CN106902715B - Three-dimensional structure composite aerogel, preparation method and application thereof - Google Patents
Three-dimensional structure composite aerogel, preparation method and application thereof Download PDFInfo
- Publication number
- CN106902715B CN106902715B CN201710188299.1A CN201710188299A CN106902715B CN 106902715 B CN106902715 B CN 106902715B CN 201710188299 A CN201710188299 A CN 201710188299A CN 106902715 B CN106902715 B CN 106902715B
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- doped carbon
- composite aerogel
- dimensional structure
- structure 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.)
- Active
Links
Images
Classifications
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a three-dimensional structure composite aerogel, a preparation method and application thereof. The method of the invention comprises the following steps: 1) adding pyrrole monomer into the nitrogen-doped carbon nanotube solution, and uniformly dispersing; 2) adding silver nitrate into the mixed solution obtained in the step 1), and fully reacting; 3) uniformly mixing the dispersion liquid obtained in the step 2) with a solution of sodium alginate and/or potassium alginate, freezing the mixture into a block, and then freezing and drying the block to obtain the three-dimensional structure composite aerogel. The three-dimensional structure composite aerogel disclosed by the invention has good mechanical properties, can well exert the electrical conductivity of the silver nanoparticles and the nitrogen-doped carbon nanotubes when being compressed, and the silver nanoparticles are mutually contacted when being compressed, so that the sensitivity of a pressure sensor prepared by adopting the three-dimensional structure composite aerogel disclosed by the invention can be obviously improved.
Description
Technical Field
The invention belongs to the field of composite material preparation, relates to a three-dimensional structure composite material, a preparation method and application thereof, and particularly relates to a three-dimensional structure composite aerogel, a preparation method thereof and application thereof in a pressure sensor.
Background
In recent years, carbon nanotube aerogels and carbon nanotube composite aerogels have become hot spots of research. The aerogel is a network structure composed of nano particles or fibers, belongs to a solid matter form, and is an ultra-light porous material with low density. Aerogels have found widespread use and research as thermal insulation materials and energy storage devices. The carbon nano tube has good electric conductivity, and a conductive path and elastic gel in suspension liquid with certain concentration can be formed through van der Waals acting force among mutual connection under the condition of low volume fraction, so that the carbon nano tube belongs to a good aerogel precursor.
In 2007, the subject group of Arjun G.Yodh, the physical astronomical system of university of Pennsylvania, utilizes a carbon nanotube hydrogel precursor to prepare carbon nanotube aerogel with good performance by a critical point drying and freeze drying method. See the prior art "Mateusz B.B, Daniel E.M, Mohammad F.I, et al carbon nanotube aerogels. adv. Mater.2007,19,661, 664.".
In 2012, the Xuetong Zhang subject group of the university of materials science and engineering of beijing university of science and engineering, china, prepared the carbon nanotube/graphene composite aerogel with good performance by using a supercritical carbon dioxide drying method. See the prior art "Zhuyin S, Qinhan M, Xuetong Z, et al.Green synthesis of carbon nanotube-graphene hybrid aerogels and the use as a versatility for waterpurification. J.Mater.chem.,2012,22, 8767-.
In 2015, the department group of Shenzhen advanced technology research institute, Guiping Zhang, Chinese academy of sciences, adopted a freeze-drying method to prepare the hyperbranched macromolecule-containing carbon nanotube/silver particle composite aerogel with good performance. See the prior art "Songfang Z, Yongju G, targeting Z, et al. coded pumped reagent-copedbornen-supported Ag hybrid sites: Synthesis, structure management, and its application for flexible conductors and string-gauge sensors. CARBON86(2015) 225. 234.".
Although the above techniques all indicate some progress in the research and application of carbon nanotube composite aerogels. However, the aerogel-based high-sensitivity pressure sensor needs to further improve the electrical conductivity and mechanical properties of the three-dimensional composite material structure, improve the dispersibility of the nanoparticles in the system, and continuously research the structural components and design of the aerogel.
Disclosure of Invention
In view of the above, the present invention aims to overcome the disadvantages and shortcomings of the prior art, and provides a three-dimensional structure composite aerogel, a preparation method and applications thereof. The three-dimensional structure composite aerogel disclosed by the invention has good mechanical properties, can well exert the electrical conductivity of the silver nanoparticles and the nitrogen-doped carbon nanotubes when being compressed, and the silver nanoparticles are mutually contacted when being compressed, so that the sensitivity of a pressure sensor prepared by adopting the three-dimensional structure composite aerogel disclosed by the invention can be obviously improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a three-dimensional structure composite aerogel, the method comprising the steps of:
(1) adding pyrrole monomers into the nitrogen-doped carbon nanotube solution, and uniformly dispersing to obtain a mixed solution;
(2) adding silver nitrate into the mixed solution obtained in the step (1) to obtain a dispersion liquid;
(3) uniformly mixing the dispersion liquid obtained in the step (2) with a solution of sodium alginate and/or potassium alginate, freezing the mixture into a block, and then freezing and drying the block to obtain the three-dimensional structure composite aerogel;
wherein the nitrogen-doped carbon nanotube is an acidified nitrogen-doped carbon nanotube.
Compared with the conventional nitrogen-doped carbon nanotube, the acidified nitrogen-doped carbon nanotube has the following advantages: the first is that the dispersibility is good, and the nitrogen-doped carbon nanotube aggregate is well dispersed through acidification treatment to obtain the nitrogen-doped carbon nanotube with good dispersibility; secondly, some functional groups (such as-COOH) are introduced through acidification, so that the water solubility and the dispersibility of the polypyrrole/organic solvent composite material are enhanced, and the bonding property of the polypyrrole/organic solvent composite material is enhanced.
According to the method, silver nitrate is selected for reaction, on one hand, the silver nitrate is used as an oxidant to initiate pyrrole monomer polymerization, and on the other hand, silver ions are reduced to obtain silver nanoparticles in the process that the silver nitrate initiates the pyrrole monomer polymerization. In addition, the prepared polypyrrole has a good polymerization effect, the bonding property of the polypyrrole and the acidified nitrogen-doped carbon nanotube is strong, and the dispersibility of the silver nanoparticles obtained by reduction is good.
In the present invention, the acidified nitrogen-doped carbon nanotube is obtained by acidifying the nitrogen-doped carbon nanotube, the method of the acidification is the prior art, and a person skilled in the art can operate according to the method of the acidification disclosed in the prior art, and more preferably, the following method is adopted to perform the acidification to prepare the acidified nitrogen-doped carbon nanotube: putting the nitrogen-doped carbon nanotube into a single-neck flask, adding concentrated sulfuric acid, performing ultrasonic treatment for 0.5h, adding concentrated nitric acid, stirring for 10min, and performing oil bath at 60 ℃ for 2h to obtain the acidified nitrogen-doped carbon nanotube.
Preferably, in the process of preparing the acidified nitrogen-doped carbon nanotube, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1.
In the present invention, the nitrogen-doped carbon nanotube may be commercially available, or may be prepared by a method disclosed in the prior art, and may be selected by those skilled in the art as needed.
In the present invention, the "sodium alginate and/or potassium alginate" refers to: the sodium alginate or potassium alginate can be used, or the mixture of sodium alginate and potassium alginate can be used.
In the present invention, the solvent of the solution of the nitrogen-doped carbon nanotube is deionized water, and the amount of the deionized water is not particularly limited, and the nitrogen-doped carbon nanotube can be dissolved.
In the invention, the solvent of the sodium alginate and/or potassium alginate solution is deionized water, the dosage of the deionized water is not particularly limited, and the sodium alginate and/or potassium alginate can be dissolved.
As a preferred embodiment of the method of the present invention, the diameter of the nitrogen-doped carbon nanotube in the solution of nitrogen-doped carbon nanotubes in step (1) is 20nm to 50nm, for example, 20nm, 25nm, 28nm, 30nm, 35nm, 38nm, 40nm, 45nm, 48nm or 50nm, preferably 30nm to 40 nm.
Preferably, the length of the nitrogen-doped carbon nanotube in the solution of nitrogen-doped carbon nanotubes in step (1) is 10 μm to 30 μm, such as 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 23 μm, 25 μm, 28 μm or 30 μm, etc., preferably 20 μm to 30 μm.
Preferably, the mass ratio of the nitrogen-doped carbon nanotube to the pyrrole monomer, the silver nitrate, the sodium alginate and/or the potassium alginate is 1 (0.1-1): 0.5-2): 1, for example, 1:0.1:0.5:1, 1:0.2:0.5:1, 1:0.5:0.5:1, 1:0.3:1.5:1, 1:0.8:1.8:1 or 1:1:0.5:1, and preferably 1 (0.5-1): 1.
Preferably, in the mixed solution in the step (1), the mass concentration of the nitrogen-doped carbon nanotube is 3 mg/mL-50 mg/mL, for example, 3mg/mL, 4mg/mL, 5mg/mL, 6mg/mL, 8mg/mL, 10mg/mL, 11mg/mL, 12mg/mL, 13.5mg/mL, 15mg/mL, 17mg/mL, 20mg/mL, 22mg/mL, 24mg/mL, 25mg/mL, 27.5mg/mL, 30mg/mL, 32mg/mL, 35mg/mL, 38mg/mL, 40mg/mL, 42.5mg/mL, 45mg/mL, 47mg/mL, or 50mg/mL, etc., preferably 3mg/mL to 10mg/mL, and more preferably 3mg/mL to 5 mg/mL.
Preferably, the mode of uniformly dispersing in step (1) is ultrasonic, and the ultrasonic time is preferably 2min to 500min, such as 2min, 5min, 10min, 20min, 26min, 30min, 35min, 40min, 50min, 55min, 60min, 70min, 75min, 80min, 90min, 100min, 110min, 120min, 135min, 150min, 160min, 175min, 190min, 200min, 220min, 235min, 245min, 260min, 280min, 300min, 325min, 350min, 400min, 420min, 450min, 470min or 500min, and more preferably 15min to 150 min.
Stirring is carried out in the process of adding the silver nitrate in the step (2).
Preferably, after adding the silver nitrate in the step (2), a stirring step is performed.
Preferably, the volume ratio of the solution of sodium alginate and/or potassium alginate in the step (3) to the dispersion obtained in the step (2) is 1:1.
In the invention, the sodium alginate and/or potassium alginate used has good compatibility with other substances (such as polypyrrole, acidified nitrogen-doped carbon nano tube and the like), and the binding property and stability of the obtained product can be improved.
Preferably, the temperature of the freeze-drying in the step (3) is-195 ℃ to 0 ℃, for example, -195 ℃, 180 ℃, 175 ℃, 170 ℃, 160 ℃, 155 ℃, 150 ℃, 140 ℃, 130 ℃, 125 ℃, 120 ℃, 110 ℃, 100 ℃, 90 ℃, 85 ℃, 80 ℃, 70 ℃, 65 ℃, 60 ℃, 50 ℃, 40 ℃, 35 ℃, 30 ℃,20 ℃, 15 ℃, 10 ℃,8 ℃, 5 ℃, 3 ℃ or 0 ℃, preferably-195 ℃ to 10 ℃.
Preferably, the freeze-drying time in the step (3) is 10-12 h.
As a preferred embodiment of the method of the present invention, a method for preparing a three-dimensional structure composite aerogel, the method comprising the steps of:
(1) adding the acidified water solution of the nitrogen-doped carbon nano tube into a beaker, adding a pyrrole monomer, and uniformly dispersing to obtain a mixed solution;
(2) adding silver nitrate into the mixed solution obtained in the step (1) to fully react to obtain a dispersion liquid;
(3) and (3) dissolving sodium alginate in deionized water, uniformly mixing the obtained sodium alginate aqueous solution with the dispersion liquid obtained in the step (2), freezing the mixture in a refrigerator to form a block, and then putting the block into a freeze dryer for freeze drying to obtain the three-dimensional structure composite aerogel.
In a second aspect, the present invention provides a three-dimensional structure composite aerogel prepared by the method of the first aspect, wherein the three-dimensional structure composite aerogel comprises a three-dimensional network framework and polypyrrole, silver nanoparticles and nitrogen-doped carbon nanotubes dispersed in the three-dimensional network framework, and the nitrogen-doped carbon nanotubes are acidified nitrogen-doped carbon nanotubes.
The three-dimensional network skeleton is a three-dimensional network skeleton formed by sodium alginate and/or potassium alginate.
In the three-dimensional structure composite aerogel, the silver nanoparticles, the nitrogen-doped carbon nanotubes and the polypyrrole are simultaneously dispersed on the network-shaped framework, and when the three-dimensional structure composite aerogel is compressed, the silver nanoparticles are mutually contacted, so that the sensitivity of the composite aerogel serving as a pressure sensor is improved.
Preferably, the silver nanoparticles have a particle size of 30nm to 200nm, such as 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 58nm, 60nm, 65nm, 68nm, 70nm, 72nm, 75nm, 78nm, 80nm, 85nm, 90nm, 95nm, 98nm, 100nm, 110nm, 115nm, 120nm, 125nm, 128nm, 130nm, 140nm, 145nm, 150nm, 160nm, 170nm, 175nm, 180nm, 185nm, 190nm or 200nm, etc., preferably 50nm to 100nm, and more preferably 50nm to 70 nm.
The silver nanoparticles not only have good conductivity, but also have a surface effect and a quantum size effect because they belong to nano-sized particles.
In the invention, polypyrrole, silver nanoparticles and nitrogen-doped carbon nanotubes are dispersed on the network framework together, so that the bonding property among all the substances is good, and good rigidity is provided.
In the composite aerogel disclosed by the invention, the sodium alginate and/or potassium alginate improve the associativity among substances, the freeze drying improves the three-dimensional network skeleton, the mechanical strength of the three-dimensional network skeleton is higher, and good compression and rebound effects are provided.
In a third aspect, the present invention provides the use of the three-dimensional structure composite aerogel according to the second aspect, for a pressure sensor.
In the present invention, the "nitrogen-doped carbon nanotube" refers to an acidified nitrogen-doped carbon nanotube.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a preparation method of three-dimensional structure composite aerogel, which adopts acidified solution of nitrogen-doped carbon nano-tubes to mix with pyrrole monomers, the acidified solution of nitrogen-doped carbon nano-tubes has good dispersibility and surface functional groups which are beneficial to uniformly dispersing in the solvent and enhancing the binding property with the pyrrole monomers, then silver nitrate is added to initiate the polymerization of the pyrrole monomers to generate polymerization reaction, the pyrrole monomers are polymerized to form conductive polypyrrole, meanwhile, silver ions are reduced to silver nano-particles, the obtained silver nano-ions have good dispersibility, the obtained dispersion liquid is continuously mixed with solution of sodium alginate and/or potassium alginate to be frozen into blocks and frozen and dried, so that the polypyrrole, nano-silver particles and the acidified solution of nitrogen-doped carbon nano-tubes can be well dispersed on a network-shaped framework formed by the sodium alginate and/or potassium alginate, thereby obtaining the three-dimensional structure composite aerogel.
(2) The invention selects the acidified nitrogen-doped carbon nano-tube with short length and uniform diameter, the invention has good water solubility and dispersibility, can be well dispersed in a three-dimensional structure composite aerogel system by the method of the invention, the silver nano-particles obtained by reduction by the method of the invention have good dispersibility in a three-dimensional structure composite aerogel system, the good dispersion of the two substances on the sodium alginate and/or potassium alginate network skeleton and the firm combination with polypyrrole lead the aerogel of the invention to have stronger rigidity and good mechanical property, the composite aerogel of the invention can well exert the conductivity of the silver nano-particles and the nitrogen-doped carbon nano-tubes when being compressed, and when the pressure sensor is compressed, the silver nano particles are contacted with each other, so that the sensitivity of the pressure sensor prepared by adopting the three-dimensional structure composite aerogel can be obviously improved.
Drawings
Fig. 1 is an SEM image of the three-dimensional structure composite aerogel obtained in example 1;
FIG. 2 is a graph comparing thermogravimetric analysis of nitrogen-doped carbon nanotubes without the acidification treatment purchased in example 1 with the acidified nitrogen-doped carbon nanotubes obtained in step (1), wherein N-CNTs represent purchased nitrogen-doped carbon nanotubes without the acidification treatment; and (2) N-CNTs-COOH represents the acidified nitrogen-doped carbon nano tube obtained in the step (1).
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
(1) Preparing the acidified nitrogen-doped carbon nano tube: putting 500mg of purchased nitrogen-doped carbon nano tube (the diameter is 20nm, the length is 20 mu m) which is not subjected to acidizing into a single-neck flask, adding 60ml of concentrated sulfuric acid with the mass fraction of 98%, performing ultrasonic treatment for 0.5h, adding 20ml of concentrated nitric acid with the mass fraction of 98%, stirring for 10min, and then performing oil bath at 60 ℃ for 2h to obtain the acidized nitrogen-doped carbon nano tube.
(2) Preparing the three-dimensional structure composite aerogel:
① weighing the raw materials according to the mass ratio of the acidified nitrogen-doped carbon nanotube, the pyrrole monomer, the silver nitrate and the sodium alginate of 1:0.1:1.6: 1;
②, preparing an acidified water solution of the nitrogen-doped carbon nano tube, adding pyrrole monomer into the water solution, and performing ultrasonic treatment for 15min to obtain a mixed solution, wherein the mass concentration of the acidified nitrogen-doped carbon nano tube in the mixed solution is 3 mg/mL;
③ stirring the above mixed solution, adding silver nitrate, and reacting to obtain dispersion;
through step ③, on one hand, the pyrrole monomer is polymerized by the initiation of the silver nitrate to obtain polypyrrole, and on the other hand, silver ions in the silver nitrate are reduced to obtain silver nanoparticles during the polymerization reaction;
④, uniformly mixing the dispersion liquid and an aqueous solution of sodium alginate according to the volume ratio of 1:1, freezing the mixture into blocks in a refrigerator, and then putting the blocks in a freeze dryer for freeze drying for 10 to 12 hours at the temperature of minus 180 ℃ to obtain the three-dimensional structure composite aerogel.
Fig. 1 is an SEM image of the three-dimensional structure composite aerogel obtained in example 1, and it can be seen from the figure that the obtained aerogel has a porous pleated structure, and the acidified nitrogen-doped carbon nanotubes, polypyrrole and silver nanoparticles are distributed therein.
FIG. 2 is a comparison graph of thermogravimetric analysis of carbon nanotubes before and after acidification in the three-dimensional structure composite aerogel of example 1, wherein N-CNTs represent nitrogen-doped carbon nanotubes purchased in example 1 without acidification; N-CNTs-COOH represents the acidified nitrogen-doped carbon nanotube in example 1, and it can be seen that untreated N-CNTs have high thermal stability, while the surface carboxyl groups of acidified N-CNTs-COOH are unstable to heat, and the weight loss ratio obviously reaches 16%, indicating that carboxyl groups are successfully introduced through step (1).
In the testing process, the aerogel obtained by the embodiment has better compressible performance, and can still recover after multiple compression-release processes, the macroscopic structure of the aerogel is not damaged, and excellent elasticity and flexibility are shown. In addition, the sensitivity characteristic of the aerogel is tested, and the change of resistance along with strain is researched, so that the result shows that the three-dimensional structure composite aerogel shows better compression resistance sensitivity; the conductivity of the composite aerogel with the three-dimensional structure is tested, and the result shows that the composite aerogel with the three-dimensional structure has high conductivity and good conductivity.
Example 2
(1) Preparing the acidified nitrogen-doped carbon nano tube: placing 600g of nitrogen-doped carbon nano tube (with the diameter of 50nm and the length of 30 mu m) into a single-mouth flask, adding 60ml of concentrated sulfuric acid with the mass fraction of 98%, performing ultrasonic treatment for 0.5h, adding 20ml of concentrated nitric acid with the mass fraction of 98%, stirring for 10min, and performing oil bath at 60 ℃ for 2h to obtain the acidified nitrogen-doped carbon nano tube.
(2) Preparing the three-dimensional structure composite aerogel:
① weighing the raw materials according to the mass ratio of the acidified nitrogen-doped carbon nanotube, the pyrrole monomer, the silver nitrate and the sodium alginate of 1:0.5:0.8: 1;
②, preparing an acidified water solution of the nitrogen-doped carbon nano tube, adding pyrrole monomer into the water solution, and performing ultrasonic treatment for 60min to obtain a mixed solution, wherein the mass concentration of the acidified nitrogen-doped carbon nano tube in the mixed solution is 10 mg/mL;
③ stirring the above mixed solution, adding silver nitrate, and reacting to obtain dispersion;
through step ③, on one hand, the pyrrole monomer is polymerized by the initiation of the silver nitrate to obtain polypyrrole, and on the other hand, silver ions in the silver nitrate are reduced to obtain silver nanoparticles during the polymerization reaction;
④, uniformly mixing the dispersion liquid and an aqueous solution of sodium alginate according to the volume ratio of 1:1, freezing the mixture into blocks in a refrigerator, and then putting the blocks in a freeze dryer for freeze drying for 10 to 12 hours at the temperature of-100 ℃ to obtain the three-dimensional structure composite aerogel.
According to SEM representation, the three-dimensional structure composite aerogel obtained by the comparative example has a porous wrinkle structure, and the acidified nitrogen-doped carbon nano tubes, polypyrrole and silver nano particles are distributed in the three-dimensional structure composite aerogel.
In the testing process, the aerogel obtained by the embodiment has better compressible performance, and can still recover after multiple compression-release processes, the macroscopic structure of the aerogel is not damaged, and excellent elasticity and flexibility are shown. In addition, the sensitivity characteristic of the aerogel is tested, and the change of resistance along with strain is researched, so that the result shows that the three-dimensional structure composite aerogel shows better compression resistance sensitivity; the conductivity of the composite aerogel with the three-dimensional structure is tested, and the result shows that the composite aerogel with the three-dimensional structure has high conductivity and good conductivity.
Example 3
(1) Preparing the acidified nitrogen-doped carbon nano tube: placing 750g of nitrogen-doped carbon nano tube (with the diameter of 40nm and the length of 25 mu m) into a single-neck flask, adding 60ml of concentrated sulfuric acid with the mass fraction of 98%, performing ultrasonic treatment for 0.5h, adding 20ml of concentrated nitric acid with the mass fraction of 98%, stirring for 10min, and performing oil bath at 60 ℃ for 2h to obtain the acidified nitrogen-doped carbon nano tube.
(2) Preparing the three-dimensional structure composite aerogel:
① weighing the raw materials according to the mass ratio of the acidified nitrogen-doped carbon nanotube, the pyrrole monomer, the silver nitrate and the sodium alginate of 1:0.5:0.6: 1;
②, preparing an acidified water solution of the nitrogen-doped carbon nano tube, adding pyrrole monomer into the water solution, and performing ultrasonic treatment for 90min to obtain a mixed solution, wherein the mass concentration of the acidified nitrogen-doped carbon nano tube in the mixed solution is 4 mg/mL;
③ stirring the above mixed solution, adding silver nitrate, and reacting to obtain dispersion;
through step ③, on one hand, the pyrrole monomer is polymerized by the initiation of the silver nitrate to obtain polypyrrole, and on the other hand, silver ions in the silver nitrate are reduced to obtain silver nanoparticles during the polymerization reaction;
④, uniformly mixing the dispersion liquid and an aqueous solution of sodium alginate according to the volume ratio of 1:1, freezing the mixture into blocks in a refrigerator, and then putting the blocks in a freeze dryer for freeze drying for 10 to 12 hours at the temperature of minus 50 ℃ to obtain the three-dimensional structure composite aerogel.
According to SEM representation, the three-dimensional structure composite aerogel obtained by the comparative example has a porous wrinkle structure, and the acidified nitrogen-doped carbon nano tubes, polypyrrole and silver nano particles are distributed in the three-dimensional structure composite aerogel.
In the testing process, the aerogel obtained by the embodiment has better compressible performance, and can still recover after multiple compression-release processes, the macroscopic structure of the aerogel is not damaged, and excellent elasticity and flexibility are shown. In addition, the sensitivity characteristic of the aerogel is tested, and the change of resistance along with strain is researched, so that the result shows that the three-dimensional structure composite aerogel shows better compression resistance sensitivity; the conductivity of the composite aerogel with the three-dimensional structure is tested, and the result shows that the composite aerogel with the three-dimensional structure has high conductivity and good conductivity.
Example 4
(1) Preparing the acidified nitrogen-doped carbon nano tube: placing 800g of nitrogen-doped carbon nano tube (the diameter is 45nm, the length is 10 mu m) into a single-mouth flask, adding 60ml of concentrated sulfuric acid with the mass fraction of 98%, carrying out ultrasonic treatment for 0.5h, adding 20ml of concentrated nitric acid with the mass fraction of 98%, stirring for 10min, and then carrying out oil bath at 60 ℃ for 2h to obtain the acidified nitrogen-doped carbon nano tube.
(2) Preparing the three-dimensional structure composite aerogel:
① weighing the raw materials according to the mass ratio of the acidified nitrogen-doped carbon nanotube, the pyrrole monomer, the silver nitrate and the sodium alginate of 1:0.3:1.5: 1;
②, preparing an acidified water solution of the nitrogen-doped carbon nano tube, adding pyrrole monomer into the water solution, and performing ultrasonic treatment for 120min to obtain a mixed solution, wherein the mass concentration of the acidified nitrogen-doped carbon nano tube in the mixed solution is 20 mg/mL;
③ stirring the above mixed solution, adding silver nitrate, and reacting to obtain dispersion;
through step ③, on one hand, the pyrrole monomer is polymerized by the initiation of the silver nitrate to obtain polypyrrole, and on the other hand, silver ions in the silver nitrate are reduced to obtain silver nanoparticles during the polymerization reaction;
④, uniformly mixing the dispersion liquid and an aqueous solution of sodium alginate according to the volume ratio of 1:1, freezing the mixture into blocks in a refrigerator, and then putting the blocks in a freeze dryer for freeze drying for 10 to 12 hours at the temperature of minus 20 ℃ to obtain the three-dimensional structure composite aerogel.
According to SEM representation, the three-dimensional structure composite aerogel obtained by the comparative example has a porous wrinkle structure, and the acidified nitrogen-doped carbon nano tubes, polypyrrole and silver nano particles are distributed in the three-dimensional structure composite aerogel.
In the testing process, the aerogel obtained by the embodiment has better compressible performance, and can still recover after multiple compression-release processes, the macroscopic structure of the aerogel is not damaged, and excellent elasticity and flexibility are shown. In addition, the sensitivity characteristic of the aerogel is tested, and the change of resistance along with strain is researched, so that the result shows that the three-dimensional structure composite aerogel shows better compression resistance sensitivity; the conductivity of the composite aerogel with the three-dimensional structure is tested, and the result shows that the composite aerogel with the three-dimensional structure has high conductivity and good conductivity.
Example 5
(1) Preparing the acidified nitrogen-doped carbon nano tube: putting 650g of nitrogen-doped carbon nano tube (with the diameter of 35nm and the length of 25 mu m) into a single-neck flask, adding 60ml of concentrated sulfuric acid with the mass fraction of 98%, performing ultrasonic treatment for 0.5h, adding 20ml of concentrated nitric acid with the mass fraction of 98%, stirring for 10min, and performing oil bath at 60 ℃ for 2h to obtain the acidified nitrogen-doped carbon nano tube.
(2) Preparing the three-dimensional structure composite aerogel:
① weighing the raw materials according to the mass ratio of the acidified nitrogen-doped carbon nanotube, the pyrrole monomer, the silver nitrate and the potassium alginate of 1:0.7:0.8: 1;
②, preparing an acidified water solution of the nitrogen-doped carbon nano tube, adding pyrrole monomer into the water solution, and performing ultrasonic treatment for 135min to obtain a mixed solution, wherein the mass concentration of the acidified nitrogen-doped carbon nano tube in the mixed solution is 45 mg/mL;
③ stirring the above mixed solution, adding silver nitrate, and reacting to obtain dispersion;
through step ③, on one hand, the pyrrole monomer is polymerized by the initiation of the silver nitrate to obtain polypyrrole, and on the other hand, silver ions in the silver nitrate are reduced to obtain silver nanoparticles during the polymerization reaction;
④ mixing the dispersion liquid and the water solution of potassium alginate uniformly according to the volume ratio of 1:1, freezing the mixture into blocks in a refrigerator, and then putting the blocks in a freeze dryer to freeze and dry the blocks for 10 to 12 hours at the temperature of minus 60 ℃ to obtain the three-dimensional structure composite aerogel.
According to SEM representation, the three-dimensional structure composite aerogel obtained by the comparative example has a porous wrinkle structure, and the acidified nitrogen-doped carbon nano tubes, polypyrrole and silver nano particles are distributed in the three-dimensional structure composite aerogel.
In the testing process, the aerogel obtained by the embodiment has better compressible performance, and can still recover after multiple compression-release processes, the macroscopic structure of the aerogel is not damaged, and excellent elasticity and flexibility are shown. In addition, the sensitivity characteristic of the aerogel is tested, and the change of resistance along with strain is researched, so that the result shows that the three-dimensional structure composite aerogel shows better compression resistance sensitivity; the conductivity of the composite aerogel with the three-dimensional structure is tested, and the result shows that the composite aerogel with the three-dimensional structure has high conductivity and good conductivity.
Comparative example 1
The preparation method and conditions were the same as in example 1 except that silver nitrate was replaced with ferric chloride hexahydrate.
The result shows that the composite aerogel obtained in the comparative example does not contain silver particles, and compared with the three-dimensional structure composite aerogel in the example 1, the conductivity is reduced by about 30-50%, and the resistance change rate under the same strain is reduced by 20-30%.
Comparative example 2
Except that the acidified nitrogen-doped carbon nanotubes were replaced with non-acidified nitrogen-doped carbon nanotubes, the preparation methods and conditions were the same as in example 1, and a composite aerogel was prepared.
The conductivity of the obtained composite aerogel becomes poor, and compared with the three-dimensional structure composite aerogel of example 1, the conductivity of the composite aerogel is reduced by about 30-50%.
Comparative example 3
The preparation method and conditions were the same as in example 1, except that sodium alginate was not added.
In the comparative example, the aerogel with a three-dimensional structure cannot be obtained because sodium alginate is not added.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (21)
1. A method for preparing a three-dimensional structure composite aerogel, characterized in that the method comprises the following steps:
(1) adding pyrrole monomers into the nitrogen-doped carbon nanotube solution, and uniformly dispersing to obtain a mixed solution;
(2) adding silver nitrate into the mixed solution obtained in the step (1), and fully stirring and mixing to obtain a dispersion liquid;
(3) uniformly mixing the dispersion liquid obtained in the step (2) with a solution of sodium alginate and/or potassium alginate, freezing the mixture into a block, and then freezing and drying the block to obtain the three-dimensional structure composite aerogel;
wherein the nitrogen-doped carbon nanotube is an acidified nitrogen-doped carbon nanotube;
the diameter of the nitrogen-doped carbon nano tube in the solution of the nitrogen-doped carbon nano tube in the step (1) is 20 nm-50 nm; the length of the nitrogen-doped carbon nano tube in the nitrogen-doped carbon nano tube solution in the step (1) is 10-30 mu m;
the solvent of the nitrogen-doped carbon nanotube solution is water;
in the three-dimensional structure composite aerogel, silver nanoparticles, nitrogen-doped carbon nanotubes and polypyrrole are simultaneously dispersed on a network framework.
2. The method of claim 1, wherein the diameter of the nitrogen-doped carbon nanotubes in the solution of nitrogen-doped carbon nanotubes of step (1) is 30nm to 40 nm.
3. The method of claim 1, wherein the length of the nitrogen-doped carbon nanotubes in the solution of nitrogen-doped carbon nanotubes in step (1) is 20 μm to 30 μm.
4. The method of claim 1, wherein the mass ratio of the nitrogen-doped carbon nanotube to the pyrrole monomer, the silver nitrate, the sodium alginate and/or the potassium alginate is 1 (0.1-1): 0.5-2): 1.
5. The method of claim 4, wherein the mass ratio of the nitrogen-doped carbon nanotube to the pyrrole monomer, the silver nitrate, the sodium alginate and/or the potassium alginate is 1 (0.5-1): 1.
6. The method of claim 1, wherein the mass concentration of the nitrogen-doped carbon nanotubes in the mixed solution of step (1) is 3mg/mL to 50 mg/mL.
7. The method of claim 6, wherein the mass concentration of the nitrogen-doped carbon nanotubes in the mixed solution of step (1) is 3mg/mL to 5 mg/mL.
8. The method according to claim 1, wherein the dispersing in step (1) is performed by using ultrasound.
9. The method of claim 8, wherein the time of the ultrasound is 2min to 500 min.
10. The method of claim 9, wherein the time of the ultrasound is 15min to 150 min.
11. The method of claim 1, wherein the silver nitrate is added in step (2) with stirring.
12. The method as claimed in claim 1, wherein the step of adding silver nitrate in step (2) is followed by a step of stirring.
13. The method according to claim 1, wherein the volume ratio of the solution of sodium alginate and/or potassium alginate in step (3) to the volume of the dispersion obtained in step (2) is 1:1.
14. The method according to claim 1, wherein the temperature of the freeze-drying in the step (3) is-195 ℃ to 0 ℃.
15. The method of claim 14, wherein the temperature of the freeze-drying in step (3) is-195 ℃ to-10 ℃.
16. The method according to claim 1, wherein the freeze-drying time in step (3) is 10 to 12 hours.
17. The three-dimensional structure composite aerogel prepared by the method of any one of claims 1 to 16, wherein the three-dimensional structure composite aerogel comprises a three-dimensional network framework and polypyrrole, silver nanoparticles and nitrogen-doped carbon nanotubes dispersed in the three-dimensional network framework, and the nitrogen-doped carbon nanotubes are acidified nitrogen-doped carbon nanotubes;
wherein the three-dimensional network skeleton is a three-dimensional network skeleton formed by sodium alginate and/or potassium alginate.
18. The three-dimensional structure composite aerogel according to claim 17, wherein the silver nanoparticles have a particle size of 30nm to 200 nm.
19. The three-dimensional structure composite aerogel according to claim 18, wherein the silver nanoparticles have a particle size of 50nm to 100 nm.
20. The three-dimensional structure composite aerogel according to claim 19, wherein the silver nanoparticles have a particle size of 50nm to 70 nm.
21. Use of the three-dimensional structured composite aerogel according to any of claims 17 to 20, wherein the three-dimensional structured composite aerogel is used in a pressure sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710188299.1A CN106902715B (en) | 2017-03-27 | 2017-03-27 | Three-dimensional structure composite aerogel, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710188299.1A CN106902715B (en) | 2017-03-27 | 2017-03-27 | Three-dimensional structure composite aerogel, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106902715A CN106902715A (en) | 2017-06-30 |
| CN106902715B true CN106902715B (en) | 2020-03-17 |
Family
ID=59194961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710188299.1A Active CN106902715B (en) | 2017-03-27 | 2017-03-27 | Three-dimensional structure composite aerogel, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106902715B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3113609A1 (en) * | 2020-09-03 | 2022-03-04 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Manufacture of an electrical conduction gradient airgel |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180991B (en) * | 2018-08-27 | 2021-02-02 | 四川理工学院 | Preparation method of nitrogen-doped HCNFS/SA-Men + composite gel |
| CN111354513B (en) * | 2018-12-20 | 2021-12-28 | 南京理工大学 | Silver-doped polypyrrole-coated graphite composite material and preparation method thereof |
| CN111333864A (en) * | 2020-03-16 | 2020-06-26 | 东北大学秦皇岛分校 | Preparation method of environment-friendly self-healing conductive hydrogel |
| CN113136096A (en) * | 2021-05-07 | 2021-07-20 | 河南银金达新材料股份有限公司 | Preparation method of three-dimensional carbon nanotube/polylactic acid conductive composite material |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201100712D0 (en) * | 2011-01-17 | 2011-03-02 | Bio Nano Consulting | Cross-linked carbon nanotube networks |
| CN102790223B (en) * | 2012-08-14 | 2014-12-10 | 上海交通大学 | Carbon-carried multi-metal polypyrrole oxygen reduction catalyst and preparation method thereof |
| CN104835650B (en) * | 2014-04-10 | 2018-04-27 | 北汽福田汽车股份有限公司 | Three-dimensional self assembly aeroge and its preparation method and application |
| CN104437279B (en) * | 2014-11-17 | 2016-08-24 | 北京大学 | Doped carbon nanometer pipe aeroge and preparation method and application |
| CN104495780B (en) * | 2014-12-30 | 2017-01-11 | 浙江碳谷上希材料科技有限公司 | Hydrophilic graphene-carbon nano-tube composite super-light elastic aerogel and preparation method thereof |
| CN105609790B (en) * | 2015-12-14 | 2018-08-07 | 青岛大学 | A kind of preparation method of nickel cobalt/carbon nanotube aerogel zinc and air cell catalyst |
| CN105733016A (en) * | 2016-03-10 | 2016-07-06 | 云南中烟工业有限责任公司 | Carbon-based polymer composite aerosol, preparation method of aerosol and application of aerosol in flue gas analysis |
-
2017
- 2017-03-27 CN CN201710188299.1A patent/CN106902715B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| Strain-Driven and Ultrasensitive Resistive Sensor/Switch Based on Conductive Alginate/Nitrogen-Doped Carbon-Nanotube-Supported Ag Hybrid Aerogels with Pyramid Design;Songfang Zhao 等;《ACS Applied Materials & Interfaces》;20141125;第22823页摘要，第22824页第2节 * |
| 银/聚吡咯纳米复合材料的制备与结构表征;安静等;《河北科技大学学报》;20101031;第31卷(第5期);第409页第1-段，第410页第1节 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3113609A1 (en) * | 2020-09-03 | 2022-03-04 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Manufacture of an electrical conduction gradient airgel |
| EP3964284A1 (en) * | 2020-09-03 | 2022-03-09 | Commissariat à l'Energie Atomique et aux Energies Alternatives | Production of an aerogel with electric conductivity gradient |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106902715A (en) | 2017-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106902715B (en) | Three-dimensional structure composite aerogel, preparation method and application thereof | |
| Xu et al. | Tunable assembly of porous three-dimensional graphene oxide-corn zein composites with strong mechanical properties for adsorption of rare earth elements | |
| Guo et al. | Graphene oxide as an anti-shrinkage additive for resorcinol–formaldehyde composite aerogels | |
| Qin et al. | Wearable and high-performance piezoresistive sensor based on nanofiber/sodium alginate synergistically enhanced MXene composite aerogel | |
| Zhou et al. | Synthesis of graphene/polyaniline composite nanosheets mediated by polymerized ionic liquid | |
| Liu et al. | Electro-active shape memory composites enhanced by flexible carbon nanotube/graphene aerogels | |
| Tang et al. | Three dimensional graphene aerogels and their electrically conductive composites | |
| Ren et al. | Current progress on the modification of carbon nanotubes and their application in electromagnetic wave absorption | |
| CN104495780B (en) | Hydrophilic graphene-carbon nano-tube composite super-light elastic aerogel and preparation method thereof | |
| Shao et al. | Ambient pressure dried shape-controllable sodium silicate based composite silica aerogel monoliths | |
| Xu et al. | Emulsion template synthesis of all conducting polymer aerogels with superb adsorption capacity and enhanced electrochemical capacitance | |
| CN107180706A (en) | The preparation method and application of dyefunctionalized grapheme/polyaniline composite material | |
| Hou et al. | Alginate-based aerogels with double catalytic activity sites and high mechanical strength | |
| CN109847661B (en) | Preparation method of graphene oxide and silver nanowire assembled ternary elastic hydrogel | |
| JP2013514963A (en) | Graphene dispersion and graphene-ionic liquid polymer composite | |
| Park et al. | Effects of functional group of carbon nanotubes on mechanical properties of carbon fibers | |
| Zhao et al. | Nanocomposites of sulfonic polyaniline nanoarrays on graphene nanosheets with an improved supercapacitor performance | |
| CN105348526A (en) | Polypyrrole (at) graphene conductive pressure-sensitive composite material and application thereof | |
| CN109399619A (en) | A kind of preparation method of nitrogen-doped graphene aeroge | |
| CN104530653A (en) | Preparation method of epoxy resin/graphene/nano copper composite material | |
| Yang et al. | Preparation and properties of three dimensional graphene/phenolic resin composites via in-situ polymerization in graphene hydrogels | |
| CN104403275A (en) | Modified grapheme/thermosetting resin composite material and preparation method thereof | |
| CN108624043A (en) | A kind of aerogel composite and preparation method thereof of polypyrrole cladding copper nano-wire | |
| CN111232967A (en) | Preparation method of aminated graphene oxide | |
| CN105949536A (en) | {0><}0{>Preparation method of high-strength natural rubber (NR)/carbon nano tube (CNT) conductive composite film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |