CN107915853A - A kind of nano-cellulose/graphene composite and flexible film and preparation method and application - Google Patents
A kind of nano-cellulose/graphene composite and flexible film and preparation method and application Download PDFInfo
- Publication number
- CN107915853A CN107915853A CN201711027485.3A CN201711027485A CN107915853A CN 107915853 A CN107915853 A CN 107915853A CN 201711027485 A CN201711027485 A CN 201711027485A CN 107915853 A CN107915853 A CN 107915853A
- Authority
- CN
- China
- Prior art keywords
- nano
- cellulose
- graphene
- preparation
- composite
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229920002678 cellulose Polymers 0.000 title claims abstract description 90
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 89
- 239000001913 cellulose Substances 0.000 title claims abstract description 83
- 230000009975 flexible effect Effects 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000005518 electrochemistry Effects 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 56
- 239000006185 dispersion Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000010409 thin film Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005411 Van der Waals force Methods 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000011017 operating method Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 239000010931 gold Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 2
- 239000008108 microcrystalline cellulose Substances 0.000 description 2
- 229940016286 microcrystalline cellulose Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B01J35/59—
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
Abstract
The invention discloses a kind of nano-cellulose/graphene composite and flexible film and preparation method and application.This method makes nano-cellulose be uniformly coated on graphene sheet body structure surface, formation is uniformly distributed, nano-cellulose/graphene that surface is smooth using the effect such as the hydrogen bond between nano-cellulose molecule and graphene molecules, Van der Waals force, Π Π keys（CNC‑G）Composite and flexible film.Nano-cellulose/graphene composite and flexible film of the present invention has good pliability and transparency, and can be dispersed in the solvent including water, remains stable over presence.The preparation method of the present invention has the advantages that raw material sources enrich, operating procedure is simple, cost is low, green, environmentally friendly, efficient.Nano-cellulose/graphene of the present invention（CNC‑G）Composite and flexible film purity is high, it is compound uniformly, composition structure it is good, all have broad application prospects in fields such as flexible electronic, catalysis, electrochemistry.
Description
Technical field
Preparation and catalytic applications the present invention relates to thin-film material, and in particular to a kind of nano-cellulose/graphene
Composite and flexible film and preparation method and application.
Background technology
Nano-cellulose（NanoCelluloses）It is a kind of natural reproducible resource, there is excellent mechanical performance, huge
Big specific surface area, high-crystallinity, high-hydrophilic, the high grade of transparency, low-density, flexible accumulator is prepared frequently as basis material
Part, fexible film carrier etc..Due to nano-cellulose have be easy to film forming, gelation, modification, biocompatibility with
And the characteristic such as good mechanical performance, so being the first choice for preparing film material with function.Therefore, exploitation it is a kind of simple, efficiently with
Nano-cellulose has important practical significance for high-flexibility thin-film material of matrix and preparation method thereof.
Graphene（Graphene）It is a kind of monocrystal material of quasi- two dimension.Because of its excellent optics, electricity, thermodynamics and machine
Tool performance etc., is widely used in every field.However, the graphene and nano-cellulose laminated film of high quality are developed at present
The technical research of material is also seldom, and develops graphene with nano-cellulose laminated film in catalysis, energy storage, flexible electronic etc.
Field application is of great significance.
Graphene film interlayer is easy to reunion, surface hydrophobicity, is difficult to form a film；And nano-cellulose surface has abundant hydroxyl
Base, surface hydrophilic, be easy to form a film.Graphene is compound with nano-cellulose, the two mutual supplement with each other's advantages, strong to combine, and prepares high-quality
Measure film material with function.Graphene can occur physically or chemically to act between nano-cellulose, be taken between induction macromolecule
To change, strengthen composite material interface interaction force, so as to improve the mechanical property and pliability of composite film material.
The content of the invention
It is an object of the invention to the development trend for flexible thin-film material, there is provided a kind of nano-cellulose/graphite
Alkene（CNC-G）Composite and flexible film, the CNC-G composite and flexibles film have self-supporting, flexibility and high stability.
The present invention also aims to provide a kind of preparation side of nano-cellulose/graphene composite and flexible film
Method.This method makes to receive using the effect such as the hydrogen bond between nano-cellulose molecule and graphene molecules, Van der Waals force, Π-Π keys
Rice cellulose is uniformly coated on graphene sheet body structure surface, and formation is uniformly distributed, nano-cellulose/graphite that surface is smooth
Alkene（CNC-G）Composite and flexible film.
The present invention also aims to provide a kind of nano-cellulose/graphene composite and flexible film as flexible
The application of cell substrate or flexible catalytic carrier.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of nano-cellulose/graphene composite and flexible film, includes the following steps：
（1）The preparation of nano-cellulose uniform dispersion：Nano-cellulose is disperseed in a solvent, to obtain nano-cellulose and uniformly divide
Dispersion liquid；
（2）The preparation of graphene uniform dispersion：Graphene is added in solvent, then ultrasonic disperse is uniform, obtains graphene uniform
Dispersion liquid；
（3）The preparation of nano-cellulose/graphene composite and flexible film：By nano-cellulose uniform dispersion and graphene uniform
After dispersion liquid mixing, ultrasound, stirring reaction, obtains dispersed colloidal solution, then removes solvent, drying, obtains Nanowire
Tie up element/graphene（CNC-G）Composite and flexible film.
Preferably, step（1）In, the nano-cellulose is obtained by acidolysis or oxidized fibre material.
Preferably, step（1）In, the solvent is deionized water, ethanol or tetrahydrofuran（DMF）.
It is further preferred that step（1）In, the nano-cellulose uniform dispersion is obtained by following steps：
By filter paper（Or microcrystalline cellulose）Add in the sulfuric acid of 64wt% and hydrolyze（Filter paper（Or microcrystalline cellulose）With the sulfuric acid of 64wt%
Solid-liquid ratio be 2:35 g/ml）, 45min is stirred at 45 DEG C, the deionized water for then adding 5 times of reaction solution terminates reaction；Instead
Answer gained suspension to be centrifuged repeatedly with deionized water and wash the unnecessary acid solution of removal, centrifugal condition 10000rmp, 6min, then thoroughly
Analysis is until the pH of water-dialyzing is constant；Dialyzate is directly dispersing in solvent and obtains nano-cellulose uniform dispersion, Huo Zheleng
Jelly is dried to obtain solid nano-cellulose, and redisperse obtains nano-cellulose uniform dispersion in a solvent.
Preferably, step（2）The graphene is obtained using the method for electrochemical stripping graphite or redox graphene
Arrive.
Preferably, step（2）The solvent is deionized water, ethanol or tetrahydrofuran.
Preferably, the concentration of the nano-cellulose uniform dispersion is 10~30 mg/ml.
Preferably, the concentration of the graphene uniform dispersion is 2~10 mg/ml.
Preferably, step（3）In, the mass ratio of graphene uniform dispersion and the nano-cellulose uniform dispersion is
0.2∼5：1.
Preferably, step（3）In, the ultrasonic time is 10~60min, more preferably 10~30min.
Preferably, step（3）In, the temperature of the stirring reaction is 25~60 DEG C, and the time is 20~120min.
Preferably, step（3）In, the solvent that removes is to remove colloid using the method for spin coating, curtain coating or vacuum filtration
Solvent in solution.
Preferably, step（3）In, the drying is the dry 12~24h of 25~60 DEG C of temperature under vacuum.
A kind of nano-cellulose as made from the preparation method described in any of the above-described/graphene composite and flexible film.
A kind of nano-cellulose/graphene composite and flexible the film is as flexible battery substrate or flexible catalytic carrier
Application.
Nano-cellulose/graphene of the present invention（CNC-G）Composite and flexible film pliability is good, and stability is strong, can improve
The service life and active ingredient load capacity of thin-film material.
Compared with prior art, the present invention has the advantage that and technique effect：
（1）Nano-cellulose/graphene of the present invention（CNC-G）Composite and flexible film pliability, stability and transparency are good, can
As transparency electrode, flexible substrates and flexible carrier thin-film material；Thin-film material surface is easy to modify, can be with active component jail
Consolidation is closed, and improves the load capacity and pliability of thin-film material, and can be dispersed in the solvent including water, keeps steady for a long time
It is fixed to exist；
（2）The preparation method raw material sources of the present invention enrich, are renewable, is green, is environmentally friendly, and operating procedure is simple, is easy to control
System, favorable reproducibility, are conducive to mass produce；
（3）Nano-cellulose/graphene of the present invention（CNC-G）Composite and flexible thin-film material purity is high, it is compound uniformly, composition knot
Structure is good, all has broad application prospects in fields such as flexible electronic, catalysis, electrochemistry.
Brief description of the drawings
Fig. 1 a, Fig. 1 b and Fig. 1 c are that nano-cellulose/graphene (CNC-G) composite and flexible film prepared by embodiment 1 exists
TEM figures under different multiplying；
Fig. 1 d are golden@nano-celluloses/graphene prepared by embodiment 1（Au@CNC-G）The TEM of composite and flexible film catalyst
Figure；
Fig. 1 e and Fig. 1 f are golden@nano-celluloses/graphene prepared by embodiment 1（Au@CNC-G）Composite and flexible film catalyst
High power TEM figures under different multiplying；
Fig. 2 is golden@nano-celluloses/graphene prepared by embodiment 1（Au@CNC-G）Composite and flexible film catalyst catalytic water
A in system3The cycle life test chart of coupling reaction.
Embodiment
Technical solution of the present invention is further illustrated below in conjunction with specific embodiment and attached drawing, but the protection of the present invention
Scope not limited to this.
In the specific embodiment of the invention, nano-cellulose aqueous solution is prepared via a method which to obtain：
20g filter paper is added in the sulfuric acid of 350ml 64wt%, 45min hydrolysis is stirred at 45 DEG C；Then add 5 times of reaction solution
Deionized water terminate reaction, terminate gained suspension after reaction and be centrifuged repeatedly washing with deionized water and remove unnecessary acid solution,
Centrifugal condition is 10000rpm, 6min；Dialyse again until water-dialyzing pH it is constant, dialyzate is then directly dispersing in deionization
In water, nano-cellulose aqueous solution is obtained.
Embodiment 1
Nano-cellulose/graphene（CNC-G）The preparation of composite and flexible film, specifically comprises the following steps：
（1）Graphene is compound with nano-cellulose：By the nano-cellulose aqueous solution and 40ml 4.8mg/ml of 10ml 19mg/ml
Graphene aqueous dispersions mixed under 25 DEG C of stirring conditions after（Graphene uniform dispersion and nano-cellulose uniform dispersion
Mass ratio is 1:1）, ultrasonic 30min, stirs 60min under room temperature, obtains uniformly mixed colloidal solution；
（2）By step（1）The colloidal solution of gained is washed using the method for vacuum filtration and is removed excess of solvent, uses deionized water
Three times, ethanol washed once for washing, then 60 DEG C of vacuum drying 12h, obtain nano-cellulose/graphene（CNC-G）Composite and flexible
Film.
（3）To step（1）The HAuCl of 0.5ml 0.12M is added in the colloidal solution of gained4Ethanol solution, at normal temperatures
60min is stirred, obtains aqueous solution of the gold nano grain uniform load in nano-cellulose/Graphene composite thin film material；It is true again
Sky filters, and is washed with deionized three times, and ethanol washed once, and then 60 DEG C of 12 h of vacuum drying, obtain golden@nanofibers
Element/graphene（Au@CNC-G）Composite and flexible film.
Nano-cellulose/graphene of preparation（CNC-G）Composite and flexible film gray, transparency is low, and pliability is good, can
Fold and restore to the original state at 0 ~ 180 °.
Nano-cellulose/graphene of preparation（CNC-G）Scanning transmission electron microscope of the composite and flexible film under different multiplying
（TEM）Figure is as shown in Fig. 1 a, Fig. 1 b and Fig. 1 c, golden@nano-celluloses/graphene of preparation（Au@CNC-G）Composite and flexible film
Scanning transmission electron microscope under different multiplying（TEM）Figure is as shown in Fig. 1 d, Fig. 1 e and Fig. 1 f；It can be seen by Fig. 1 a, Fig. 1 b and Fig. 1 c
The pattern smooth to graphene surface, illustrates that nano-cellulose is uniformly covered on graphene film layer surface；By Fig. 1 d, Fig. 1 e and
Fig. 1 f can be seen that the formation for having gold nano grain in preparation process and uniformly be scattered in nano-cellulose/graphene
（CNC-G）On composite and flexible film surface, formation and growth course of the film to gold nano grain play regulating and controlling effect.
Golden@nano-celluloses/graphene of preparation（Au@CNC-G）Composite and flexible film stablizes immersion after three weeks in water,
Pattern and structure keep complete, it is shown that the strong hydrothermal stability of the thin-film material and pliability.
Nano-cellulose/graphene（CNC-G）Application of the composite and flexible film as flexible carrier：
By golden@nano-celluloses/graphene of preparation（Au@CNC-G）Composite and flexible film is used as catalyst, is catalyzed in water system
Aldehyde, alkynes, amine（A3）Three components " one pot " organic synthesis, golden@nano-celluloses/graphene（Au@CNC-G）Composite and flexible is thin
A in film catalyst catalysis water system3The cycle life test chart of coupling reaction is as shown in Fig. 2, as seen from Figure 2, the golden@of preparation
Nano-cellulose/graphene composite and flexible film has excellent catalytic performance（Efficiency of pcr product is 95%）With long recycling
Service life（After 10 times recycle, catalytic activity is held essentially constant）.
Embodiment 2
Nano-cellulose/graphene（CNC-G）The preparation of composite and flexible film, specifically comprises the following steps：
（1）Graphene is compound with nano-cellulose：By the nano-cellulose aqueous solution and 8ml 4.8mg/ml of 10ml 19mg/ml
Graphene aqueous dispersions after 40 DEG C are stirred（Graphene uniform dispersion and nano-cellulose uniform dispersion mass ratio
For 0.2:1）, ultrasonic 30min, stirs 60min under room temperature, obtains uniformly mixed colloidal solution；
（2）By step（1）The colloidal solution of gained is washed using the method for vacuum filtration and is removed excess of solvent, uses deionized water
Three times, ethanol washed once for washing, then 60 DEG C of 12 h of vacuum drying, obtain nano-cellulose/graphene（CNC-G）Composite and flexible
Film.
Nano-cellulose/graphene of preparation（CNC-G）Composite and flexible film is presented colourful transparent and presents very well
Pliability, fold 180 ° after resilient and keep original performance constant.
Embodiment 3
Nano-cellulose/graphene（CNC-G）The preparation of composite and flexible film, specifically comprises the following steps：
（1）Graphene is compound with nano-cellulose：By the nano-cellulose aqueous solution and 20ml 4.8mg/ml of 1ml 19mg/ml
Graphene aqueous dispersions after 60 DEG C are stirred（Graphene uniform dispersion and nano-cellulose uniform dispersion mass ratio
For 5:1）, ultrasonic 30min, stirs 60min under room temperature, obtains uniformly mixed colloidal solution；
（2）By step（1）The colloidal solution of gained is washed using the method for vacuum filtration and is removed excess of solvent, uses deionized water
Three times, ethanol washed once for washing, then 60 DEG C of 12 h of vacuum drying, obtain nano-cellulose/graphene（CNC-G）Composite and flexible
Film.
Nano-cellulose/graphene of preparation（CNC-G）Composite and flexible film is presented black and opaque, film also compared with
Thickness, but pliability still can be kept after 180 ° of folding.
Nano-cellulose/graphene prepared by comparative example 1 ~ 3（CNC-G）Composite and flexible film, graphene uniform point
Dispersion liquid and nano-cellulose uniform dispersion mass ratio are followed successively by 1:1、0.2:1 and 5:1, with the increase of graphene ratio,
Nano-cellulose/graphene composite and flexible film（CNC-G）Transparency reduce, but flexility preferably maintains.This is main
It is due to that the amount of graphene is continuously increased so that nano-cellulose/graphene composite film is colored and transparency constantly declines, and
Thickness, electric conductivity and the mechanical tensile strength of composite membrane are continuously improved, and pliability is kept substantially.
Above example is only preferrred embodiment of the present invention, is only used for explaining the present invention, is not intended to limit the present invention, this
Change that field technology personnel are made under without departing from spirit of the invention, replacement, modification etc. should all belong to the guarantor of the present invention
Protect scope.
Claims (10)
1. the preparation method of a kind of nano-cellulose/graphene composite and flexible film, it is characterised in that include the following steps：
（1）The preparation of nano-cellulose uniform dispersion：Nano-cellulose is disperseed in a solvent, to obtain nano-cellulose and uniformly divide
Dispersion liquid；
（2）The preparation of graphene uniform dispersion：Graphene is added in solvent, then ultrasonic disperse is uniform, obtains graphene uniform
Dispersion liquid；
（3）The preparation of nano-cellulose/graphene composite and flexible film：By nano-cellulose uniform dispersion and graphene uniform
After dispersion liquid mixing, ultrasound, stirring reaction, obtains dispersed colloidal solution, then removes solvent, drying, obtains Nanowire
Tie up element/graphene composite and flexible film.
2. preparation method according to claim 1, it is characterised in that step（1）In, the nano-cellulose is to pass through acid
Solution or oxidized fibre material obtain；The solvent is deionized water, ethanol or tetrahydrofuran.
3. preparation method according to claim 1, it is characterised in that step（2）In, the graphene is to use electrochemistry
The method for peeling off graphite or redox graphene obtains；The solvent is deionized water, ethanol or tetrahydrofuran.
4. preparation method according to claim 1, it is characterised in that the concentration of the nano-cellulose uniform dispersion is
10∼30 mg/ml。
5. preparation method according to claim 1, it is characterised in that the concentration of the graphene uniform dispersion is 2~10
mg/ml。
6. preparation method according to claim 1, it is characterised in that step（3）In, the graphene uniform dispersion and
The mass ratio of nano-cellulose uniform dispersion is 0.2~5：1.
7. preparation method according to claim 1, it is characterised in that step（3）In, the ultrasonic time for 10~
60min；The temperature of the stirring reaction is 25~60 DEG C, and the time is 20~120min.
8. preparation method according to claim 1, it is characterised in that step（3）In, the removing solvent is using rotation
The method for applying, being cast or being filtered by vacuum removes the solvent in colloidal solution；The drying is temperature 25~60 under vacuum
DEG C dry 12~24h.
9. a kind of nano-cellulose/graphene composite and flexible as made from claim 1-8 any one of them preparation methods is thin
Film.
10. a kind of nano-cellulose/graphene composite and flexible film described in claim 9 is as flexible battery substrate or flexibility
The application of catalytic carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711027485.3A CN107915853A (en) | 2017-10-27 | 2017-10-27 | A kind of nano-cellulose/graphene composite and flexible film and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711027485.3A CN107915853A (en) | 2017-10-27 | 2017-10-27 | A kind of nano-cellulose/graphene composite and flexible film and preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107915853A true CN107915853A (en) | 2018-04-17 |
Family
ID=61895076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711027485.3A Pending CN107915853A (en) | 2017-10-27 | 2017-10-27 | A kind of nano-cellulose/graphene composite and flexible film and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107915853A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108584934A (en) * | 2018-04-26 | 2018-09-28 | 湖南大学 | A kind of sulfonic functional graphene dispersion system and preparation method thereof |
| CN108794815A (en) * | 2018-02-12 | 2018-11-13 | 王清扬 | Including the composite material of graphene, preparation method and gas sensor |
| CN109378110A (en) * | 2018-09-26 | 2019-02-22 | 浙江理工大学 | Cellulose with pressure drag sensitivity/graphene nanometer sheet flexible conductive composite material preparation method |
| CN109385928A (en) * | 2018-11-02 | 2019-02-26 | 陕西科技大学 | A kind of nano-cellulose/aramid nano-fiber film composite Nano paper and preparation method thereof |
| CN109762206A (en) * | 2019-01-23 | 2019-05-17 | 陕西科技大学 | Photochromic adjustable fluorescence oxidation nanometer cellophane of one kind and preparation method thereof |
| CN109942720A (en) * | 2019-03-29 | 2019-06-28 | 济南圣泉集团股份有限公司 | A kind of nano cellulose material and its preparation method and application |
| CN110090563A (en) * | 2019-04-12 | 2019-08-06 | 华南理工大学 | A kind of nano hybrid film and the preparation method and application thereof of self-cleaning GO modification CNC |
| CN110204791A (en) * | 2019-07-03 | 2019-09-06 | 桂林理工大学 | A kind of acid imide functionalization graphene/sisal cellulose nano microcrystalline composite heat-conducting film and preparation method thereof |
| CN110240238A (en) * | 2019-06-19 | 2019-09-17 | 北京化工大学 | A kind of rolled electrode preparation method for capacitor desalination |
| CN110292864A (en) * | 2019-06-12 | 2019-10-01 | 时代沃顿科技有限公司 | A kind of preparation method of composite nano materials hybridized film and the hybridized film thus prepared |
| CN110581267A (en) * | 2019-09-16 | 2019-12-17 | 哈尔滨工业大学 | nano-cellulose-silicon-graphite micron sheet flexible electrode material and preparation method and application thereof |
| WO2020113430A1 (en) * | 2018-12-04 | 2020-06-11 | 京东方科技集团股份有限公司 | Graphene-based conductive structure, manufacturing method for same, and self-repairing method |
| CN111518317A (en) * | 2020-05-13 | 2020-08-11 | 上海交通大学 | High-thermal-conductivity and water-transmission composite film material and preparation method and application thereof |
| CN111896593A (en) * | 2020-08-13 | 2020-11-06 | 陕西科技大学 | Asymmetric film type humidity sensor and preparation method thereof |
| CN114920995A (en) * | 2022-04-01 | 2022-08-19 | 西北工业大学 | Graphene/nano-cellulose laminated microstructure, preparation method, device and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910398A (en) * | 2014-03-12 | 2015-09-16 | 中国科学院金属研究所 | Nanocellulose-assisted preparation method of high-content graphene flexible conductive composite membrane |
| CN105860143A (en) * | 2016-05-14 | 2016-08-17 | 上海大学 | Flexible nanocellulose-graphene composite membrane and preparation method thereof |
| US20160340520A1 (en) * | 2014-09-17 | 2016-11-24 | National University Corporation Nagoya University | Conducting composition and method for producing the same |
| CN106633791A (en) * | 2016-10-20 | 2017-05-10 | 国家纳米科学中心 | Preparation method of nano-cellulose-based flexible conductive film |
| CN107293377A (en) * | 2017-07-07 | 2017-10-24 | 齐鲁工业大学 | A kind of preparation method of tough graphene/cellulose composite heat-conducting conductive film |
-
2017
- 2017-10-27 CN CN201711027485.3A patent/CN107915853A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910398A (en) * | 2014-03-12 | 2015-09-16 | 中国科学院金属研究所 | Nanocellulose-assisted preparation method of high-content graphene flexible conductive composite membrane |
| US20160340520A1 (en) * | 2014-09-17 | 2016-11-24 | National University Corporation Nagoya University | Conducting composition and method for producing the same |
| CN105860143A (en) * | 2016-05-14 | 2016-08-17 | 上海大学 | Flexible nanocellulose-graphene composite membrane and preparation method thereof |
| CN106633791A (en) * | 2016-10-20 | 2017-05-10 | 国家纳米科学中心 | Preparation method of nano-cellulose-based flexible conductive film |
| CN107293377A (en) * | 2017-07-07 | 2017-10-24 | 齐鲁工业大学 | A kind of preparation method of tough graphene/cellulose composite heat-conducting conductive film |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794815A (en) * | 2018-02-12 | 2018-11-13 | 王清扬 | Including the composite material of graphene, preparation method and gas sensor |
| CN108794815B (en) * | 2018-02-12 | 2021-07-06 | 王清扬 | Composite material containing graphene, preparation method and gas sensor |
| CN108584934A (en) * | 2018-04-26 | 2018-09-28 | 湖南大学 | A kind of sulfonic functional graphene dispersion system and preparation method thereof |
| CN109378110B (en) * | 2018-09-26 | 2020-01-21 | 浙江理工大学 | Preparation method of cellulose/graphene nanosheet flexible conductive composite material with piezoresistive sensing performance |
| CN109378110A (en) * | 2018-09-26 | 2019-02-22 | 浙江理工大学 | Cellulose with pressure drag sensitivity/graphene nanometer sheet flexible conductive composite material preparation method |
| CN109385928A (en) * | 2018-11-02 | 2019-02-26 | 陕西科技大学 | A kind of nano-cellulose/aramid nano-fiber film composite Nano paper and preparation method thereof |
| CN109385928B (en) * | 2018-11-02 | 2021-04-06 | 陕西科技大学 | Nano cellulose/aramid nano fiber film composite nano paper and preparation method thereof |
| WO2020113430A1 (en) * | 2018-12-04 | 2020-06-11 | 京东方科技集团股份有限公司 | Graphene-based conductive structure, manufacturing method for same, and self-repairing method |
| CN111566157A (en) * | 2018-12-04 | 2020-08-21 | 京东方科技集团股份有限公司 | Graphene conductive structure, preparation method thereof and self-repairing method thereof |
| CN111566157B (en) * | 2018-12-04 | 2022-08-09 | 京东方科技集团股份有限公司 | Graphene conductive structure, preparation method thereof and self-repairing method thereof |
| CN109762206A (en) * | 2019-01-23 | 2019-05-17 | 陕西科技大学 | Photochromic adjustable fluorescence oxidation nanometer cellophane of one kind and preparation method thereof |
| CN109942720A (en) * | 2019-03-29 | 2019-06-28 | 济南圣泉集团股份有限公司 | A kind of nano cellulose material and its preparation method and application |
| CN110090563A (en) * | 2019-04-12 | 2019-08-06 | 华南理工大学 | A kind of nano hybrid film and the preparation method and application thereof of self-cleaning GO modification CNC |
| WO2020248433A1 (en) * | 2019-06-12 | 2020-12-17 | 时代沃顿科技有限公司 | Method for preparing composite nano-material hybrid membrane and hybrid membrane prepared thereby |
| CN110292864B (en) * | 2019-06-12 | 2021-05-28 | 时代沃顿科技有限公司 | Preparation method of composite nano-material hybrid membrane and hybrid membrane prepared by same |
| CN110292864A (en) * | 2019-06-12 | 2019-10-01 | 时代沃顿科技有限公司 | A kind of preparation method of composite nano materials hybridized film and the hybridized film thus prepared |
| CN110240238A (en) * | 2019-06-19 | 2019-09-17 | 北京化工大学 | A kind of rolled electrode preparation method for capacitor desalination |
| CN110240238B (en) * | 2019-06-19 | 2020-11-27 | 北京化工大学 | Preparation method of coiled electrode for capacitive desalination |
| CN110204791A (en) * | 2019-07-03 | 2019-09-06 | 桂林理工大学 | A kind of acid imide functionalization graphene/sisal cellulose nano microcrystalline composite heat-conducting film and preparation method thereof |
| CN110581267A (en) * | 2019-09-16 | 2019-12-17 | 哈尔滨工业大学 | nano-cellulose-silicon-graphite micron sheet flexible electrode material and preparation method and application thereof |
| CN111518317A (en) * | 2020-05-13 | 2020-08-11 | 上海交通大学 | High-thermal-conductivity and water-transmission composite film material and preparation method and application thereof |
| CN111518317B (en) * | 2020-05-13 | 2021-12-28 | 上海交通大学 | High-thermal-conductivity and water-transmission composite film material and preparation method and application thereof |
| CN111896593A (en) * | 2020-08-13 | 2020-11-06 | 陕西科技大学 | Asymmetric film type humidity sensor and preparation method thereof |
| CN111896593B (en) * | 2020-08-13 | 2023-03-31 | 陕西科技大学 | Asymmetric film type humidity sensor and preparation method thereof |
| CN114920995A (en) * | 2022-04-01 | 2022-08-19 | 西北工业大学 | Graphene/nano-cellulose laminated microstructure, preparation method, device and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107915853A (en) | A kind of nano-cellulose/graphene composite and flexible film and preparation method and application | |
| CN105949512B (en) | Intercalation assembling boron nitride-graphene composite material, using and preparation method thereof | |
| CN104724699B (en) | Method for preparing biomass graphene employing cellulose as raw material | |
| CN102581267B (en) | Silver-graphene composite material and method for conveniently producing silver-graphene composite material | |
| CN105601966B (en) | A kind of nano micro crystal cellulose based conductive film preparation method | |
| CN103956470B (en) | Preparation method of a kind of two-dimensional layer laminated film and products thereof and application | |
| CN106920696B (en) | Nano hybridization aeroge electrode material for super capacitor and its preparation method and application | |
| CN105502342A (en) | Method for preparing nanometer hollow carbon spheres with dopamine serving as carbon source | |
| JP6127446B2 (en) | Battery electrode composition and method for producing the same, battery electrode and method for producing the same | |
| CN105719850A (en) | Grapheme@polypyrrole/layer double hydroxide nanowire ternary composite and preparation method and application thereof | |
| CN105111507A (en) | Preparation method and application of bacterial cellulose/polyaniline/carbon nanotube conducting film material | |
| CN103480406A (en) | Nitrogen-doped graphene/nitrogen-doped carbon nanotube/tricobalt tetraoxide composite paper and preparation method thereof | |
| CN109592684B (en) | Petal spherical titanium carbide Ti3C2Mxene and preparation method and application thereof | |
| CN106012678A (en) | Process for preparing cobalt selenide composite carbon paper | |
| CN103762356B (en) | Ni nano wire, NiO/Ni self-supported membrane and its preparation method and application | |
| CN104852069A (en) | Preparation method and application of self-support sulfonic acid funtionalized graphene oxide paper having holes in surface | |
| CN111574738B (en) | Preparation method of nano cellulose-based bionic heterogeneous membrane material | |
| CN107001699A (en) | Cellulose base functional composite material, energy storage device and preparation method thereof | |
| CN105070522B (en) | Graphene/titania nanotube prepares flexible bending folding thin-film electrode | |
| CN115260551A (en) | Preparation method of light graphene film for aerospace cable | |
| CN106098396B (en) | It is a kind of for upright opening carbon compound film of ultracapacitor and preparation method thereof | |
| CN103388197A (en) | Preparation method of graphene fiber | |
| CN107195937A (en) | Compound alkalescence polyelectrolyte film and preparation method thereof and alkaline polyelectrolyte fuel cell | |
| CN109742363A (en) | One kind may be implemented graphene and closely coats SiO negative materials and preparation method thereof | |
| CN110438845B (en) | Hydrophilic graphene, cellulose-based graphene flexible conductive nano-paper and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180417 |
|
| RJ01 | Rejection of invention patent application after publication |