CN103734958B - Preparation method for filling materials in ultra-light warm clothes and application of filling material in ultra-light warm clothes - Google Patents
Preparation method for filling materials in ultra-light warm clothes and application of filling material in ultra-light warm clothes Download PDFInfo
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Abstract
The invention provides a preparation method for filling materials in ultra-light warm clothes and application of the filling materials in the ultra-light warm clothes, and relates to a preparation method for sponge materials of filling materials in warm clothes. The problem that the heat retention property and the attractiveness of filling materials, which are prepared by using the existing method, in the warm clothes are conflicting is solved. The preparation method comprises the following steps of (1), preparing oxidized graphene by using natural crystalline flake graphite; (2) preparing oxidized graphene dispersion liquid; (3) preparing dispersion liquid by using a carbon nano tube and surface active agents; (4) preparing oxidized graphene and carbon nano tube solution; (5) performing freeze drying on the oxidized graphene and carbon nano tube solution; (6) performing reduction on an oxidized graphene and carbon nano tube sponge; and (7) drying the sponge so that the preparation on the ultra-light sponge is finished. The application comprises that the prepared ultra-light graphene and carbon nano tube sponge is filled between an outer fabric and an interlining fabric of the warm clothes. The sponge has ultra-low density and ultra-low heat conductivity coefficient; and the thickness of the warm clothes is reduced, so that the warm clothes are light and attractive.
Description
Technical field
The present invention relates to a kind of preparation method and the application thereof that can be used for the sponge material of warm-up inside stuffing.
Background technology
Warm-up is people's topmost one resisting cold clothes in very long winter, and its thermal property under severe cold condition is excellent, wears easy, therefore receives the welcome of consumers in general.And people often make the cotton inner bag of more abundant suede when improving the resisting cold ability of warm-up, although improve the warmth retention property of warm-up to a certain extent, this also also directly increases the quality of warm-up on the other hand.Meanwhile, blocked up warm-up also destroys the aesthetic property of insulation garment, and this does not meet people's requirement more and more higher to insulation garment yet.Therefore the warmth retention property of warm-up and aesthetic property is solved and the problem of depositing also just becomes urgent need to solve the problem.
The sponge material prepared from Graphene, CNT makes the solution of this Tough questions become possibility.Graphene is defined as only by the bi-dimensional cellular shape lattice structure of the tightly packed one-tenth of monolayer carbon atom, and each carbon atom and adjacent three carbon atoms form covalent bond.Although Graphene is only made up of one deck carbon atom, its pattern can observe by multiple instrument, characterize the number of plies, the important information such as thickness and crystallization degree thereof of Graphene with this.In Graphene, each carbon atom has a s track and three p tracks, three carbon atoms that wherein s track is adjacent with surrounding with two p tracks form chemical bond, the electrical conductivity of Graphene is not contributed, and the remaining mutual hydridization of p track, form valence band and conduction band, affect the electric property of Graphene.
Simultaneously Graphene also has unique two dimensional crystal structure and determines it and have excellent electricity, mechanics and thermal property.Not easily there is scattering in the transmission of free electron on Graphene, electron mobility can reach 2 × 10
5cm/Vs is more than 100 times of electron mobility in silicon; Its electrical conductivity is up to 10
6s/m is best conductive material under room temperature.Graphene elastic modelling quantity is up to 1TPa, and fracture strength is 125GPa, and room temperature thermal conductivity is 5.3 × 10
3w/mK, specific area is 2630m
2/ g.Graphene has excellent optical property, and the visible-light absorptivity of single-layer graphene is only 2.3%, can estimate the number of plies of Graphene thus according to the visible light transmissivity of thin graphene.In addition, ultraviolet light has corrasion to Graphene, and along with the increase of UV-irradiation time, the structure of graphene film is constantly destroyed, and its visible light transmissivity and pellicular front resistance are all in rising.The graphene film of this two dimension, except having high conductivity and transmitance, also shows excellent chemical stability and heat endurance, can be used as the substitute of solar energy transparency electrode.
CNT is monodimension nanometer material, and the hexagonal structure that its carbon atom is formed connects perfect, has many superior mechanics, electricity and chemical property.The C=C covalent bond of composition CNT is the most stable chemical bond of occurring in nature, and this also makes CNT have very superior mechanical property.CNT intensity and toughness are all far superior to any fiber, are considered to following " super fiber ".It not only has the peculiar person's character of carbon materials, has the electric conductivity with metal material, the heat-resisting and corrosion resistance of ceramic material, the lightweight of macromolecular material, workability.The intensity of composite, elasticity, fatigue resistance can be made to be significantly increased as the wild phase of composite CNT, this will bring a qualitative leap to composite property.Therefore Graphene and CNT have sizable using value in fields such as composite, catalysis material, energy storage material, gas sensors, have also therefore attracted numerous scholar to launch deeply systematically to study to it.
In sum, there is certain contradiction in the product warmth retention property of existing warm-up and aesthetic property, and exigence people address this problem.
Summary of the invention
The present invention seeks to the warmth retention property in order to solve packing material in warm-up prepared by existing method and the afoul problem of aesthetic property, and provide a kind of preparation method and application thereof of ultralight warm-up inside stuffing.
The preparation method of the ultralight warm-up inside stuffing of the present invention follows these steps to realize:
One, prepare graphene oxide: joined by natural flake graphite in strong oxidizing property nitration mixture, low whipping speed is stir 10min ~ 60min under the condition of 100r/min ~ 800r/min, divide again and add strong oxidizer potassium permanganate for 3 ~ 10 times and obtain mixture A, then mixture A is placed in 30 DEG C ~ 80 DEG C water-baths, low whipping speed is after under the condition of 200r/min ~ 800r/min, constant temperature stirs 4h ~ 20h, obtain mixture B, again mixture B is joined in frozen water, and in frozen water, add the hydrogen peroxide that mass fraction is 30%, obtain graphite oxide suspension, through filtering and washing, after centrifuge washing process and drying, obtain graphene oxide,
Two, graphene oxide dispersion is prepared: it is even that graphene oxide step one obtained adds deionized water for stirring, obtain graphene oxide deionized water dispersion liquid, then in frequency be under the condition of 10KHz ~ 90KHz by graphene oxide deionized water dispersion liquid ultrasonic process 20min ~ 60min, obtain the graphene oxide dispersion that concentration is 0.5mg/mL ~ 22mg/mL;
Three, carbon nano tube dispersion liquid is prepared: add in deionized water by CNT and surfactant, be that under the condition of 10KHz ~ 100KHz, ultrasonic process evenly spreads in deionized water to CNT and surfactant in frequency, obtain the carbon nano tube dispersion liquid that mass concentration is 0.5mg/mL ~ 15mg/mL;
Wherein, in described carbon nano tube dispersion liquid, surfactant qualities concentration is 1% ~ 30%;
Four, graphene oxide-carbon nano-tube solution is prepared: the carbon nano tube dispersion liquid mixing that the graphene oxide dispersion first step 2 obtained and step 3 obtain, low whipping speed is stir 10min ~ 60min under the condition of 200r/min ~ 800r/min again, finally ultrasonic process 10min ~ 120min under frequency is the condition of 10KHz ~ 100KHz, obtains graphene oxide-carbon nano-tube solution;
Wherein, described graphene oxide dispersion and the volume ratio of carbon nano tube dispersion liquid are (1 ~ 30): 1;
Five, freeze drying: graphene oxide-carbon nano-tube solution step 4 obtained carries out pre-freeze process, then puts into freeze drier is dry 24h ~ 50h under the condition of-45 DEG C ~ 20 DEG C in temperature, takes out and obtains graphene oxide-CNT sponge;
Six, redox graphene-CNT sponge: take graphene oxide-CNT sponge of obtaining in step 5 and reaction vessel put into by reducing agent, after reaction vessel is sealed, under the condition of 50 DEG C ~ 150 DEG C, react 3h ~ 50h, obtain the graphene-carbon nano tube sponge after electronation;
Seven, dry: the graphene-carbon nano tube sponge after electronation step 6 obtained carries out drying process at 40 DEG C ~ 120 DEG C, and drying time is 10h ~ 30h, obtains ultralight warm-up inside stuffing.
The application process of the present invention's ultralight warm-up inside stuffing is filled between the outer cloth of warm-up and satinet by ultralight warm-up inside stuffing, then outer cloth, satinet and ultralight warm-up inside stuffing are fixed by quilting line.
Ultralight prepared by the present invention, ultralow thermal conductivity graphite alkene-CNT sponge can be used for the filler of warm-up inside, its preparation method technique is simply with low cost, production efficiency is high, controllability good, and large scale sample can be prepared, solve the present situation of big size graphene sponge preparation in the past by experimental facilities restriction.The ultralight warm-up inside stuffing graphene-carbon nano tube sponge adopting the inventive method to prepare has extremely-low density, and least density can reach 1mg/cm
3, graphene-carbon nano tube sponge density regulates by changing technological parameter, and density range is 1mg/cm
3~ 20mg/cm
3; The graphene-carbon nano tube sponge of preparation has 3 D stereo network structure, shows good compression performance, is under the condition of 70%, still can restores to the original state completely in compression ratio; This graphene-carbon nano tube sponge has very low thermal conductivity factor simultaneously, be 0.0231W/mK without the thermal conductivity factor under contractive condition, and graphene-carbon nano tube sponge still can keep lower thermal conductivity factor under the condition of compression, compression ratio is under the condition of 50%, the thermal conductivity factor of graphene-carbon nano tube sponge is also only 0.0300W/mK, and the thermal conductivity factor of air is 0.0230W/mK under the same terms, the graphene-carbon nano tube sponge that therefore prepared by the present invention has a good application prospect in warm-up packing material.
Accompanying drawing explanation
Fig. 1 is the shape appearance figure of the graphene oxide obtained in embodiment one step one;
Fig. 2 is the shape appearance figure of the graphene oxide-CNT sponge obtained in embodiment one step 5;
Fig. 3 is the shape appearance figure of the graphene-carbon nano tube sponge after the electronation obtained in embodiment one step 6;
Fig. 4 is the scanning electron microscope (SEM) photograph of the ultralight warm-up inside stuffing that embodiment one prepares.
Detailed description of the invention
Technical solution of the present invention is not limited to following cited detailed description of the invention, also comprises any combination between each detailed description of the invention.
Detailed description of the invention one: the preparation method of the ultralight warm-up inside stuffing of present embodiment follows these steps to implement:
One, prepare graphene oxide: joined by natural flake graphite in strong oxidizing property nitration mixture, low whipping speed is stir 10min ~ 60min under the condition of 100r/min ~ 800r/min, divide again and add strong oxidizer potassium permanganate for 3 ~ 10 times and obtain mixture A, then mixture A is placed in 30 DEG C ~ 80 DEG C water-baths, low whipping speed is after under the condition of 200r/min ~ 800r/min, constant temperature stirs 4h ~ 20h, obtain mixture B, again mixture B is joined in frozen water, and in frozen water, add the hydrogen peroxide that mass fraction is 30%, obtain graphite oxide suspension, through filtering and washing, after centrifuge washing process and drying, obtain graphene oxide,
Two, graphene oxide dispersion is prepared: it is even that graphene oxide step one obtained adds deionized water for stirring, obtain graphene oxide deionized water dispersion liquid, then in frequency be under the condition of 10KHz ~ 90KHz by graphene oxide deionized water dispersion liquid ultrasonic process 20min ~ 60min, obtain the graphene oxide dispersion that concentration is 0.5mg/mL ~ 22mg/mL;
Three, carbon nano tube dispersion liquid is prepared: add in deionized water by CNT and surfactant, be that under the condition of 10KHz ~ 100KHz, ultrasonic process evenly spreads in deionized water to CNT and surfactant in frequency, obtain the carbon nano tube dispersion liquid that mass concentration is 0.5mg/mL ~ 15mg/mL;
Wherein, in described carbon nano tube dispersion liquid, surfactant qualities concentration is 1% ~ 30%;
Four, graphene oxide-carbon nano-tube solution is prepared: the carbon nano tube dispersion liquid mixing that the graphene oxide dispersion first step 2 obtained and step 3 obtain, low whipping speed is after stirring 10min ~ 60min under the condition of 200r/min ~ 800r/min again, finally ultrasonic process 10min ~ 120min under frequency is the condition of 10KHz ~ 100KHz, obtains graphene oxide-carbon nano-tube solution;
Wherein, the graphene oxide dispersion described in step 4 and the volume ratio of carbon nano tube dispersion liquid are (1 ~ 30): 1;
Five, freeze drying: graphene oxide-carbon nano-tube solution step 4 obtained carries out pre-freeze process, then puts into freeze drier is dry 24h ~ 50h under the condition of-45 DEG C ~ 20 DEG C in temperature, takes out and obtains graphene oxide-CNT sponge;
Six, redox graphene-CNT sponge: take graphene oxide-CNT sponge of obtaining in step 5 and reaction vessel put into by reducing agent, after reaction vessel is sealed, under the condition of 50 DEG C ~ 150 DEG C, react 3h ~ 50h, obtain the graphene-carbon nano tube sponge after electronation;
Seven, dry: the graphene-carbon nano tube sponge after electronation step 6 obtained carries out drying process at 40 DEG C ~ 120 DEG C, and drying time is 10h ~ 30h, obtains ultralight warm-up inside stuffing.
Compared with traditional warm-up inner core, the sponge material of what present embodiment obtained can be used for warm-up inside stuffing has lower density, more low thermal conductivity, and has good elasticity.While keeping good warmth retention property, reduce the thickness of warm-up, keep good aesthetic property, thus make the warmth retention property of warm-up and aesthetic property reach unified becoming possibility.
Detailed description of the invention two: present embodiment and detailed description of the invention one are (10mL ~ 400mL): 1g unlike the volume of the strong oxidizing property nitration mixture described in step one and natural flake graphite mass ratio.Other parameters are identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two unlike the strong oxidizing property nitration mixture described in step one by the phosphoric acid of mass fraction 10% ~ 85% and the sulfuric acid of mass fraction 10% ~ 98% according to volume ratio (3 ~ 10): 1 forms.Other parameters are identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three are 5g/L ~ 100g/L unlike the mass concentration of potassium permanganate in the mixture A described in step one.Other parameters are identical with one of detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four are 1g:(1mL ~ 6mL unlike the quality of the natural flake graphite described in step one and the volume ratio of hydrogen peroxide).Other parameters are identical with one of detailed description of the invention one to four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five are carried out according to the following steps unlike the centrifuge washing process described in step one:
Utilize centrifugal separator, the solid matter obtained after suction filtration to be joined in deionized water centrifugal rinsing 3 ~ 6 times, and then the solid matter obtained after rinsed with deionized water to be joined mass fraction be centrifugal rinsing 3 ~ 6 times in the hydrochloric acid solution of 0.1mol/L ~ 0.9mol/L, finally again the solid matter obtained after hydrochloric acid solution rinsing to be joined in absolute ethyl alcohol centrifugal rinsing 3 ~ 6 times.Other parameters are identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six are SWCN, double-walled carbon nano-tube or multi-walled carbon nano-tubes unlike the CNT described in step 3, carbon nanotube diameter is 5 nanometer ~ 50 nanometers, and length is 0.5 micron ~ 50 microns.Other parameters are identical with one of detailed description of the invention one to four.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven are neopelex, dodecyl sodium sulfate or softex kw unlike surfactant described in step 3.Other parameters are identical with one of detailed description of the invention one to seven.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention one to eight are treated to liquid nitrogen quick freeze unlike pre-freeze described in step 5 or application cold-trap instrument carries out pre-freeze process.Other is identical with one of detailed description of the invention one to eight.
Detailed description of the invention ten: one of present embodiment and detailed description of the invention one to nine unlike the reducing agent described in step 6 to be mass fraction be 80% hydrazine hydrate.Other is identical with one of detailed description of the invention one to nine.
Present embodiment when reducing agent is mass fraction be the hydrazine hydrate of 80% time, the quality of described graphene oxide-CNT sponge and the volume ratio of reducing agent are 1g:(5mL ~ 50mL).
Detailed description of the invention 11: one of present embodiment and detailed description of the invention one to ten are hydrothermal reaction kettle unlike the reaction vessel used described in step 6.Other is identical with one of detailed description of the invention one to ten.
Detailed description of the invention 12: the application process of present embodiment ultralight warm-up inside stuffing is filled between the outer cloth of warm-up and satinet by ultralight warm-up inside stuffing, then outer cloth, satinet and ultralight warm-up inside stuffing are fixed by quilting line.
Embodiment one: the preparation method of the ultralight warm-up inside stuffing of the present embodiment follows these steps to implement:
One, prepare graphene oxide: joined by 3.6g natural flake graphite in 360ml strong oxidizing property nitration mixture, low whipping speed is stir 15min under the condition of 200r/min, divide again and add strong oxidizer potassium permanganate for 5 times and obtain mixture A, then mixture A is placed in 42 DEG C of water-baths, low whipping speed is after under the condition of 300r/min, constant temperature stirs 7h, obtain mixture B, again mixture B is joined in frozen water, and in frozen water, add the hydrogen peroxide that mass fraction is 30%, obtain graphite oxide suspension, through filtering and washing, after centrifuge washing process and drying, obtain graphene oxide,
The quality of wherein said natural flake graphite and the volume ratio of hydrogen peroxide are 1g:2.5mL;
Two, graphene oxide dispersion is prepared: it is even that graphene oxide step one obtained adds deionized water for stirring, obtain graphene oxide deionized water dispersion liquid, then in frequency be under the condition of 40KHz by graphene oxide deionized water dispersion liquid ultrasonic process 45min, obtain the graphene oxide dispersion that concentration is 0.7mg/mL;
Three, carbon nano tube dispersion liquid is prepared: add in deionized water by CNT and surfactant, be that under the condition of 30KHz, ultrasonic process evenly spreads in deionized water to CNT and surfactant in frequency, obtain the carbon nano tube dispersion liquid that mass concentration is 0.7mg/mL;
Wherein, in described carbon nano tube dispersion liquid, surfactant qualities concentration is the neopelex of 2%;
Four, graphene oxide-carbon nano-tube solution is prepared: the carbon nano tube dispersion liquid that the graphene oxide dispersion first step 2 obtained and step 3 obtain mixes by the volume ratio of 4:1, low whipping speed is after stirring 25min under the condition of 300r/min, finally ultrasonic process 25min under frequency is the condition of 10KHz, obtains graphene oxide-carbon nano-tube solution;
Five, freeze drying: graphene oxide-carbon nano-tube solution step 4 obtained carries out pre-freeze process, then puts into freeze drier is dry 35h under the condition of-30 DEG C in temperature, takes out and obtains graphene oxide-CNT sponge;
Six, redox graphene-CNT sponge: take 0.1g graphene oxide-CNT sponge of obtaining in step 5 and 5ml mass fraction be 80% hydrazine hydrate put into reaction vessel, after reaction vessel is sealed, under the condition of 70 DEG C, react 13h, obtain the graphene-carbon nano tube sponge after electronation;
Seven, dry: the graphene-carbon nano tube sponge after electronation step 6 obtained carries out drying process at 50 DEG C, and drying time is 20h, obtains ultralight warm-up inside stuffing.
Strong oxidizing property nitration mixture wherein described in step one is the mixture of the phosphoric acid of mass fraction 85% and the sulfuric acid of mass fraction 98%; The volume ratio of the phosphoric acid of described mass fraction 85% and the sulfuric acid of mass fraction 98% is 1:4; In described mixture A, the mass concentration of potassium permanganate is 5g/L; CNT described in step 3 is SWCN, and carbon nanotube diameter is 5-40 nanometer, and length is 0.5-40 micron.
The density of the ultralight warm-up inside stuffing graphene-carbon nano tube sponge that the present embodiment obtains is 6mg/cm
3, this graphene-carbon nano tube sponge has 3 D stereo network structure simultaneously, shows good compression performance, is under the condition of 75%, still can restores to the original state completely in compression ratio; The graphene-carbon nano tube sponge that simultaneously prepared by present embodiment has very low thermal conductivity factor, be 0.024W/mK without the thermal conductivity factor under contractive condition, and graphene-carbon nano tube sponge still can keep lower thermal conductivity factor under the condition of compression, compression ratio is under the condition of 50%, and the thermal conductivity factor of graphene-carbon nano tube sponge is also only 0.0320W/mK.
Embodiment two: the preparation method of the ultralight warm-up inside stuffing of the present embodiment follows these steps to implement:
One, prepare graphene oxide: joined by 4.6g natural flake graphite in 460ml strong oxidizing property nitration mixture, low whipping speed is stir 25min under the condition of 200r/min, divide again and add strong oxidizer potassium permanganate for 8 times and obtain mixture A, then mixture A is placed in 55 DEG C of water-baths, low whipping speed is after under the condition of 300r/min, constant temperature stirs 15h, obtain mixture B, again mixture B is joined in frozen water, and in frozen water, add the hydrogen peroxide that mass fraction is 30%, obtain graphite oxide suspension, through filtering and washing, after centrifuge washing process and drying, obtain graphene oxide,
The quality of wherein said natural flake graphite and the volume ratio of hydrogen peroxide are 1g:4mL;
Two, graphene oxide dispersion is prepared: it is even that graphene oxide step one obtained adds deionized water for stirring, obtain graphene oxide deionized water dispersion liquid, then in frequency be under the condition of 70KHz by graphene oxide deionized water dispersion liquid ultrasonic process 40min, obtain the graphene oxide dispersion that concentration is 15mg/mL;
Three, carbon nano tube dispersion liquid is prepared: add in deionized water by CNT and surfactant, be that under the condition of 50KHz, ultrasonic process evenly spreads in deionized water to CNT and surfactant in frequency, obtain the carbon nano tube dispersion liquid that mass concentration is 5mg/mL;
Wherein, in described carbon nano tube dispersion liquid, surfactant qualities concentration is the neopelex of 10%;
Four, graphene oxide-carbon nano-tube solution is prepared: the carbon nano tube dispersion liquid that the graphene oxide dispersion first step 2 obtained and step 3 obtain mixes by the volume ratio of 10:1, low whipping speed is after stirring 20min under the condition of 300r/min, finally ultrasonic process 100min under frequency is the condition of 40KHz, obtains graphene oxide-carbon nano-tube solution;
Five, freeze drying: graphene oxide-carbon nano-tube solution step 4 obtained carries out pre-freeze process, then puts into freeze drier is dry 30h under the condition of-20 DEG C in temperature, takes out and obtains graphene oxide-CNT sponge;
Six, redox graphene-CNT sponge: take 0.8g graphene oxide-CNT sponge of obtaining in step 5 and 20ml mass fraction be 80% hydrazine hydrate put into reaction vessel, after reaction vessel is sealed, under the condition of 80 DEG C, react 15h, obtain the graphene-carbon nano tube sponge after electronation;
Seven, dry: the graphene-carbon nano tube sponge after electronation step 6 obtained carries out drying process at 100 DEG C, and drying time is 20h, obtains ultralight warm-up inside stuffing.
Strong oxidizing property nitration mixture wherein described in step one is the mixture of the phosphoric acid of mass fraction 85% and the sulfuric acid of mass fraction 98%; The volume ratio of the phosphoric acid of described mass fraction 85% and the sulfuric acid of mass fraction 98% is 1:8; In described mixture A, the mass concentration of potassium permanganate is 5g/L; CNT described in step 3 is double-walled carbon nano-tube, and carbon nanotube diameter is 10-40 nanometer, and length is 10-50 micron.
The density of the ultralight warm-up inside stuffing graphene-carbon nano tube sponge that the present embodiment obtains is 8mg/cm
3, this graphene-carbon nano tube sponge has 3 D stereo network structure simultaneously, shows good compression performance, is under the condition of 80%, still can restores to the original state completely in compression ratio; The graphene-carbon nano tube sponge that simultaneously prepared by present embodiment has very low thermal conductivity factor, be 0.026W/mK without the thermal conductivity factor under contractive condition, and graphene-carbon nano tube sponge still can keep lower thermal conductivity factor under the condition of compression, compression ratio is under the condition of 50%, and the thermal conductivity factor of graphene-carbon nano tube sponge is also only 0.034W/mK.
Ultralight warm-up inside stuffing embodiment one and embodiment two obtained is filled between the outer cloth of warm-up and satinet, then outer cloth, satinet and ultralight warm-up inside stuffing are fixed by quilting line, and then prepares warm-up.Because the density of the Ultralight graphene-carbon nano tube sponge as packing material is lower, there is again very low thermal conductivity factor simultaneously, therefore ultralight warm-up inside stuffing graphene-carbon nano tube sponge of the present invention is applied in warm-up, while ensureing good insulation warming effect, the thickness of warm-up can be reduced again, make its light and beautiful.
Claims (6)
1. a preparation method for ultralight warm-up inside stuffing, is characterized in that the preparation method of ultralight warm-up inside stuffing follows these steps to realize:
One, prepare graphene oxide: joined by natural flake graphite in strong oxidizing property nitration mixture, low whipping speed is stir 10min ~ 60min under the condition of 100r/min ~ 800r/min, divide again and add strong oxidizer potassium permanganate for 3 ~ 10 times and obtain mixture A, then mixture A is placed in 30 DEG C ~ 80 DEG C water-baths, low whipping speed is after under the condition of 200r/min ~ 800r/min, constant temperature stirs 4h ~ 20h, obtain mixture B, again mixture B is joined in frozen water, and in frozen water, add the hydrogen peroxide that mass fraction is 30%, obtain graphite oxide suspension, through filtering and washing, after centrifuge washing process and drying, obtain graphene oxide,
Two, graphene oxide dispersion is prepared: it is even that graphene oxide step one obtained adds deionized water for stirring, obtain graphene oxide deionized water dispersion liquid, then in frequency be under the condition of 10KHz ~ 90KHz by graphene oxide deionized water dispersion liquid ultrasonic process 20min ~ 60min, obtain the graphene oxide dispersion that concentration is 0.5mg/mL ~ 22mg/mL;
Three, carbon nano tube dispersion liquid is prepared: add in deionized water by CNT and surfactant, be that under the condition of 10KHz ~ 100KHz, ultrasonic process evenly spreads in deionized water to CNT and surfactant in frequency, obtain the carbon nano tube dispersion liquid that mass concentration is 0.5mg/mL ~ 15mg/mL;
Wherein, in described carbon nano tube dispersion liquid, surfactant qualities concentration is 1% ~ 30%;
Four, graphene oxide-carbon nano-tube solution is prepared: the carbon nano tube dispersion liquid mixing that the graphene oxide dispersion first step 2 obtained and step 3 obtain, low whipping speed is stir 10min ~ 60min under the condition of 200r/min ~ 800r/min again, finally ultrasonic process 10min ~ 120min under frequency is the condition of 10KHz ~ 100KHz, obtains graphene oxide-carbon nano-tube solution;
Wherein, described graphene oxide dispersion and the volume ratio of carbon nano tube dispersion liquid are (1 ~ 30): 1;
Five, freeze drying: graphene oxide-carbon nano-tube solution step 4 obtained carries out pre-freeze process, then puts into freeze drier is dry 24h ~ 50h under the condition of-45 DEG C ~ 20 DEG C in temperature, takes out and obtains graphene oxide-CNT sponge;
Six, redox graphene-CNT sponge: take graphene oxide-CNT sponge of obtaining in step 5 and reaction vessel put into by reducing agent, after reaction vessel is sealed, under the condition of 50 DEG C ~ 150 DEG C, react 3h ~ 50h, obtain the graphene-carbon nano tube sponge after electronation;
Seven, dry: the graphene-carbon nano tube sponge after electronation step 6 obtained carries out drying process at 40 DEG C ~ 120 DEG C, and drying time is 10h ~ 30h, obtains ultralight warm-up inside stuffing;
Strong oxidizing property nitration mixture described in step one by the phosphoric acid of mass fraction 10% ~ 85% and the sulfuric acid of mass fraction 10% ~ 98% according to volume ratio (3 ~ 10): 1 forms;
Surfactant described in step 3 is neopelex, dodecyl sodium sulfate or softex kw;
Reducing agent described in step 6 to be mass fraction be 80% hydrazine hydrate.
2. the preparation method of a kind of ultralight warm-up inside stuffing according to claim 1, is characterized in that the volume of the strong oxidizing property nitration mixture described in step one and natural flake graphite mass ratio are (10mL ~ 400mL): 1g.
3. the preparation method of a kind of ultralight warm-up inside stuffing according to claim 1, is characterized in that the centrifuge washing process described in step one is carried out according to the following steps:
Utilize centrifugal separator, the solid matter obtained after suction filtration to be joined in deionized water centrifugal rinsing 3 ~ 6 times, and then the solid matter obtained after rinsed with deionized water to be joined mass fraction be centrifugal rinsing 3 ~ 6 times in the hydrochloric acid solution of 0.1mol/L ~ 0.9mol/L, finally again the solid matter obtained after hydrochloric acid solution rinsing to be joined in absolute ethyl alcohol centrifugal rinsing 3 ~ 6 times.
4. the preparation method of a kind of ultralight warm-up inside stuffing according to claim 1, it is characterized in that the CNT described in step 3 is SWCN, double-walled carbon nano-tube or multi-walled carbon nano-tubes, carbon nanotube diameter is 5 nanometer ~ 50 nanometers, and length is 0.5 micron ~ 50 microns.
5. the preparation method of a kind of ultralight warm-up inside stuffing according to claim 1, is characterized in that pre-freeze described in step 5 is treated to liquid nitrogen frozen or application cold-trap instrument carries out pre-freeze process.
6. the application of a kind of ultralight warm-up inside stuffing that obtains of preparation method as claimed in claim 1, it is characterized in that the application process of ultralight warm-up inside stuffing is filled between the outer cloth of warm-up and satinet by ultralight warm-up inside stuffing, then outer cloth, satinet and ultralight warm-up inside stuffing are fixed by quilting line.
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