CN105504093A - Method for preparing membrane electrode from chitin nano fiber/carbon nanotube composite - Google Patents
Method for preparing membrane electrode from chitin nano fiber/carbon nanotube composite Download PDFInfo
- Publication number
- CN105504093A CN105504093A CN201610030429.4A CN201610030429A CN105504093A CN 105504093 A CN105504093 A CN 105504093A CN 201610030429 A CN201610030429 A CN 201610030429A CN 105504093 A CN105504093 A CN 105504093A
- Authority
- CN
- China
- Prior art keywords
- chitin
- nano fiber
- carbon nanotube
- chitin nano
- membrane electrode
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- 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
-
- 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
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for preparing a flexible bendable membrane electrode from a chitin nano fiber/carbon nanotube composite, which comprises the following steps: a) preparing the chitin nano fiber/carbon nanotube composite from carapace kitchen waste products by a simple chemical-mechanical process; and b) mixing the chitin nano fiber/carbon nanotube composite with a carbon nanotube dispersion solution. The membrane electrode maintains more pore structures, is beneficial to permeation and absorption of the electrolyte, and enhances the electron and ion transfer speed; the chitin nano fibers have higher mechanical strength, and have favorable biocompatibility with the carbon nanotubes, so that the mixture of the chitin nano fibers and carbon nanotubes eliminates the phenomenon of high agglomeration tendency when the chitin nano fibers and carbon nanotubes are used respectively; the chitin nano fibers used as the substrate provide firm attachment and support for the carbon nanotubes, and are a flexible sheet; and in the microscopic view, the two materials are wound and penetrate mutually to form the three-dimensional porous interpenetrating firm network. No adhesive is added, so the membrane electrode has favorable heat stability and flexibility, and can be used as an electrode material for portable electronic products.
Description
Technical field
What the present invention relates to is the method that a kind of chitin nano fiber/carbon nanotube compound prepares flexible membrane electrode, belongs to combined electrode field.
Background technology
Chitin is that occurring in nature is only second to cellulosic second largest renewable resources in the world, with product abandonment shrimp, crab shell more than kitchen for starting material, abundance, output are considerable, both save energy, reduce the waste of resource, alleviate environmental pollution, give full play to again the residue function of discarded shrimp, crab shell, reclaiming, to turn waste into wealth.
Along with the development of science and technology, the use of electronic component enters huge numbers of families, and electrode is as the energy-storage travelling wave tube be concerned in recent years, and it has, and energy density is large, power density advantages of higher, have a wide range of applications in future, particularly portable electronics, redundant electrical power etc.At present, countries in the world all in preparation technology and the use thereof of Electrode material, also just develop rapidly in China, thus show huge application potential.
Many as the research in electrode materials about carbon nanotube, but, the research that chitin compound prepares electrode is almost had no.In order to improve the actual application prospect of this type of material as electrode materials, be badly in need of exploring a kind of cheap, technology easily process means carry out batch and prepare chitin nano fiber/carbon nano-tube combination electrode material.The present invention is devoted to " animal fiber " of abundance---chitin is as the source of nanofiber, compound is carried out as matrix and carbon nanotube, both are interweaved winding, UNICOM's conductive network, belong to the more novel forward-looking research direction of whole world electrode field.
Summary of the invention
The present invention proposes the method that a kind of chitin nano fiber/carbon nanotube compound prepares flexible membrane electrode, object is to prepare that mechanical strength is high, stable charge/discharge strong, have extended cycle life and can the thin-film electrode material of bending fold, is applied to ultracapacitor.
Technical solution of the present invention: chitin nano fiber/carbon nanotube compound prepares the method for flexible membrane electrode, comprises following processing step: a) more than crustaceans kitchen product by simple chemical-mechanical legal system for chitin nano fiber; B) the mixing of chitin nano fiber and carbon nano tube dispersion liquid.
Advantage of the present invention:
1) remain more pore texture, be conducive to the osmotic absorption of electrolytic solution, improve electronics and ion-transfer speed; Simultaneously, chitin nano fiber has higher physical strength, with carbon nanotube, there is good biocompatibility, both not only eliminate the phenomenon of easily reuniting separately at mixing, and using chitin nano fiber as substrate, give carbon nanotube and firmly adhere to support, macroscopically it seems it is a flexible sheet material, under microcosmic, bi-material is mutually wound around and runs through, and forms the firm network of three-dimensional porous IPN.
2) composite film electrode prepared does not add any sizing agent, and thermostability and snappiness are all fine, can use as the electrode materials of portable type electronic product.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention 1 provides the ~ Electronic Speculum figure of laminated film.
Fig. 2 is mechanical property figure and the film pictorial diagram of the composite film electrode that the embodiment of the present invention 1 provides.
Fig. 3 is the electric conductivity comparison diagram of the composite film electrode that the embodiment of the present invention 1 provides.
Fig. 4 is the electrochemical analysis figure of the composite film electrode that the embodiment of the present invention 1 provides.
Embodiment
Chitin nano fiber/carbon nanotube compound prepares the method for flexible membrane electrode, comprises following processing step: a) more than crustaceans kitchen product by simple chemical-mechanical legal system for chitin nano fiber; B) the mixing of chitin nano fiber and carbon nano tube dispersion liquid.
More than described step a) crustaceans kitchen, product is by simple chemical-mechanical legal system for chitin nano fiber, and its method comprises the following steps:
(1) shrimp of recovery, crab husk as raw material is chosen, use electronic balance accurately to take 10g after cleaning, drying and put into beaker, add 600ml deionized water, leave standstill 24h with under the hydrochloric acid HCl normal temperature condition of 5-7wt%, to remove the calcium carbonate in chitin, use a large amount of deionized water rinsing to neutral afterwards;
(2) shrimp, crab shell being soaked in concentration is in the potassium hydroxide solution of 5%, is placed in the water-bath 6h of 95 DEG C, removes the protein in shrimp, crab shell, uses a large amount of deionized water rinsings to neutral afterwards; This process repeats four times, to guarantee fully to remove protein;
(3) shrimp, the crab shell after process is placed in the ethanolic soln 24h of 75%, sealing and standing, to remove pigment, post-flush can obtain purifying chitin to neutrality;
(4) glacial acetic acid solution of 0.1 ~ 0.5wt% is adopted, purifying chitin 1 ~ 2h that treatment step (3) obtains at 35 DEG C;
(5) the purifying chitin that step (4) step obtains is made into the suspension that concentration is 0.8 ~ 1wt%, milled processed 10 ~ 15 minutes, obtains the chitin nano fiber of diameter at 10 ~ 30nm.
Described step b) chitin nano fiber mixes with carbon nano tube dispersion liquid, and its method comprises the following steps:
(1) after being dried by carbon nanotube, accurate weighing 10 ~ 50mg adds in 250ml deionized water;
(2) weigh Sodium dodecylbenzene sulfonate 50 ~ 200mg, add the solution in step (1), glass stick stirs 2 minutes;
(3) carbon nano tube suspension that step (2) obtains is placed in ice-water bath, utilize ultrasonic grinding instrument supersound process 30 ~ 90 minutes, the solution after ultrasonic presents homodisperse state, and sediment-free amasss at the bottom of cup; Supersound process refers to that the ultrasonication time is 1s, gap 2s, ultrasonic power 800W;
(4) carbon nano tube dispersion liquid 250ml step (3) obtained places in ice-water bath;
(5) the chitin nano fiber 1 ~ 5g getting 0.8 ~ 1wt% of step a) gained joins in step (4) gained dispersion liquid, utilizes the ultrasonic mixing of ultrasonic grinding instrument 15 ~ 30 minutes; Ultrasonic mixing refers to that the ultrasonication time is 1s, gap 2s, ultrasonic power 500 ~ 800W, in ultrasonic mixing, because Sodium dodecylbenzene sulfonate contains aromatic ring structure, the while that the hydrophobic part of aliphatic chain and carbon nanotube being interactional, aromatic nucleus also interacts with the P-P of carbon nanotube, dispersiveness is relatively high, and the uniform dispersion stability formed is better;
(6) the ultrasonic mixed solution 100-300ml of step (5) gained is got, carry out vacuum filtration, after film forming, put into the moisture that ethanolic soln replaces film, and after filter membrane stripping, utilize freeze drier drying treatment under setting pressure, after 2 ~ 5h, can composite film electrode be obtained.
More than described crustaceans kitchen, product refers to the biological material containing chitin, and carbon nanotube comprises Single Walled Carbon Nanotube and multi-walled carbon nano-tubes.
Described simple chemistry-mechanical process is use four kinds of pharmaceutical chemicalss: hydrochloric acid, Glacial acetic acid, potassium hydroxide and ethanol just can reach well separates fine effect, and mechanical process uses shredder, compared to ultrasonic method and homogeneous method, more effectively, energy-conservation and be more conducive to realize suitability for industrialized production.
More than described biomass kitchen, product adopts the Glacial acetic acid stirring at normal temperature of 0.1 ~ 0.5wt% by the step (4) that simple chemistry-mechanical process is prepared in chitin nano fiber, to reach, moistening rises separates fine object, because there is crystallizing field and noncrystalline domain in biomacromolecule chain; The spacing of crystallizing field is little, very large by hydrogen bonded intensity between molecular chain; And noncrystalline domain distance is comparatively large, combined by Van der Waals force between molecular chain, intensity is more weak; In the process of soaking and stirring, Glacial acetic acid immerses pars amorpha, by noncrystalline domain profit, widen the distance of crystallizing field molecular chain simultaneously, most of hydrogen bond is destroyed and forms Van der Waals force, play and separate fine object, then can obtain chitin nano fiber by mechanical force process.
More than described biomass kitchen, product is adopt shredder to carry out " one-timepass " (polishing) to obtain chitin nano fiber by step (5) milled processed that simple chemistry-mechanical process is prepared in chitin nano fiber/carbon nanotube compound, the rotating speed of grinding is 1500r/min, scale is about-8.5, through Glacial acetic acid process, hydroxyl in chitin fiber molecular chain is opened by swollen, add the fricting shearing of grinding stone in shredder and the centrifugal force of high-speed rotation generation, distance between chitin fiber tube bank is widened, bonding force is destroyed, by once grinding the chitin nano fiber just can prepared and have compared with high length-diameter ratio.
The present invention is introduced in detail below in conjunction with accompanying drawing and embodiment thereof.
Embodiment 1
The preparation method of chitin extraction nanofiber from shrimp shell, comprise step (1) and choose the shrimp shell eaten, use electronic balance accurately to take 10g after cleaning, drying and put into beaker, add 600ml deionized water, 24h is left standstill with under hydrochloric acid (HCl) normal temperature condition of 7wt%, to remove the calcium carbonate in shrimp shell, use a large amount of deionized water rinsing to neutral afterwards;
It is in potassium hydroxide (KOH) solution of 5% that shrimp shell is soaked in concentration by step (2), is placed in the water-bath 6h of 95 DEG C, removes the protein in shrimp shell, uses a large amount of deionized water rinsings to neutral afterwards; This process repeats four times, to guarantee fully to remove protein;
Step (3) by process after shrimp shell be placed in 75% ethanolic soln 24h, sealing and standing, to remove pigment, post-flush can obtain purifying chitin to neutrality;
Step (4) adopts the glacial acetic acid solution of 0.5wt%, processes the purifying chitin 2h that the 3rd step obtains at 35 DEG C;
The purifying chitin that 4th step obtains is made into the suspension that concentration is 0.8wt% by step (5), milled processed 15 minutes, obtains the chitin nano fiber of diameter at 10 ~ 30nm;
The preparation method of chitin nano fiber and carbon nano-tube coextruded film electrode: comprise
Carbon nanotube is dried rear accurate weighing 20mg and is added in 250ml deionized water by step (1);
Step (2) weighs Sodium dodecylbenzene sulfonate (SDBS) 100mg, and add (1) solution, glass stick stirs 2 minutes;
The carbon nano tube suspension that step (2) obtains is placed in ice-water bath by step (3), utilize ultrasonic grinding instrument supersound process 60 minutes (ultrasonication time 1s, gap 2s, power 800W), solution after ultrasonic presents homodisperse state, and sediment-free amasss at the bottom of cup;
The carbon nano tube dispersion liquid 250ml that step (3) obtains by step (4) places in ice-water bath;
The chitin nano fiber 2.5g that step (5) gets the 0.8wt% of step a) gained joins in step (4) gained dispersion liquid, utilizes the ultrasonic mixing of ultrasonic grinding instrument 15 minutes (ultrasonication time 1s, gap 2s, power 800W);
The ultrasonic mixed solution that step (6) gets step (5) gained carries out vacuum filtration, the moisture that ethanolic soln replaces film is put into after film forming, after peeling off with filter membrane, utilize freeze drier drying treatment under a certain pressure, after 5h, can composite film electrode be obtained.
Carry out field emission scanning electron microscope observation to chitin nano fiber, carbon nanotube and laminated film that the embodiment of the present invention provides, result is see Fig. 1; As shown in Figure 1, the chitin nano fiber diameter range prepared by the present invention at 10 ~ 30nm, be woven into tridimensional network (in Fig. 1 a); The carbon nanotube that business is buied, diameter Distribution is also between 10 ~ 30nm (b in Fig. 1); Laminated film Electronic Speculum figure (d in c, Fig. 1 in Fig. 1) can see that chitin nano fiber and carbon nanotube are interweaved, and film surface is smooth bright and clean, and chitin becomes three-dimensional porous conductive network structure as substrate, carbon nanotube UNICOM; As shown in Figure 2, composite materials property is excellent; Can be found out by Fig. 2,4, conductivity is good, and matrix material can bend, and snappiness is good, and available its forms path as wire, makes LED luminous; By electro-chemical test, comprise cyclic voltammetry test (in Fig. 4 a), cycle life test (b in Fig. 4), from Fig. 4 comprehensively, composite film electrode has outstanding cycle charge discharge electrical property, and ratio capacitance is functional, and stability is strong.
Embodiment 2
From Carapax Eriocheir sinensis, the preparation method of chitin extraction nanofiber, comprises
Step (1) chooses the Carapax Eriocheir sinensis eaten, use electronic balance accurately to take 10g after cleaning, drying and put into beaker, add 600ml deionized water, leave standstill 24h with under hydrochloric acid (HCl) normal temperature condition of 6wt%, to remove the calcium carbonate in Carapax Eriocheir sinensis, use a large amount of deionized water rinsing to neutral afterwards;
It is in potassium hydroxide (KOH) solution of 6% that Carapax Eriocheir sinensis is soaked in concentration by step (2), is placed in the water-bath 6h of 100 DEG C, removes the protein in Carapax Eriocheir sinensis, uses a large amount of deionized water rinsings to neutral afterwards; This process repeats four times, to guarantee fully to remove protein;
Step (3) by process after Carapax Eriocheir sinensis be placed in 95% ethanolic soln 48h, sealing and standing, to remove pigment, post-flush can obtain purifying chitin to neutrality;
Step (4) adopts the glacial acetic acid solution of 0.5wt%, processes the purifying chitin 2h that the 3rd step obtains at 40 DEG C;
The purifying chitin that 4th step obtains is made into the suspension that concentration is 1wt% by step (5), milled processed 20 minutes, obtains the chitin nano fiber of diameter at 10 ~ 30nm;
The preparation method of chitin nano fiber and carbon nano-tube coextruded film electrode: comprise
Carbon nanotube is dried rear accurate weighing 50mg and is added in 250ml deionized water by step (1);
Step (2) weighs Sodium dodecylbenzene sulfonate (SDBS) 200mg, and add (1) solution, glass stick stirs 2 minutes;
The carbon nano tube suspension that step (2) obtains is placed in ice-water bath by step (3), utilize ultrasonic grinding instrument supersound process 90 minutes (ultrasonication time 1s, gap 2s, power 800W), solution after ultrasonic presents homodisperse state, and sediment-free amasss at the bottom of cup;
The carbon nano tube dispersion liquid 250ml that step (3) obtains by step (4) places in ice-water bath;
The chitin nano fiber 5g that step (5) gets the 1wt% of step a) gained joins in step (4) gained dispersion liquid, utilizes the ultrasonic mixing of ultrasonic grinding instrument 10 minutes (ultrasonication time 1s, gap 2s, power 800W);
The ultrasonic mixed solution that step (6) gets step (5) gained carries out vacuum filtration, the moisture that ethanolic soln replaces film is put into after film forming, after peeling off with filter membrane, utilize freeze drier drying treatment under a certain pressure, after 5h, can composite film electrode be obtained.
Embodiment 3
From the chitin powder that business is bought, the preparation method of chitin extraction nanofiber, comprises
Step (1) sieve gets 40 ~ 60 object chitin powder, use electronic balance accurately to take 10g after drying and put into beaker, add 600ml deionized water, leave standstill 24h with under hydrochloric acid (HCl) normal temperature condition of 5wt%, to remove the calcium carbonate in chitin, use a large amount of deionized water rinsing to neutral afterwards;
It is in potassium hydroxide (KOH) solution of 7% that chitin is soaked in concentration by step (2), is placed in the water-bath 6h of 90 DEG C, removes the protein in chitin, uses a large amount of deionized water rinsings to neutral afterwards;
Step (3) leaves standstill 12h with the hydrochloric acid normal temperature of 5wt% again, uses a large amount of deionized water rinsing to neutral afterwards;
It is in potassium hydroxide (KOH) solution of 5% that chitin is soaked in concentration by step (4), soak at room temperature 24h, and this process repeats twice, to guarantee fully to remove protein;
Step (5) by process after chitin be placed in 50% ethanolic soln 48h, sealing and standing, to remove pigment, post-flush can obtain purifying chitin to neutrality;
Step (6) adopts the glacial acetic acid solution of 0.3wt%, processes the purifying chitin 1h that the 5th step obtains at 25 DEG C;
The purifying chitin that 6th step obtains is made into the suspension that concentration is 0.8wt% by step (7), milled processed 20 minutes, obtains the chitin nano fiber of diameter at 10 ~ 30nm.
The preparation method of chitin nano fiber and carbon nano-tube coextruded film electrode, comprising:
Carbon nanotube is dried rear accurate weighing 50mg and is added in 250ml deionized water by step (1);
Step (2) weighs Sodium dodecylbenzene sulfonate (SDBS) 200mg, and add step (1) solution, glass stick stirs 2 minutes;
The carbon nano tube suspension that step (2) obtains is placed in ice-water bath by step (3), utilize ultrasonic grinding instrument supersound process 90 minutes (ultrasonication time 1s, gap 2s, power 800W), solution after ultrasonic presents homodisperse state, and sediment-free amasss at the bottom of cup;
The carbon nano tube dispersion liquid 250ml that step (3) obtains by step (4) places in ice-water bath;
The chitin nano fiber 5g that step (5) gets the 1wt% of step a) gained joins in step (4) gained dispersion liquid, utilizes the ultrasonic mixing of ultrasonic grinding instrument 10 minutes (ultrasonication time 1s, gap 2s, power 800W);
The ultrasonic mixed solution that step (6) gets step (5) gained carries out vacuum filtration, the moisture that ethanolic soln replaces film is put into after film forming, after peeling off with filter membrane, utilize freeze drier drying treatment under a certain pressure, after 5h, can composite film electrode be obtained.
The foregoing is only selection process of the present invention, it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can make some improvements and modifications, these improvement also should be considered as protection scope of the present invention.
Claims (9)
1. chitin nano fiber/carbon nanotube compound prepares the method for flexible membrane electrode, it is characterized in that comprising following processing step:
A) more than crustaceans kitchen product by simple chemical-mechanical legal system for chitin nano fiber;
B) the mixing of chitin nano fiber and carbon nano tube dispersion liquid.
2. chitin nano fiber according to claim 1/carbon nanotube compound prepares the method for flexible membrane electrode, it is characterized in that, more than described step a) crustaceans kitchen, product is by simple chemical-mechanical legal system for chitin nano fiber, and its method comprises the following steps:
(1) shrimp of recovery, crab husk as raw material is chosen, use electronic balance accurately to take 10g after cleaning, drying and put into beaker, add 600ml deionized water, leave standstill 24h with under the hydrochloric acid HCl normal temperature condition of 5-7wt%, to remove the calcium carbonate in chitin, use a large amount of deionized water rinsing to neutral afterwards;
(2) shrimp, crab shell being soaked in concentration is in the potassium hydroxide solution of 5%, is placed in the water-bath 6h of 95 DEG C, removes the protein in shrimp, crab shell, uses a large amount of deionized water rinsings to neutral afterwards; This process repeats four times, to guarantee fully to remove protein;
(3) shrimp, the crab shell after process is placed in the ethanolic soln 24h of 75%, sealing and standing, to remove pigment, post-flush can obtain purifying chitin to neutrality;
(4) glacial acetic acid solution of 0.1 ~ 0.5wt% is adopted, purifying chitin 1 ~ 2h that treatment step (3) obtains at 35 DEG C;
(5) the purifying chitin that step (4) step obtains is made into the suspension that concentration is 0.8 ~ 1wt%, milled processed 10 ~ 15 minutes, obtains the chitin nano fiber of diameter at 10 ~ 30nm.
3. chitin nano fiber according to claim 1 prepares the method for flexible membrane electrode, it is characterized in that, described step b) chitin nano fiber mixes with carbon nano tube dispersion liquid, and its method comprises the following steps:
(1) after being dried by carbon nanotube, accurate weighing 10 ~ 50mg adds in 250ml deionized water;
(2) weigh Sodium dodecylbenzene sulfonate 50 ~ 200mg, add the solution in step (1), glass stick stirs 2 minutes;
(3) carbon nano tube suspension that step (2) obtains is placed in ice-water bath, utilize ultrasonic grinding instrument supersound process 30 ~ 90 minutes, the solution after ultrasonic presents homodisperse state, and sediment-free amasss at the bottom of cup;
(4) carbon nano tube dispersion liquid 250ml step (3) obtained places in ice-water bath;
(5) the chitin nano fiber 1 ~ 5g getting 0.8 ~ 1wt% of step a) gained joins in step (4) gained dispersion liquid, utilizes the ultrasonic mixing of ultrasonic grinding instrument 15 ~ 30 minutes;
(6) the ultrasonic mixed solution 100-300ml of step (5) gained is got, carry out vacuum filtration, after film forming, put into the moisture that ethanolic soln replaces film, and after filter membrane stripping, utilize freeze drier drying treatment under setting pressure, after 2 ~ 5h, can composite film electrode be obtained.
4. chitin nano fiber according to claim 3/carbon nanotube compound prepares the method for flexible membrane electrode, it is characterized in that the supersound process of described step (3) refers to that the ultrasonication time is 1s, gap 2s, ultrasonic power 800W.
5. chitin nano fiber according to claim 3/carbon nanotube compound prepares the method for flexible membrane electrode, it is characterized in that the ultrasonic mixing of described step (5) refers to that the ultrasonication time is 1s, gap 2s, ultrasonic power 500 ~ 800W, in ultrasonic mixing, because Sodium dodecylbenzene sulfonate contains aromatic ring structure, the while that the hydrophobic part of aliphatic chain and carbon nanotube being interactional, aromatic nucleus also interacts with the P-P of carbon nanotube, dispersiveness is relatively high, and the uniform dispersion stability formed is better.
6. chitin nano fiber according to claim 2/carbon nanotube compound prepares the method for flexible membrane electrode, it is characterized in that product refers to the biological material containing chitin more than described crustaceans kitchen, carbon nanotube comprises Single Walled Carbon Nanotube and multi-walled carbon nano-tubes.
7. chitin nano fiber according to claim 2/carbon nanotube compound prepares the method for flexible membrane electrode, it is characterized in that described simple chemistry-mechanical process is use four kinds of pharmaceutical chemicalss: hydrochloric acid, Glacial acetic acid, potassium hydroxide and ethanol just can reach well separates fine effect, and mechanical process uses shredder, compared to ultrasonic method and homogeneous method, more effectively, energy-conservation and be more conducive to realize suitability for industrialized production.
8. chitin nano fiber according to claim 2/carbon nanotube compound prepares the method for flexible membrane electrode, it is characterized in that product adopts the Glacial acetic acid stirring at normal temperature of 0.1 ~ 0.5wt% by the step (4) that simple chemistry-mechanical process is prepared in chitin nano fiber more than described biomass kitchen, to reach, moistening rises separates fine object, because there is crystallizing field and noncrystalline domain in biomacromolecule chain; The spacing of crystallizing field is little, very large by hydrogen bonded intensity between molecular chain; And noncrystalline domain distance is comparatively large, combined by Van der Waals force between molecular chain, intensity is more weak; In the process of soaking and stirring, Glacial acetic acid immerses pars amorpha, by noncrystalline domain profit, widen the distance of crystallizing field molecular chain simultaneously, most of hydrogen bond is destroyed and forms Van der Waals force, play and separate fine object, then can obtain chitin nano fiber by mechanical force process.
9. chitin nano fiber according to claim 2/carbon nanotube compound prepares the method for flexible membrane electrode, it is characterized in that product is adopt shredder to carry out " one-timepass " (polishing) to obtain chitin nano fiber by step (5) milled processed that simple chemistry-mechanical process is prepared in chitin nano fiber/carbon nanotube compound more than described biomass kitchen, the rotating speed of grinding is 1500r/min, scale is about-8.5, through Glacial acetic acid process, hydroxyl in chitin fiber molecular chain is opened by swollen, add the fricting shearing of grinding stone in shredder and the centrifugal force of high-speed rotation generation, distance between chitin fiber tube bank is widened, bonding force is destroyed, by once grinding the chitin nano fiber just can prepared and have compared with high length-diameter ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610030429.4A CN105504093A (en) | 2016-01-18 | 2016-01-18 | Method for preparing membrane electrode from chitin nano fiber/carbon nanotube composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610030429.4A CN105504093A (en) | 2016-01-18 | 2016-01-18 | Method for preparing membrane electrode from chitin nano fiber/carbon nanotube composite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105504093A true CN105504093A (en) | 2016-04-20 |
Family
ID=55712438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610030429.4A Pending CN105504093A (en) | 2016-01-18 | 2016-01-18 | Method for preparing membrane electrode from chitin nano fiber/carbon nanotube composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105504093A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106057485A (en) * | 2016-08-19 | 2016-10-26 | 南京林业大学 | Method for preparing super capacitor aerogel electrode material |
| CN106206054A (en) * | 2016-08-19 | 2016-12-07 | 南京林业大学 | A kind of chitin nano fiber is combined the method preparing ultracapacitor wire electrode |
| CN106192073A (en) * | 2016-08-19 | 2016-12-07 | 南京林业大学 | A kind of method preparing line-shaped conductive material based on chitin nano fiber |
| CN106378101A (en) * | 2016-10-17 | 2017-02-08 | 武汉大学 | Chitin/carbon nanotube composite adsorbent for blood perfusion and preparation method thereof |
| CN107151276A (en) * | 2017-06-23 | 2017-09-12 | 武汉理工大学 | The method of chitin extraction nanometer fento from marine biomass |
| CN109251342A (en) * | 2018-07-12 | 2019-01-22 | 南京林业大学 | A kind of nano-cellulose/carbon nano-tube/poly dimethyl siloxane conductive composite film and preparation method thereof |
| CN113024688A (en) * | 2021-05-24 | 2021-06-25 | 贝尔纳丝新材料(江苏)有限公司 | Preparation method of water phase and organic phase solvent stable dispersion nano chitin |
| CN113185711A (en) * | 2021-05-24 | 2021-07-30 | 贝尔纳丝新材料(江苏)有限公司 | Preparation method of acidic, neutral and alkaline stable dispersed nano chitin |
| CN113265014A (en) * | 2021-04-20 | 2021-08-17 | 南京林业大学 | Multi-grade chitin micro/nano fiber material |
| CN114292495A (en) * | 2022-01-10 | 2022-04-08 | 深圳市佳迪达新材料科技有限公司 | Epoxy resin composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489259A (en) * | 2011-11-10 | 2012-06-13 | 河南大学 | Graphene oxide/cellulose compound material as well as preparation method and application of same |
| CN103342821A (en) * | 2013-07-10 | 2013-10-09 | 南京林业大学 | Method for preparing chitin nanofibre by using shrimp and crab shells |
| CN104992853A (en) * | 2015-07-27 | 2015-10-21 | 南京林业大学 | Method of preparing flexible bendable thin film electrode of supercapacitor |
-
2016
- 2016-01-18 CN CN201610030429.4A patent/CN105504093A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489259A (en) * | 2011-11-10 | 2012-06-13 | 河南大学 | Graphene oxide/cellulose compound material as well as preparation method and application of same |
| CN103342821A (en) * | 2013-07-10 | 2013-10-09 | 南京林业大学 | Method for preparing chitin nanofibre by using shrimp and crab shells |
| CN104992853A (en) * | 2015-07-27 | 2015-10-21 | 南京林业大学 | Method of preparing flexible bendable thin film electrode of supercapacitor |
Non-Patent Citations (1)
| Title |
|---|
| CHUCHU CHEN等: "A three-dimensionally chitin nanofiber/carbon nanotube hydrogelnetwork for foldable conductive paper", 《CARBOHYDRATE POLYMERS》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106057485A (en) * | 2016-08-19 | 2016-10-26 | 南京林业大学 | Method for preparing super capacitor aerogel electrode material |
| CN106206054A (en) * | 2016-08-19 | 2016-12-07 | 南京林业大学 | A kind of chitin nano fiber is combined the method preparing ultracapacitor wire electrode |
| CN106192073A (en) * | 2016-08-19 | 2016-12-07 | 南京林业大学 | A kind of method preparing line-shaped conductive material based on chitin nano fiber |
| CN106206054B (en) * | 2016-08-19 | 2018-01-30 | 南京林业大学 | A kind of compound method for preparing ultracapacitor wire electrode of chitin nano fiber |
| CN106192073B (en) * | 2016-08-19 | 2018-03-06 | 南京林业大学 | A kind of method that wire conductive material is prepared based on chitin nano fiber |
| CN106378101A (en) * | 2016-10-17 | 2017-02-08 | 武汉大学 | Chitin/carbon nanotube composite adsorbent for blood perfusion and preparation method thereof |
| CN106378101B (en) * | 2016-10-17 | 2019-01-18 | 武汉大学 | A kind of blood perfusion chitin/carbon nano tube composite adsorbent and preparation method thereof |
| CN107151276A (en) * | 2017-06-23 | 2017-09-12 | 武汉理工大学 | The method of chitin extraction nanometer fento from marine biomass |
| CN109251342A (en) * | 2018-07-12 | 2019-01-22 | 南京林业大学 | A kind of nano-cellulose/carbon nano-tube/poly dimethyl siloxane conductive composite film and preparation method thereof |
| CN109251342B (en) * | 2018-07-12 | 2021-02-02 | 南京林业大学 | Nano-cellulose/carbon nano-tube/polydimethylsiloxane conductive composite membrane and preparation method thereof |
| CN113265014A (en) * | 2021-04-20 | 2021-08-17 | 南京林业大学 | Multi-grade chitin micro/nano fiber material |
| CN113024688A (en) * | 2021-05-24 | 2021-06-25 | 贝尔纳丝新材料(江苏)有限公司 | Preparation method of water phase and organic phase solvent stable dispersion nano chitin |
| CN113185711A (en) * | 2021-05-24 | 2021-07-30 | 贝尔纳丝新材料(江苏)有限公司 | Preparation method of acidic, neutral and alkaline stable dispersed nano chitin |
| CN113024688B (en) * | 2021-05-24 | 2021-09-17 | 贝尔纳丝新材料(江苏)有限公司 | Preparation method of water phase and organic phase solvent stable dispersion nano chitin |
| CN114292495A (en) * | 2022-01-10 | 2022-04-08 | 深圳市佳迪达新材料科技有限公司 | Epoxy resin composite material and preparation method and application thereof |
| CN114292495B (en) * | 2022-01-10 | 2022-08-19 | 深圳市佳迪达新材料科技有限公司 | Epoxy resin composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105504093A (en) | Method for preparing membrane electrode from chitin nano fiber/carbon nanotube composite | |
| Liu et al. | Cellulose nanopaper: fabrication, functionalization, and applications | |
| CN106496639B (en) | A kind of nano-cellulose-polypyrrole-polyvinyl alcohol composite conducting hydrogel and its preparation method and application | |
| CN103966907B (en) | A kind of compliant conductive paper based on nano-cellulose and preparation method thereof | |
| Selvaraj et al. | The recent development of polysaccharides biomaterials and their performance for supercapacitor applications | |
| CN102619128B (en) | Graphene-containing multi-functional composite paper and preparation method as well application thereof | |
| CN100400579C (en) | Method for preparing functional material of regenerated cellulose | |
| Zhou et al. | Cellulose for sustainable triboelectric nanogenerators | |
| Na et al. | Novel egg white gel polymer electrolyte and a green solid-state supercapacitor derived from the egg and rice waste | |
| CN104992853A (en) | Method of preparing flexible bendable thin film electrode of supercapacitor | |
| CN106158426A (en) | A kind of method preparing flexible super capacitor wire electrode | |
| CN102391535A (en) | Bacterial cellulose conductive thin film and preparation method thereof | |
| Wang et al. | Facile production of natural silk nanofibers for electronic device applications | |
| CN108559112A (en) | A kind of preparation method of graphene-cellulose conductive composite film | |
| Anthony et al. | Bioresource-derived polymer composites for energy storage applications: Brief review | |
| CN104627977A (en) | Graphene oxide reinforced composite carbon nanopaper and production method thereof | |
| Kasprzak et al. | Sustainable and flexible energy storage devices: A review | |
| Heng et al. | Raw cellulose/polyvinyl alcohol blending separators prepared by phase inversion for high-performance supercapacitors | |
| CN106192073B (en) | A kind of method that wire conductive material is prepared based on chitin nano fiber | |
| Xiong et al. | Recent progress of green biomass based composite materials applied in supercapacitors, sensors, and electrocatalysis | |
| Brooke et al. | Nanocellulose and PEDOT: PSS composites and their applications | |
| Ahmed et al. | Nature-derived polymers and their composites for energy depository applications in batteries and supercapacitors: Advances, prospects and sustainability | |
| Akhlaq et al. | Carboxymethyl cellulose-based materials as an alternative source for sustainable electrochemical devices: a review | |
| Lin et al. | Natural cellulose substance based energy materials | |
| Song et al. | Recent progress on nature‐derived biomaterials for eco‐friendly triboelectric nanogenerators |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160420 |
|
| RJ01 | Rejection of invention patent application after publication |