241784 B CN106241784 B CN 106241784B CN 201610611560 A CN201610611560 A CN 201610611560A CN 106241784 B CN106241784 B CN 106241784B
- Authority
- CN
- China
- Prior art keywords
- graphene
- electrolyte
- solution
- preparation
- present
- 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.)
- Active
Links
Classifications
-
- 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
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention provides a kind of preparation methods of the grapheme material of multilevel structure, include the following steps, first by graphene solution after filtering, form graphene film；After graphene oxide solution is mixed with electrolyte, mixed solution is obtained；Then mixed solution above-mentioned steps obtained obtains admixed graphite alkene material after filtering again using graphene film as filter membrane；The admixed graphite alkene material that finally above-mentioned steps are obtained obtains multilevel structure, the different grapheme material of function after freeze-drying.The present invention reduces the un-densified property during grapheme material is constructed using electrolyte, the multiple suction filtration process between different grapheme materials is utilized simultaneously, the conflict between method and structure, function is not only reduced, and the different material of the function of different structure and property is combined in into same grapheme material；The arrangement mode for also changing graphene sheet layer simultaneously has obtained the orderly controllable multilevel structure grapheme material of graphene film.
Description
Technical field
The invention belongs to carbon material technical field more particularly to a kind of preparation methods of the grapheme material of multilevel structure.
Background technique
Graphene (Graphene) by carbon atom form only one layer of atomic thickness two dimensional crystal, and at present into
Enter material most thin in application field and most tough material, 200 times more taller than steel of breaking strength, there is good bullet
Property, stretch range can reach the 20% of own dimensions；Also there is huge theoretical specific surface area simultaneously, physicochemical properties are steady
It is fixed, also there is excellent electric conductivity.There is many excellent physical chemical property just because of grapheme material, in energy storage material
Expect, environmental project, is widely applied in terms of highly sensitive pressure sensing, but the application in existing field, still still concentrate on
In graphene nanosheet.
As the fast development and every profession and trade of science and technology are to the high level need of grapheme material, in order to break through practical application
Barrier adapts to industry demand, relies solely on the graphene nanosheet as made of single layer of carbon atom planar structure graphene stacking
Existing technical problem is not can effectively solve, therefore to preparing the multifunctional graphite vinyl macroscopic view material with different structures
Material proposes requirement.Graphene is because of its unique two-dimensional nano lamella structure, for graphene constructs different structures and provides
Built-up foundation, such as graphene nano volume, three-dimensional porous graphene etc. not only alleviate heap of the graphene film in reduction process
Folded problem, and the advantage of various structure is also using opening road.
But the design of current grapheme material structure and function is still excessively single, is unfavorable for many-sided extension of application,
Grapheme material is allowed to be suitable for widely application, expanding to the multi-functional grapheme material of multilevel structure also becomes in recent years
Development and research tendency.However actual expansion application but receives obstruction at present, mainly grapheme material is multi-functional
The missing of aspect, and the structural requirement inside the more grapheme materials of different functions also can be different.The design of grapheme material
In the process, when on the one hand due to grapheme material being assembled into macroscopic material by nanoscale twins, using single method to structure and function
The regulation of energy is not strong, but will receive distinct methods and different structure, function when on the other hand preparing this material using a variety of methods
Cannot be harmonious between energy, and great difficulty is caused to manufacturing process, or even cannot form.
In recent years, there is process of the research by graphene oxide by laser reduction at graphene, original area and depth are gone back in control
Degree, prepares the grapheme material of two kinds of different function, also has research by ozone treatment grapheme material, makes originally hydrophobic
Grapheme material becomes hydrophilic graphene oxide composite material, but such methods are high to Preparation equipment and environmental requirement, and can only
Prepare internal structure of the material of different function without being adjustable two kinds of functionalization materials.
Therefore, a kind of preparation method how is obtained, the different function with different internal structure can be prepared
Grapheme material is of great significance to the application of extension grapheme material, and lays the foundation for the application of later period material.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of preparation of the grapheme material of multilevel structure
Method, preparation method provided by the invention can effectively control graphene microchip arrangement mode in an assembling process, to adjust
Standby graphene macroscopic material is controlled, the more excellent graphene macroscopic material with ordered micro-configuration of function is obtained.
The present invention provides a kind of preparation methods of the grapheme material of multilevel structure, comprising the following steps:
A) by graphene solution after filtering, graphene film is formed；
After graphene oxide solution is mixed with electrolyte, mixed solution is obtained；
B) mixed solution for obtaining above-mentioned steps obtains admixed graphite alkene material after filtering again using graphene film as filter membrane
Material；
C) the admixed graphite alkene material for obtaining above-mentioned steps obtains the graphene material of multilevel structure after freeze-drying
Material.
Preferably, the concentration of the graphene oxide solution is 0.1~3.5mg/mL.
Preferably, the concentration of the graphene oxide solution is 0.5~1.0mg/mL.
Preferably, the concentration of the graphene solution is 0.1~10mg/mL.
Preferably, the electrolyte includes strong electrolyte and/or weak electrolyte；
The strong electrolyte includes one of halide, strong acid and highly basic or a variety of；
The weak electrolyte includes one of carbonate, alkali metal salt, alkali salt, weak acid and weak base or a variety of.
Preferably, the electrolyte is in ammonium hydrogencarbonate, ammonium carbonate, nickel acetate, nickel chloride, potassium chloride and sodium hydroxide
It is one or more.
Preferably, when the electrolyte is weak electrolyte, electrolyte described in the mixed solution and the graphite oxide
The mass ratio of alkene is (5~400): 1.
Preferably, when the electrolyte is strong electrolyte, electrolyte described in the mixed solution and the graphite oxide
The mass ratio of alkene is (5~100): 1.
Preferably, the temperature of the freeze-drying is -100~-10 DEG C；The time of the freeze-drying is 12~48h.
Preferably, the filter medium filtered again is the filter medium of graphene filter membrane and filter device；
Along filtering direction, the graphene film is the first filter medium, and the filter medium of the filter device is the second mistake
Filter medium.
The present invention provides the present invention provides a kind of preparation methods of the grapheme material of multilevel structure, including following step
Suddenly, first by graphene solution after filtering, graphene film is formed；After graphene oxide solution is mixed with electrolyte, obtain
To mixed solution；Then mixed solution above-mentioned steps obtained obtains mixing stone using graphene film as filter membrane after filtering again
Black alkene material；The admixed graphite alkene material that finally above-mentioned steps are obtained obtains the graphite of multilevel structure after freeze-drying
Alkene material.Compared with prior art, the present invention reduces the un-densified property during grapheme material is constructed using electrolyte, together
The suction filtration in the external world Shi Liyong acts on, and not only reduces the conflict between method and structure, function, and utilize different grapheme materials
Between the different structure that shows during multiple filter and the property of itself and obtain the different material of structure and function and combine in together
One grapheme material；The arrangement mode for also changing graphene sheet layer simultaneously obtains the orderly controllable porous graphite of graphene film
Alkene material, the grapheme material for overcoming prior art preparation is fine and close, unordered defect.Preparation method provided by the invention uses
The method of simple extraneous filtering, the function and structure single compared to other grapheme materials, the method pass through different originals
Material is prepared for the labyrinth with the graphene/graphene oxide of multilevel structure, has different functionality, while can also
The arrangement mode of enough effective control graphene microchips in an assembling process obtains so that regulation prepares graphene macroscopic material
The more excellent multifunctional graphite vinyl macroscopic material with multilevel structure and ordered micro-configuration of function.The experimental results showed that
The grapheme material structure of multilevel structure prepared by the present invention, hydrophilic and hydrophobic difference not only has and to be made of graphene oxide
Porous structure with extremely strong hydrophilic sequential 2 D, but also it is extremely strong hydrophobic with having for being made of grapheme material
Property three-dimensional perforation porous structure.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of grapheme material prepared by the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of grapheme material prepared by the embodiment of the present invention 2；
Fig. 3 is the scanning electron microscope (SEM) photograph of grapheme material prepared by the embodiment of the present invention 3.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or capacitor area
The conventional purity used.
The present invention provides a kind of preparation methods of the grapheme material of multilevel structure, comprising the following steps:
A) by graphene solution after filtering, graphene film is formed；
After graphene oxide solution is mixed with electrolyte, mixed solution is obtained；
B) mixed solution for obtaining above-mentioned steps obtains admixed graphite alkene material after filtering again using graphene film as filter membrane
Material；
C) the admixed graphite alkene material for obtaining above-mentioned steps obtains the graphene material of multilevel structure after freeze-drying
Material.
The present invention forms graphene film first by graphene solution after filtering；By graphene oxide solution and electrolysis
After matter mixing, mixed solution is obtained.
The graphene solution is not particularly limited in the present invention, is with graphene solution well known to those skilled in the art
Can, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, the present invention
The concentration of the graphene solution is preferably 0.1~10mg/mL, more preferably 3.0~8.0mg/mL, more preferably 4.5~
6.5mg/mL, most preferably 5.0~6.0mg/mL.
The graphene is not particularly limited in the present invention, with graphene well known to those skilled in the art, ability
Field technique personnel can select and adjust according to practical condition, product requirement and quality requirement.
The source of the graphene solution is not particularly limited in the present invention, with graphene well known to those skilled in the art
The source of solution, commercially available buy can also prepare according to the conventional preparation method, graphene solution of the present invention
It obtains after preferably being mixed by graphene solvent and water, is more preferably obtained after graphene solvent and deionized water dispersion mixing,
It is obtained after more specific preferably the graphene solvent and deionized water ultrasonic disperse of intercalation stripping.The present invention is to the ultrasonic disperse
Condition be not particularly limited, with the condition of ultrasonic disperse well known to those skilled in the art, those skilled in the art can
To be selected and be adjusted according to practical condition, product requirement and quality requirement, the power of ultrasonic disperse of the present invention
Preferably less than it is equal to 200W, is more preferably less than equal to 180W, is more preferably less than equal to 150W, is most preferably less than equal to
120W；The time of the ultrasonic disperse, which is preferably less than, is equal to 2h, is more preferably less than equal to 1.5h, is most preferably less than equal to
1h。
The filtering is not particularly limited in the present invention, is filtered with filter type well known to those skilled in the art,
Those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, institute of the present invention
Filtering is stated preferably to filter under the effect of extraneous pressure field；The present invention to it is described extraneous pressure field effect under filter it is not special
Definition, preferably refer to and be filtered under conditions of with pressure difference, be particularly preferred as filter or filters pressing, more preferably take out
Filter.The device of the filtering is not particularly limited in the present invention, with well known to those skilled in the art using ambient pressure field, i.e.,
There are the filter plants of pressure difference, are particularly preferred as Suction filtration device, paper machine or filter-pressing device, and more preferably sand core is taken out
Filter device.The selection of the filter medium (filter membrane filter core) of the filtering, suction filtration or filters pressing is not particularly limited in the present invention, with this
Filtering known to the technical staff of field filters or the conventional arrangement of filters pressing grapheme material, and those skilled in the art can be with
It is selected and is adjusted according to practical condition, product requirement and quality requirement, filter medium of the present invention -- filter membrane is excellent
It is selected as one of Kynoar filter membrane, composite fibre resin film and anodic alumina films or a variety of；Filtering of the present invention
Medium -- filter core is preferably one of PP filter core, ceramic element, resin filter element and glass sand core or a variety of.The present invention is to described
The conditions such as pressure, the temperature and time of filtering are not particularly limited, with above-mentioned filter condition well known to those skilled in the art
Conventional arrangement, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the pressure of suction filtration of the present invention is preferably 0.05~0.5MPa, more preferably 0.1~0.45MPa, more preferably 0.15
~0.4MPa, most preferably 0.2~0.3MPa.The present invention is to prevent suction filtration process from causing collapsing for graphene-structured, the pumping
The time of filter/amount is preferably smaller than equal to 10min/mL, is more preferably less than equal to 8min/mL, is more preferably less than equal to 5min/
mL.The end point of the process of filtering of the present invention, preferably using surface solution without obvious mobility as standard.
The graphene oxide solution is not particularly limited in the present invention, with graphite oxide well known to those skilled in the art
Alkene solution, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement
Whole, the concentration of graphene oxide solution of the present invention is preferably 0.1~3.5mg/mL, more preferably 0.5~3.0mg/mL, more
Preferably 1.0~2.0mg/mL, most preferably 1.25~1.75mg/mL；More particularly, when electrolyte middle-jiao yang, function of the spleen and stomach of the present invention from
When son is trivalent, the concentration of the graphene oxide solution is preferably 0.5~1.0mg/mL, more preferably 0.6~0.9mg/mL,
Most preferably 0.7~0.8mg/mL.
The graphene oxide is not particularly limited in the present invention, is with graphene oxide well known to those skilled in the art
Can, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement.
The source of the graphene oxide solution is not particularly limited in the present invention, with oxygen well known to those skilled in the art
The source of graphite alkene solution, commercially available buy can also prepare according to the conventional preparation method, oxygen of the present invention
Graphite alkene source is preferably obtained after ultrasonic disperse by graphite oxide aqueous solution；The present invention is to the graphite oxide without spy
Do not limit, with graphite oxide well known to those skilled in the art, those skilled in the art can according to practical condition,
Product requirement and quality requirement are selected and are adjusted, and graphite oxide of the present invention obtains after preferably being prepared by crystalline flake graphite,
It is obtained after the crystalline flake graphite preparation of more specific preferably piece diameter (size) more than or equal to 50 μm, or more than or equal to 60 μm
Crystalline flake graphite, or the crystalline flake graphite more than or equal to 70 μm, or the crystalline flake graphite more than or equal to 90 μm.The present invention is to institute
The condition for stating ultrasonic disperse is not particularly limited, with the condition of ultrasonic disperse well known to those skilled in the art, this field
Technical staff can select and adjust according to practical condition, product requirement and quality requirement, ultrasound of the present invention
The power of dispersion, which is preferably less than, is equal to 200W, is more preferably less than equal to 180W, is more preferably less than equal to 150W, most preferably
For less than or equal to 120W；The time of the ultrasonic disperse, which is preferably less than, is equal to 2h, is more preferably less than equal to 1.5h, most preferably
For less than or equal to 1h.
The electrolyte is not particularly limited in the present invention, with electrolyte well known to those skilled in the art, ability
Field technique personnel can select and adjust according to practical condition, product requirement and quality requirement, electricity of the present invention
Solution matter preferably includes strong electrolyte or weak electrolyte, and the strong electrolyte preferably includes one of halide, strong acid and highly basic
Or it is a variety of；The weak electrolyte preferably includes one of carbonate, alkali metal salt, alkali salt, weak acid and weak base or more
Kind；The electrolyte is more preferably in carbonate, alkali metal salt, alkali salt, halide, strong acid, highly basic, weak acid and weak base
One or more, more preferably one of carbonate, alkali metal salt, halide, highly basic or weak base or a variety of；It is more specific excellent
Selected from one of ammonium hydrogencarbonate, ammonium carbonate, nickel acetate, nickel chloride, potassium chloride and sodium hydroxide or a variety of, more specifically carbonic acid
Hydrogen ammonia, ammonium carbonate, nickel acetate, nickel chloride, potassium chloride or sodium hydroxide.It should be strongly noted that electrolyte of the present invention
It cannot be strong reducing property electrolyte；When the zwitterion of the electrolyte is weak electrolyte, cation cannot be to be hydrolyzed to hydrogen-oxygen
The weak electrolyte of compound, such as Al3+, Fe2+, Fe3+Deng.
The present invention is added form to the electrolyte and is not particularly limited, and those skilled in the art can be according to practical life
It produces situation, product requirement and quality requirement to be selected and adjusted, electrolyte of the present invention can be electrolyte or electrolyte
Solution, more preferably electrolyte solution.
The additional amount of the electrolyte is not particularly limited in the present invention, and those skilled in the art can be according to actual production
Situation, product requirement and quality requirement are selected and are adjusted, and when electrolyte of the present invention is weak electrolyte, the mixing is molten
The mass ratio of electrolyte described in liquid and the graphene oxide is preferably (5~400): 1, more preferably (10~250): 1, more
Preferably (25~75): 1, most preferably (30~50): 1；When the electrolyte is strong electrolyte, the electrolyte is molten in mixing
In liquid preferably (5~100) with the mass ratio of graphene oxide: 1, more preferably (5~75): 1, more preferably (10~50):
1, most preferably (20~45): 1.
The mixing is not particularly limited in the present invention, is with hybrid mode well known to those skilled in the art and condition
Can, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, the present invention
The mixing is preferably stirred；The mixed time is preferably greater than 1h, more preferably 1~2h, particularly, for carbon
The easy decomposition of sour hydrogen Ammonia or the electrolyte for having week reduction prevent the dispersion behavior for changing graphene oxide, when stirring
Between cannot be greater than 2h.
The mixed solution that the present invention then obtains above-mentioned steps is mixed after filtering again using graphene film as filter membrane
Grapheme material.
It is of the present invention using graphene film as filter membrane, filtering preferably refers to consolidating with graphene filter membrane and filter device again
There is filter medium to be filter medium while being filtered, is successively the first filtering with graphene film more preferably along filtering direction
The filter medium of medium, filter device itself is the second filter medium, that is, when being filtered, the mixed solution filtered is first passed through
Graphene film is filtered, then is filtered by the filter membrane or filter core of filter device itself.
Filtering again of the present invention is preferably filtered under the effect of extraneous pressure field；The present invention is to described in ambient pressure
It filters under field action and does not define particularly, preferably refer to and be filtered under conditions of with pressure difference, be particularly preferred as taking out
Filter or filters pressing, more preferably filter.The device filtered again is not particularly limited in the present invention, with those skilled in the art
Member known to utilize ambient pressure field, that is, there is the filter plant of pressure difference, be particularly preferred as Suction filtration device, paper machine or
Person's filter-pressing device, more preferably sand core Suction filtration device.The present invention is to the inherent filtration medium (filter membrane filter core) filtered again
Selection be not particularly limited, with it is well known to those skilled in the art filtering, filter or filters pressing grapheme material conventional arrangement
, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright filter medium (filter membrane) is preferably one of Kynoar filter membrane, composite fibre resin film and anodic alumina films
Or it is a variety of；Filter medium (filter core) of the present invention is preferably one in PP filter core, ceramic element, resin filter element and glass sand core
Kind is a variety of.The conditions such as the pressure filtered again, temperature and time are not particularly limited in the present invention, with art technology
The conventional arrangement of above-mentioned filter condition known to personnel, those skilled in the art can be according to practical conditions, product
It is required that and quality requirement selected and adjusted, the present invention is preferably adjusted according to liquor capacity and ionic strength, described
The pressure of suction filtration is preferably 0.05~0.5MPa, more preferably 0.1~0.45MPa, more preferably 0.15~0.4MPa, most preferably
For 0.2~0.3MPa.The present invention is to prevent suction filtration process from causing collapsing for graphene-structured, and time/amount of the suction filtration is preferred
Less than or equal to 10min/mL, more preferably less than it is equal to 8min/mL, is more preferably less than equal to 5min/mL.Mistake of the present invention
The end point of the process of filter, preferably using surface solution without obvious mobility as standard.
The admixed graphite alkene material that the present invention finally obtains above-mentioned steps, i.e. graphene oxide/graphene mixing material,
After freeze-drying, the grapheme material with multilevel structure is obtained.
The condition of the freeze-drying is not particularly limited in the present invention, with freeze-drying well known to those skilled in the art
Condition, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement
Whole, the temperature of freeze-drying of the present invention is preferably -100~-10 DEG C, more preferably -90~-30 DEG C, more preferably -90
~-50 DEG C, most preferably -85~-75 DEG C.The time of freeze-drying of the present invention is preferably 12-48 hours, more preferably
20-40 hours, most preferably 24-36 hours.Particularly, it is preferable to use liquid nitrogen etc. can provide the freezing of low temperature rapidly when freezing
Condition.Particularly, it is preferable to use liquid nitrogen etc. can provide the freezing conditions of low temperature rapidly when freezing.
Graphene macroscopic material in practical applications not only needs effectively closely to combine graphene nanosheet,
According to different application demands, the stacking behavior mutual to graphene nanosheet has certain controllability, also will be into one
Required by step has multi-functional aspect, and the structural requirement inside the more grapheme materials of different functions also can be different, still
In existing package technique, when grapheme material is assembled into macroscopic material by nanoscale twins, using single method to structure and function
The regulation of energy is not strong, but will receive distinct methods and different structure, function when on the other hand preparing this material using a variety of methods
Cannot be harmonious between energy, and great difficulty is caused to manufacturing process, or even cannot form.It is micro- that it is difficult to control graphene nano simultaneously
The assembling and arrangement of piece, the only single or extensive assembling for graphene nano material, lead to shape in material assembling process
At three-dimensional perforation disordered networks structure, optimal mechanical performance cannot be played, can not have more structure multifunctionals.Thus,
The present invention is in such a way that pressure field during suction filtration is for graphene microchip ordered arrangement, in addition by the oxidation stone of faint crosslinking
Black alkene mixed solution during suction filtration can gradually gel and fix the graphene microchip of ordered arrangement, to reach regulation graphite
The arrangement mode of alkene microplate；Simultaneously using the spinning of multiple stacking filtering, is acted on using extraneous suction filtration, not only reduce method
Conflict between structure, function, and using the different structure showed during multiple filter between different grapheme materials and
The property of itself and obtain the different material of structure and function and combine in same grapheme material.
Above-mentioned steps of the present invention provide a kind of preparation method of the grapheme material of multilevel structure, on the one hand using electrolysis
Matter can be such that pore structure order increases on the basis for preparing graphene macroscopic material, so that porous graphene structure is orderly controllable；
On the other hand due to having used the mode filtered under ambient pressure field action, prior art preparation grapheme material structure is changed
Densification, the long disadvantage of preparation time, while being acted on using extraneous suction filtration, not only reduce rushing between method and structure, function
It is prominent, and tied using the different structure and the property of itself that show during multiple filter between different grapheme materials
Structure and the different material of function combine in same grapheme material.
Preparation method provided by the invention is prepared for the graphene with multilevel structure/oxidation stone by different raw material
The labyrinth of black alkene has different functionality, while can also effectively control graphene microchip and arrange in an assembling process
Column mode, so that regulation prepares graphene macroscopic material, obtain function it is more excellent there is multilevel structure and orderly microcosmic knot
The graphene macroscopic material of structure.The experimental results showed that the grapheme material of multilevel structure prepared by the present invention, hydrophilic and hydrophobic difference
Structure not only with the porous structure with extremely strong hydrophilic sequential 2 D being made of graphene oxide, but also has
The porous structure with extremely strong hydrophobic three-dimensional perforation being made of grapheme material.
In order to further illustrate the present invention, with reference to embodiments to a kind of graphene of multilevel structure provided by the invention
The preparation method of material (graphene composite material) is described in detail, but it is to be understood that these embodiments are with this hair
Implemented under premised on bright technical solution, the detailed implementation method and specific operation process are given, is only further
Illustrate the features and advantages of the present invention, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to
Following embodiments.
Embodiment 1
1. taking 0.1mg/mL graphene dispersing solution, graphene solution is poured into sand core Suction filtration device, under 0.5MPa pressure
Filter film forming.
2. taking 0.1mg/mL graphene oxide solution, carbon is measured according to graphene oxide and ammonium hydrogen carbonate mass ratio 1:400
Sour hydrogen ammonium, is add to deionized water, and stirring is completely dissolved ammonium hydrogencarbonate, obtains mixed solution.
It is loaded in the sand core Suction filtration device of graphene film 3. mixed solution is poured into, film forming is filtered under 0.5MPa pressure.
4. obtaining having the graphene/graphene oxide of multilevel structure multiple by above-mentioned material in -70 DEG C of freeze-drying 12h
Condensation material.
The ordered porous grapheme material prepared to the embodiment of the present invention 1 detects, and is the present invention referring to Fig. 1, Fig. 1
The scanning electron microscope (SEM) photograph of grapheme material prepared by embodiment 1, the section tool of ordered porous grapheme material prepared by the present invention
There is ordered porous stacked in layers structure, and another section has three-dimensional porous structure, the porous structure of these sequential 2 Ds
It is existed simultaneously with the porous structure of three-dimensional perforation.
Embodiment 2
1. taking 10.0mg/mL graphene dispersing solution, graphene solution is poured into sand core Suction filtration device, 0.05MPa pressure
Lower suction filtration film forming.
2. taking 1.0mg/mL graphene oxide solution, hydrogen-oxygen is measured according to graphene oxide and potassium hydroxide quality ratio 1:5
Change potassium, be add to deionized water, stirs, be completely dissolved potassium hydroxide, obtain mixed solution.
It is loaded in the sand core Suction filtration device of graphene film 3. mixed solution is poured into, film forming is filtered under 0.05MPa pressure.
4. above-mentioned material is obtained the composite material of graphene/graphene oxide in -10 DEG C of freeze-drying 48h.
The ordered porous grapheme material prepared to the embodiment of the present invention 2 detects, and referring to fig. 2, Fig. 2 is the present invention
The scanning electron microscope (SEM) photograph of grapheme material prepared by embodiment 2.
Embodiment 3
1. taking 1.0mg/mL graphene dispersing solution, graphene solution is poured into filter-pressing device, is filtered under 0.10MPa pressure
Film forming.
2. taking 0.5mg/mL graphene oxide solution, chlorination is measured according to graphene oxide and nickel chloride mass ratio 1:25
Nickel is add to deionized water, and stirring is completely dissolved nickel chloride, obtains mixed solution.
3. mixed solution is poured into the filter-pressing device for being loaded with graphene film, film forming is filtered under 0.10MPa pressure.
4. for 24 hours by -100 DEG C of above-mentioned material freeze-dryings, obtaining the composite material of graphene/graphene oxide.
The ordered porous grapheme material prepared to the embodiment of the present invention 3 detects, and is the present invention referring to Fig. 3, Fig. 3
The scanning electron microscope (SEM) photograph of grapheme material prepared by embodiment 3.
Embodiment 4
1. taking 5mg/mL graphene dispersing solution, graphene solution is poured into paper machine, under 0.20MPa pressure filter at
Film.
2. taking 1.75mg/mL graphene oxide solution, measured according to graphene oxide and glacial acetic acid (98%) mass ratio 1:5
Glacial acetic acid (98%), is add to deionized water, stirring, makes glacial acetic acid dilution completely, obtains mixed solution.
3. mixed solution is poured into the paper machine for being loaded with graphene film, film forming is drained under 0.20MPa pressure.
3. above-mentioned material is obtained the composite material of graphene/graphene oxide in -25 DEG C of freeze-drying 36h.
Embodiment 5
1. taking 3.0mg/mL graphene dispersing solution, graphene solution is poured into paper machine, under 0.15MPa pressure filter at
Film.
2. taking 0.1mg/mL graphene oxide solution, nickel chloride is measured according to graphene oxide and sodium chloride mass ratio 100,
It is add to deionized water, stirs, be completely dissolved sodium chloride, obtain mixed solution.
3. mixed solution is poured into the paper machine for being loaded with graphene film, film forming is drained under 0.15MPa pressure.
4. above-mentioned material is obtained the composite material of graphene/graphene oxide in -45 DEG C of freeze-drying 30h.
Detailed Jie has been carried out to a kind of grapheme material of multilevel structure provided by the invention and preparation method thereof above
It continues, used herein a specific example illustrates the principle and implementation of the invention, and the explanation of above embodiments is only
Be be used to help to understand method and its core concept of the invention, including best mode, and but also this field any skill
Art personnel can practice the present invention, including any device or system of manufacture and use, and implement the method for any combination.It should
It points out, it for those skilled in the art, without departing from the principle of the present invention, can also be to this hair
Bright some improvement and modification can also be carried out, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.The present invention is special
The range of benefit protection is defined by the claims, and may include those skilled in the art it is conceivable that other embodiments.Such as
These other embodiments of fruit have the structural element for being not different from claim character express, or if they include and power
Equivalent structural elements of the character express without essence difference that benefit requires, then these other embodiments should also be included in claim
In the range of.
Claims (10)
1. a kind of preparation side of the compound macroscopic material of graphene/graphene oxide with multilevel structure and ordered micro-configuration
Method, which comprises the following steps:
A) by graphene solution after filtering, graphene film is formed；
After graphene oxide solution is mixed with electrolyte, mixed solution is obtained；B) mixed solution for obtaining above-mentioned steps with
Graphene film is filter membrane, obtains admixed graphite alkene material after filtering again；It is described to be filtered into suction filtration again；
The pressure of the suction filtration is 0.05~0.5MPa；
The time of the suction filtration/amount is less than or equal to 10min/mL；
The filter medium filtered again is the filter medium of graphene filter membrane and filter device；
C) the admixed graphite alkene material for obtaining above-mentioned steps by freeze-drying after, obtain with multilevel structure and orderly it is microcosmic
The compound macroscopic material of the graphene/graphene oxide of structure；
The microcosmic ordered structure is specifically, have ordered porous stacked in layers structure, and stacking between layers is formed
Duct in good order.
2. preparation method according to claim 1, which is characterized in that the concentration of the graphene oxide solution be 0.1~
3.5mg/mL。
3. preparation method according to claim 1, which is characterized in that the concentration of the graphene oxide solution be 0.5~
1.0mg/mL。
4. preparation method according to claim 1, which is characterized in that the concentration of the graphene solution is 0.1~10mg/
mL。
5. preparation method according to claim 1, which is characterized in that the electrolyte includes strong electrolyte and/or light current
Xie Zhi；
The strong electrolyte includes one of halide, strong acid and highly basic or a variety of；
The weak electrolyte includes one of carbonate, alkali metal salt, alkali salt, weak acid and weak base or a variety of.
6. preparation method according to claim 1, which is characterized in that the electrolyte is selected from ammonium hydrogencarbonate, ammonium carbonate, second
One of sour nickel, nickel chloride, potassium chloride and sodium hydroxide are a variety of.
7. preparation method according to claim 1, which is characterized in that when the electrolyte is weak electrolyte, the mixing
The mass ratio of electrolyte described in solution and the graphene oxide is (5~400): 1.
8. preparation method according to claim 1, which is characterized in that when the electrolyte is strong electrolyte, the mixing
The mass ratio of electrolyte described in solution and the graphene oxide is (5~100): 1.
9. preparation method according to claim 1, which is characterized in that the temperature of the freeze-drying is -100~-10 DEG C；
The time of the freeze-drying is 12~48h.
10. preparation method according to claim 1, which is characterized in that along filtering direction, the graphene film is the first mistake
Filter medium, the filter medium of the filter device are the second filter medium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610611560.XA CN106241784B (en) | 2016-07-27 | 2016-07-27 | A kind of preparation method of the grapheme material of multilevel structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610611560.XA CN106241784B (en) | 2016-07-27 | 2016-07-27 | A kind of preparation method of the grapheme material of multilevel structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106241784A CN106241784A (en) | 2016-12-21 |
| CN106241784B true CN106241784B (en) | 2019-03-15 |
Family
ID=57605424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610611560.XA Active CN106241784B (en) | 2016-07-27 | 2016-07-27 | A kind of preparation method of the grapheme material of multilevel structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106241784B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992313A (en) * | 2012-12-12 | 2013-03-27 | 常州第六元素材料科技股份有限公司 | High specific surface area graphene with well-developed mesopores, and preparation method thereof |
| CN103508442A (en) * | 2012-06-19 | 2014-01-15 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| CN103663438A (en) * | 2013-11-18 | 2014-03-26 | 南京久和纳米科技有限公司 | Preparation method of porous graphene |
| CN104261392A (en) * | 2014-09-22 | 2015-01-07 | 东南大学 | Preparation method of borate ion crosslinked conductive graphene paper |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833015A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene and preparation method thereof |
| TWI531407B (en) * | 2014-11-20 | 2016-05-01 | 中原大學 | Graphene filtering membrane and method of fabricating the same |
-
2016
- 2016-07-27 CN CN201610611560.XA patent/CN106241784B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508442A (en) * | 2012-06-19 | 2014-01-15 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| CN102992313A (en) * | 2012-12-12 | 2013-03-27 | 常州第六元素材料科技股份有限公司 | High specific surface area graphene with well-developed mesopores, and preparation method thereof |
| CN103663438A (en) * | 2013-11-18 | 2014-03-26 | 南京久和纳米科技有限公司 | Preparation method of porous graphene |
| CN104261392A (en) * | 2014-09-22 | 2015-01-07 | 东南大学 | Preparation method of borate ion crosslinked conductive graphene paper |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106241784A (en) | 2016-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | The assembly of MXenes from 2D to 3D | |
| CN106315563B (en) | A kind of grapheme material of ordered structure and preparation method thereof | |
| Parveen et al. | Manganese oxide as an effective electrode material for energy storage: A review | |
| Yu et al. | Precisely tailoring ZIF-67 nanostructures from cobalt carbonate hydroxide nanowire arrays: toward high-performance battery-type electrodes | |
| Jalili et al. | Processable 2D materials beyond graphene: MoS 2 liquid crystals and fibres | |
| Duan et al. | 3D hierarchical CuO mesocrystals from ionic liquid precursors: towards better electrochemical performance for Li-ion batteries | |
| Sha et al. | Synthesis of well-crystallized Li 4 Ti 5 O 12 nanoplates for lithium-ion batteries with outstanding rate capability and cycling stability | |
| Kumar et al. | Cutting edge composite materials based on MXenes: Synthesis and electromagnetic interference shielding applications | |
| Yang et al. | The hydrothermal synthesis and formation mechanism of single-crystalline perovskite BiFeO 3 microplates with dominant (012) facets | |
| Derakhshan et al. | Review on applications of carboxylate–alumoxane nanostructures | |
| US20130130109A1 (en) | Nanostructured Metal Oxides Comprising Internal Voids and Methods of Use Thereof | |
| Mohammadi et al. | Low temperature nanostructured lithium titanates: controlling the phase composition, crystal structure and surface area | |
| Xie et al. | L-cysteine-assisted preparation of porous NiO hollow microspheres with enhanced performance for lithium storage | |
| CN109110825B (en) | Nickel oxide hollow microsphere with three-level pore structure and preparation method thereof | |
| Cai et al. | TiO 2 mesocrystals: Synthesis, formation mechanisms and applications | |
| Seok et al. | Piezoelectric composite of BaTiO3-coated SnO2 microsphere: Li-ion battery anode with enhanced electrochemical performance based on accelerated Li+ mobility | |
| TWI515949B (en) | Method for making anode material of lithium ion battery | |
| Riaz et al. | Synthesis of stabilized zirconia hollow nanoparticles: sugar as a template | |
| Tang et al. | Synthesis of Micro–Nano-assembled manganese carbonate via aqueous precipitation assisted by ethanol | |
| CN103435037A (en) | Method for preparing graphene/Pt nanocomposite material by liquid phase reduction method | |
| Yin et al. | Synthesis of Mn 3 O 4 octahedrons and other manganese-based nanostructures through a simple and green route | |
| Huang et al. | Graphene-based materials for the separator functionalization of lithium-ion/metal/sulfur batteries | |
| CN106241784B (en) | A kind of preparation method of the grapheme material of multilevel structure | |
| Corr et al. | Spontaneously formed porous and composite materials | |
| KR102152215B1 (en) | Preparation method of needle type metal -silica complex aerogel particle and needle type metal-silica complex aerogel particle prepared by the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220831 Address after: No. 1818, Zhongguan West Road, Zhuangshi street, Zhenhai District, Ningbo City, Zhejiang Province, 315000 Patentee after: NINGBO GRAPHENE INNOVATION CENTER Co.,Ltd. Address before: 315201, No. 519, Zhuang Avenue, Zhenhai District, Zhejiang, Ningbo Patentee before: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES |
|
| TR01 | Transfer of patent right |