CN111250007A - Preparation method of pure metal aerogel and flexible composite material - Google Patents
Preparation method of pure metal aerogel and flexible composite material Download PDFInfo
- Publication number
- CN111250007A CN111250007A CN202010052115.0A CN202010052115A CN111250007A CN 111250007 A CN111250007 A CN 111250007A CN 202010052115 A CN202010052115 A CN 202010052115A CN 111250007 A CN111250007 A CN 111250007A
- Authority
- CN
- China
- Prior art keywords
- aerogel
- solvent
- metal
- pure
- preparing
- 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.)
- Granted
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
Abstract
The invention provides a preparation method of a pure metal aerogel and a flexible composite material, and the preparation method of the pure metal aerogel comprises the following steps: adding an active material matrix into a solvent for mixing to obtain a three-dimensional growth active agent; melting a required metal precursor and a surfactant into a solvent, adding a three-dimensional growth activator, uniformly mixing, and putting into a closed reaction mold for reaction; and heating the mould to obtain a metal gel structure which has the same shape as the mould and contains a solvent inside, taking out the metal gel structure, cleaning to remove residual solvent, free nanowire monomer and an active agent, and drying to finally obtain the pure metal aerogel with the three-dimensional structure. By adopting the technical scheme of the invention, the three-dimensional growth and spontaneous crosslinking of the nanowire material are realized by controlling the growth path of the nanowire, the pure metal aerogel with high specific surface area, low density and high conductivity is obtained, and the preparation process is simple and easy to control.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of a pure metal aerogel and a flexible composite material.
Background
With the rapid development of flexible electronic technology, the requirements of new generation wearable electronic devices on flexible materials, especially flexible strain sensing materials, are continuously increased, and the new generation wearable electronic devices are often required to have excellent mechanical, conductive and sensing properties, biocompatibility and stability. At present, the traditional flexible sensing materials mainly comprise conductive polymers, metal-doped polymer matrix composite materials, two-dimensional flexible conductive films and the like. Wherein, the conductive polymer has better conductivity but insufficient stability and strain perception performance; the metal-doped polymer-based composite material has the advantages of optimal mechanical property and stability, and poor flexibility, conductivity and biocompatibility; the two-dimensional flexible conductive film prepared by coating nano conductive particles, wires and the like has excellent conductivity and stability, but cannot be widely applied because the nano material has high preparation cost and cannot be crosslinked into a highly sensitive three-dimensional integral structure while keeping flexibility. In order to solve the problems, the invention develops a method for growing a three-dimensional nano network gel structure in one step on the basis of the traditional nano metal wire, thereby realizing the low-cost and large-scale manufacture of a flexible composite material with high flexibility, high conductivity and high sensitivity, and showing huge application prospect in the field of flexible electronic devices and systems.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a preparation method of a pure metal aerogel and a flexible composite material, which can obtain a flexible composite material with high flexibility, high conductivity and high sensitivity and solve the problems of poor conductivity and limited flexible deformation capability of the conventional flexible material.
In contrast, the technical scheme adopted by the invention is as follows:
the preparation method of the pure metal aerogel is characterized by comprising the following steps of:
step S1, adding an active material matrix into a solvent for mixing to obtain a three-dimensional growth active agent;
step S2, melting the needed metal precursor and surfactant into solvent, adding the three-dimensional growth activator obtained in step S1, mixing uniformly, and putting into a closed reaction mold for chemical reduction reaction;
step S3, heating the reaction mould of step S2, and continuously reacting to obtain a metal gel structure which has the same shape with the mould and contains a solvent inside;
and S4, taking out the metal gel tissue obtained in the step S3, cleaning to remove residual solvent, free nanowire monomer and active agent, and drying to finally obtain the pure metal aerogel with the three-dimensional structure.
By adopting the technical scheme, the growth mode of the nanowire can be adjusted through the three-dimensional growth activator, and the nanowire network with the three-dimensional cross-linked structure is formed, which is a necessary condition for preparing the pure metal aerogel. The active material matrix may be dissolved in a solvent or may be formed into a suspension.
As a further improvement of the present invention, in step S1, the active material matrix is one or a mixture of several of lignin, cellulose, amino acid, paraffin, and the like, and decomposition products of the foregoing materials.
As a further improvement of the present invention, the solvent in the three-dimensional growth activator is the same as the solvent used in the reaction in step S2, so that the growth of the nanowires is not affected.
As a further improvement of the invention, the mass ratio of the solvent in the three-dimensional growth active agent is not less than 70%. By adopting the technical scheme, the agglomeration of active substances and the formation of nanowire agglomerates and holes in the growth process of the aerogel can be effectively avoided.
In a further improvement of the present invention, the solvent is an organic solvent such as acetone, ethanol or polyhydric alcohol.
Further, in step S1, the mixing is performed by heating, stirring, ball milling, or the like.
As a further improvement of the present invention, in step S1, the active material matrix is washed and activated and then added to a solvent for dissolution. The dissolution is dissolution or dispersion by means of heating, stirring, ball milling, or the like.
As a further improvement of the present invention, in step S2, the metal precursor is a corresponding salt or organic compound required for preparing metal nanowires of Ag, Cu, Ni, or Au, and the surfactant is a corresponding common surfactant such as PVP, hydrazine hydrate, or glucose.
Further, the mixing mode is electromagnetic or mechanical stirring, and the stirring speed is 100-400 rpm, so as to ensure the stability of nucleation and inhibit the overgrowth of crystal nuclei.
Further, the closed reaction mold is a mold with an internal cavity made of polytetrafluoroethylene, stainless steel or other materials which do not react with the solvent physically and chemically.
As a further improvement of the invention, the depth of the inner cavity of the closed reaction mould<50 mm. This is because the growth of aerogels and nanowires is often influenced by the oxidation process, and even with deeper cavities, larger size aerogels cannot be obtained, only when other oxidants such as H are added2O2、O3、Fe3+When the reactivity is improved, a deeper cavity can be used.
Further, the metal gel structure obtained in step S3 is a jelly-like block, and the internal structure thereof is a nanowire continuous network structure cross-linked to each other in a foam shape.
As a further improvement of the present invention, in step S4, the cleaning is performed by soaking and continuous solvent replacement. Furthermore, in the replacement process, the solvent completely submerges the metal aerogel tissue, deionized water-acetone/ethanol-deionized water or a single solvent is sequentially used in the replacement process, the replacement speed of the solvent is 1-50 ml/min, and the replacement time is 0.5-24 h. The solvent replacement speed is too fast, the damage of the gel structure is easy to cause, the cleaning of the interior of the gel cannot be realized if the replacement speed is too slow, and 0.5h is the shortest replacement time required for ensuring the cleaning effect under the condition of high replacement speed.
As a further improvement of the present invention, in step S4, supercritical drying or ultralow temperature N is adopted2Drying is carried out in a freezing and vacuum freeze drying mode. The pure metal aerogel obtained by adopting the technical scheme of the invention has a three-dimensional structure and is a foam-shaped flexible block material completely formed by crosslinking nano wires. The drying method can avoid collapse or damage of the aerogel network structure caused by the surface tension of the liquid.
The reaction, cleaning and drying method has simple process flow and low requirements on environment and equipment, can ensure that the three-dimensional growth process of the nanowire is performed quickly and fully to form a gel tissue, can effectively remove incompletely-reacted precursors, surfactants, organic solvents and the like, and can avoid collapse or damage of the aerogel structure due to the action of liquid surface tension in the drying process.
The invention also discloses a preparation method of the flexible composite material, which comprises the following steps:
step S11, carrying out surface modification on the pure metal aerogel to obtain modified pure metal aerogel, and improving the interface coupling performance of the pure metal aerogel; wherein the pure metal aerogel is prepared by adopting the preparation method of the pure metal aerogel;
and S12, filling liquid polymer material monomer or nano-particle material into the modified pure metal aerogel obtained in the step S11, and curing or crosslinking to obtain the flexible composite material containing the metal network structure and the heterogeneous reinforcing material inside.
Further, the surface modification is to prepare a transition metal layer of Ni, Au, Ti and the like by chemical plating, electroplating, vapor deposition and the like or prepare a coating layer by using a coupling agent and a high molecular polymer. By the method, the interface coupling matching effect between the metal aerogel matrix and other materials can be improved under the condition of not damaging the metal aerogel matrix, and the uniformity and reliability of the compounding process are ensured.
As a further improvement of the present invention, the liquid polymer material monomer is at least one of Polydimethylsiloxane (PDMS), Polyimide (PI), polyethylene terephthalate (PET), and Polyaniline (PANI), and the nanoparticle material is at least one of micro-nano particles of ceramic, resin spheres, and metal particles.
As a further improvement of the present invention, in step S12, the filling is performed by using a method of three-dimensional ultrasonic vibration, vacuum-assisted flow or capillary adsorption, the liquid polymer material monomer is cured by heating or adding a reaction reagent, and the micro-nano particles are cross-linked by initiating an interfacial reaction by low-temperature heating. The materials can improve the comprehensive performance, structural strength and stability of the obtained composite material, and the filling method can ensure the integrity of a colloid structure and the effective filling of heterogeneous materials in the compounding process, and avoid the problems of local segregation, unfilled or stress concentration and the like caused by the limitation of internal air and structure size in the compounding process.
In addition, the preparation steps and the treatment method of the material are completely compatible with the preparation process of the common metal composite material, the requirements on external process conditions such as environment, equipment and the like are low, and the industrial production requirements can be met by enlarging the size of the die. The obtained composite material has the advantages of good flexibility, high conductivity, low density, strong environmental compatibility, more stable manufacturing yield and obvious application advantage.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the technical scheme of the invention realizes three-dimensional growth and spontaneous crosslinking of the nanowire material by controlling the growth path of the nanowire by utilizing the principle of crystal surface preferential growth, and obtains the pure metal aerogel with high specific surface area, low density and high conductivity. Furthermore, the surface treatment technology is adopted, so that the obtained pure metal aerogel has better performance. The pure metal gel tissue is obtained by one-step growth, a complete and continuous flexible aerogel structure can be obtained only by cleaning and drying, the preparation process is simple, the requirements on materials, equipment and processes are low, and large-scale industrial production can be realized.
Second, the existing nano silverWires or nanoparticles cannot be sintered directly to form a three-dimensional network structure and tend to exhibit significant rigidity or brittleness when larger in size. The pure metal aerogel obtained by the one-step growth of the invention has excellent flexibility and structural stability and extremely low density (<10 mg/cm3) The conductivity is high (up to 75000S/m), the integrity of a three-dimensional structure is ensured, meanwhile, the ultrasonic and vibration can be borne, the plastic deformation is less than 75%, the manufacturing consistency and the yield are very stable, and therefore, the material performance and the process advantage are obvious.
Thirdly, the flexible composite material obtained by the technical scheme of the invention has excellent flexibility, electrical conductivity, thermal conductivity, electromagnetic shielding performance, stability and reliability and good material and process compatibility, is especially suitable for flexible electronic devices or systems, has lower manufacturing and application cost, higher application range and more excellent comprehensive performance compared with the traditional flexible materials such as conductive adhesive, printing ink, metal coating layers and the like, can simultaneously meet the performance requirements of rigid and flexible devices, and has wide application prospect in the fields of thermal interface interconnection, flexible electronic manufacturing, heterogeneous material integration and packaging.
Drawings
FIG. 1 is a comparison graph of the metal gel structure obtained in the embodiment of the present invention and the macroscopic structure of the suspension and the precipitate of the conventional silver nanowire; wherein (a) is an appearance diagram of a traditional nano silver wire suspension, (b) is an appearance diagram of a traditional nano silver wire precipitate, and (c) is an appearance diagram of a metal gel structure obtained by the embodiment of the invention.
FIG. 2 is a macroscopic and microscopic structural morphology chart of the pure metal aerogel obtained after drying according to the embodiment of the present invention; wherein (a) is a macroscopic picture of the pure metal aerogel, and (b) is a microstructure topography of the pure metal aerogel.
FIG. 3 is a schematic tissue morphology of a PDMS-based flexible composite obtained by an embodiment of the present invention.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
Example 1
A pure Ag aerogel with a continuous nano-silver wire network structure inside, which is prepared by the following steps:
(1) the method comprises the following steps of using a mixture of lignin and cellulose as an active matrix, wherein the mass ratio of the lignin to the cellulose is 1:1.5, sequentially using 10 vol.% of hydrochloric acid alcohol solution and hydrogen peroxide solution to clean the active matrix, extracting the clean active matrix and a hydrolysate thereof in a freeze drying mode, and adding the extract into an ethylene glycol solvent to obtain the required three-dimensional growth active agent, wherein the mass ratio of active substances is 10%.
(2) PVP (0.35 g) is used as a surfactant and added into ethylene glycol (25 ml), the mixture is stirred at a high speed (>350 rpm) for 6 hours to obtain a transparent and uniform solution, then silver nitrate (0.4 g) and the above-mentioned active agent (3 ml) are added in sequence, the mixture is fully stirred and poured into a reaction kettle made of polytetrafluoroethylene, and nucleation of the nano silver wires is initiated.
(3) Sealing the reaction kettle by external pressure, placing in a constant temperature heating furnace at 165 deg.C, heating for 6-12h to ensure the growth of the silver nanowires to fully proceed, and obtaining the jelly-like gel tissue composed of silver nanowires as shown in FIG. 1 (c). Compared with the morphology of the macroscopic structure of the traditional nano silver wire suspension and nano silver wire deposition of fig. 1 (a) and 1 (b), the nano silver wire of the embodiment forms a three-dimensional block structure.
(4) Sequentially washing the obtained gel tissue with deionized water-ethanol-deionized water by solute replacement method to remove residual ethylene glycol, PVP and nano silver wire monomer, and passing through supercritical CO2The obtained gel is dried by a drying method to obtain pure silver aerogel with a three-dimensional structure, as shown in fig. 2.
The pure silver aerogel obtained by the embodiment has excellent elasticity, conductivity and structural stability, the recoverable deformation amount is 50% -80%, the ion conversion rate is high, the preparation cost is low, and the pure silver aerogel can be used as a structural matrix to prepare other flexible composite materials or thermal interface materials with elasticity and conductivity requirements.
Example 2
A PDMS-based flexible composite material with a continuous nano copper wire network structure inside, which is prepared by the following steps:
(1) the method comprises the following steps of using a mixture of glutamic acid, alanine and cellulose as an active matrix, wherein the mass ratio of the glutamic acid to the alanine to the cellulose is 1: 2: and 1.5, cleaning by using acetone, heating for 30 minutes at 50 ℃ to complete drying, and adding the dried product into deionized water to obtain the required three-dimensional growth activator, wherein the mass ratio of active substances is 15%.
(2) Copper nitrate (0.1mol/L, 1 ml) is used as a precursor, hydrazine hydrate (35 wt.%, 0.025 ml) is used as a reducing agent, ethylenediamine (0.15 ml) is used as a surfactant and added into sodium hydroxide (15mol/L, 20 ml) solution, the obtained solution is placed into a flask for fully stirring, heating is carried out for 10min to initiate liquid phase reduction reaction, and then the obtained solution is placed into an ice water bath for 1h to promote the reaction to fully proceed, so that a jelly-shaped gel tissue consisting of nano copper wires is obtained.
(3) Sequentially using deionized water-acetone-ethanol-deionized water to perform solvent replacement on the obtained gel tissue, and passing through liquid N2And removing residual deionized water by a cooling and vacuum freeze drying method to obtain the copper aerogel with a three-dimensional structure.
(4) Removing the oxide on the surface of the copper aerogel by using 0.5% formic acid alcohol solution, drying again, meanwhile, preparing two reagents required by PDMS curing in proportion, adding a coupling agent with the mass ratio of 0.2%, fully stirring, pouring the obtained mixed reagent on the copper aerogel, fully filling PDMS in the aerogel by means of a vacuum pump, finally heating at 100 ℃ for 1h to complete curing, and performing surface cleaning and cutting to obtain the PDMS-based composite material with high elasticity, flexibility and high conductivity, as shown in FIG. 3.
The composite material obtained by the embodiment can effectively ensure that a continuous copper wire network is formed in the PDMS matrix, and the conductivity is guaranteed to be 10%-5Omega m) and simultaneously provides excellent stability and processability, can be used as a conductive path or a protective layer after being processed to be applied to electronic devices and flexible systems, and simultaneously has certain density due to the extremely low density of the aerogelThe obtained composite material also has the characteristics of light weight and excellent elastic flexibility.
Example 3
An aerogel reinforced semi-sintered silver composite material is characterized in that a continuous nano silver wire network structure exists inside nano silver particles, and the preparation method comprises the following steps:
(1) silver nitrate (3 g) is used as a precursor, sodium citrate (100 g) is used as a surfactant, ferrous chloride (15 g) is used as a reducing agent, deionized water (200 ml) is used as a solvent to prepare nano silver particles, and the average particle size of the obtained nano silver particles is 20-40 nm.
(2) The method comprises the steps of using a mixture of lignin and cellulose as an active matrix, wherein the mass ratio of the lignin to the cellulose is 1:1.5, sequentially using 10 vol.% of hydrochloric acid alcohol solution and hydrogen peroxide solution to clean the active matrix, extracting the active matrix and hydrolysate thereof in a freeze drying mode, and mixing the active matrix and hydrolysate thereof into an ethylene glycol solvent to obtain the required three-dimensional growth activator, wherein the mass ratio of active substances is 17.5%.
(2) Adding PVP (0.35 g) serving as a surfactant into ethylene glycol (25 ml), stirring at a high speed (>350 rpm) for 6 hours to obtain a transparent and uniform solution, then sequentially adding silver nitrate (0.4 g) and the above-mentioned active agent (3 ml), fully stirring and pouring into a reaction kettle made of polytetrafluoroethylene; the reaction kettle is sealed by means of external pressure, and is placed in a constant-temperature heating furnace at 165 ℃ for heating for 6-12 hours, so that the growth of the nano silver wires is fully carried out, and the jelly-like gel tissue is obtained.
(4) Respectively cleaning the obtained nano silver particles and the obtained gel tissue by using a deionized water, ethanol and solvent replacement method; and then dispersing the nano silver particles in ethanol, soaking the cleaned gel tissue in the obtained suspension, sequentially performing three-dimensional ultrasonic vibration and solvent replacement, and spontaneously filling the nano silver particles in the gaps in the gel under the action of ultrasound and capillary adsorption.
(5) Subjecting the obtained gel tissue filled with nano silver particles to supercritical CO2Drying to obtain silver aerogel filled with nano silver particles, and heating at 50-100 deg.C for solidifyingAnd (5) dissolving for 30min to finish the pre-fixing of the nano silver particles and the nano silver wire network.
The composite aerogel obtained by the embodiment has more excellent conductivity, the volume resistance is only 2-5 times of that of bulk silver, the composite aerogel can be sintered at room temperature or 300 ℃ of 200-.
Comparative example 1
A fiber-based aerogel material and a metal composite material are prepared by the following steps:
(1) firstly, preparing a fiber suspension or a fiber/functionalized particulate matter composite suspension;
(2) solidifying the suspension, and removing the solvent in the solidified block to form the uncrosslinked fiber-based aerogel;
(3) forming a three-dimensional network material through crosslinking stabilization treatment or modification treatment;
(4) and filling metal into the three-dimensional nano hollow structure of the aerogel by taking the fiber aerogel as a matrix to obtain the metal-fiber aerogel composite material.
Under the process conditions of the embodiment, in order to obtain aerogel and metal composite materials with high activity and high performance, nano-sized fibers or particles are used as a substrate to prepare suspension, so that the network-shaped aerogel can be obtained only by 'nano-material preparation-cleaning-suspension dispersion-solidification treatment-drying-crosslinking', and the material cost and the process complexity are far higher than those of the 'one-step synthesis-cleaning-drying' process; meanwhile, in the solidification process, pores or gaps (micron order) caused by crystallization of the solvent are far larger than pores (50-200 nm) formed by spontaneous growth of the nanowires, so that the specific surface area and the reaction activity of the nano-wire are far lower than those of the nano-wire; in addition, the performance of the metal aerogel is close to that of bulk metal and is higher than that of a metal particle sintered body under the same quality, and the temperature required by polymer crosslinking-curing and intermetallic interdiffusion is far lower than the sintering temperature of the metal particles, so that the metal aerogel is taken as a substrate for compounding, the performance of the composite material is improved, and the process temperature required by compounding is reduced. In summary, the present invention has significant process and performance advantages over this embodiment.
Comparative example 2
A common flexible polymer-based composite material is prepared by the following steps:
(1) preparing micro-nano silver particles by a spray drying method or a liquid phase reduction method;
(2) and mixing the obtained silver particles with a polymer matrix, uniformly dispersing and directly curing to form the conductive composite material containing the silver particles inside.
Under the process conditions of the embodiment, uniform dispersion and interconnection of micro-nano particles are a key problem which cannot be controlled, and the electric conduction or heat conduction performance of the obtained composite material can be ensured only by greatly increasing the content (> 60%) of the metal particles, however, the cost is greatly increased and the flexibility is obviously reduced due to the excessively high content of the metal particles, so that the comprehensive cost performance is far lower than that of the composite material.
Comparative example 3
A commonly used nano-silver paste is prepared by the following steps:
(1) preparing nano-silver or nano-silver-coated copper particles by a liquid phase reduction method or a laser method, wherein the average particle size of the nano-silver or nano-silver-coated copper particles is 10-50 nm;
(2) repeatedly cleaning the obtained nano particles, flocculating, centrifuging and drying at low temperature to obtain pure nano metal particles;
(3) and compounding the obtained nano metal particles with soldering flux or other reinforcing phases such as nano sheets, nano wires and the like, wherein the mass ratio of the soldering flux is about 10-14%, and thus obtaining the nano silver paste.
Compared with other embodiments, the embodiment directly uses the nano material with higher activity, can realize the interconnection among metal materials such as Cu, Ag, Au and the like, and obtains the mechanical property close to that of bulk metal. However, the material must be heated at >220 ℃ for 1h to complete sintering, and the obtained joint has no flexibility or deformability, so that the aerogel disclosed by the invention cannot be applied to the preparation and integration of flexible devices.
Comparative example 4
A flexible electrode of an Ag-Zn battery is prepared by the following steps:
(1) preparing nano silver wire, repeatedly cleaning, and fully dispersing in ethanol to form conductive ink
(2) And (2) repeatedly spraying conductive ink on the surface of the substrate PET or paper, heating and drying to form a layer of compact nano silver wire network, wherein the silver wire network and the substrate form an Ag electrode of the Ag-Zn battery.
Under the process condition of the embodiment, the nano silver wires are mutually stacked to form an Ag electrode structure, and the Ag-Zn battery has higher porosity, so that the energy density and the volt-ampere characteristic of the Ag-Zn battery can be obviously improved. However, the nano silver wires are mainly stacked to form a continuous network structure, the structural stability is poor, the void density and the specific surface area are both lost, and the overall modification capacity of the electrode is remarkably reduced due to the increase of the thickness, so that the energy storage density and the electrochemical performance of the nano silver wires are lower than those of the pure Ag aerogel.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. The preparation method of the pure metal aerogel is characterized by comprising the following steps of:
step S1, adding an active material matrix into a solvent for mixing to obtain a three-dimensional growth active agent;
step S2, melting the needed metal precursor and surfactant into solvent, adding the three-dimensional growth activator obtained in step S1, mixing uniformly, and putting into a closed reaction mold for chemical reduction reaction;
step S3, heating the reaction mould of step S2, and continuously reacting to obtain a metal gel structure which has the same shape with the mould and contains a solvent inside;
and S4, taking out the metal gel tissue obtained in the step S3, cleaning to remove residual solvent, free nanowire monomer and active agent, and drying to finally obtain the pure metal aerogel with the three-dimensional structure.
2. The method for preparing a pure metallic aerogel according to claim 1, characterized in that: in step S1, the active material matrix is one or a mixture of lignin, cellulose, amino acids, paraffin materials, and decomposition products of the foregoing materials.
3. The method for preparing a pure metallic aerogel according to claim 1, characterized in that: the mass ratio of the solvent in the three-dimensional growth activator is not less than 70 percent; the solvent is acetone, ethanol or polyalcohol; in step S1, the active material matrix is washed and activated and then added to a solvent.
4. The method for preparing a pure metallic aerogel according to claim 1, characterized in that: in step S2, the metal precursor and the surfactant are corresponding reaction reagents required for preparing nanowires of Ag, Cu, Ni, Au, or the like.
5. The method for preparing a pure metallic aerogel according to claim 4, characterized in that: the depth of the inner cavity of the closed reaction mould is not more than 50 mm.
6. The method for preparing a pure metallic aerogel according to claim 1, characterized in that: in step S4, the cleaning is performed by soaking and continuous solvent replacement; in the replacement process, the solvent completely submerges the metal aerogel tissue, deionized water-acetone/ethanol-deionized water or a single solvent is used in the replacement process in sequence, the replacement speed of the solvent is 1-50 ml/min, and the replacement time is 0.5-24 h.
7. The method for preparing a pure metallic aerogel according to claim 1, characterized in that: in step S4, supercritical drying or ultralow temperature N is adopted2Drying is carried out in a freezing and vacuum freeze drying mode.
8. A preparation method of a flexible composite material is characterized by comprising the following steps: which comprises the following steps:
step S11, carrying out surface modification on the pure metal aerogel to obtain modified pure metal aerogel; the pure metal aerogel is prepared by the preparation method of the pure metal aerogel according to any one of claims 1 to 7;
and S12, filling liquid polymer material monomer or nano-particle material into the modified pure metal aerogel obtained in the step S11, and curing or crosslinking to obtain the flexible composite material containing the metal network structure and the heterogeneous reinforcing material inside.
9. The method of preparing a flexible composite material according to claim 8, wherein: the liquid polymer material monomer is at least one of polydimethylsiloxane, polyimide, polyethylene terephthalate and polyaniline, and the nano-particle material is at least one of micro-nano particles of ceramics, resin balls and metal particles.
10. The method of preparing a flexible composite material according to claim 9, wherein: in step S12, the filling is performed by three-dimensional ultrasonic vibration, vacuum assisted flow or capillary adsorption, the liquid polymer monomer is cured by heating or adding a reaction reagent, and the micro-nano particles are cross-linked by initiating an interface reaction by low-temperature heating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010052115.0A CN111250007B (en) | 2020-01-17 | 2020-01-17 | Preparation method of pure metal aerogel and flexible composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010052115.0A CN111250007B (en) | 2020-01-17 | 2020-01-17 | Preparation method of pure metal aerogel and flexible composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111250007A true CN111250007A (en) | 2020-06-09 |
| CN111250007B CN111250007B (en) | 2022-04-22 |
Family
ID=70945285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010052115.0A Active CN111250007B (en) | 2020-01-17 | 2020-01-17 | Preparation method of pure metal aerogel and flexible composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111250007B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111702368A (en) * | 2020-06-23 | 2020-09-25 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Preparation method and packaging method of metal aerogel-based preformed soldering lug |
| CN111992149A (en) * | 2020-08-12 | 2020-11-27 | 中山大学 | Preparation method of porous carrier supported metal aerogel composite material |
| CN112222672A (en) * | 2020-10-09 | 2021-01-15 | 哈尔滨工业大学（深圳） | Composite material for low-temperature packaging, preparation method thereof and packaging method |
| CN112264628A (en) * | 2020-10-28 | 2021-01-26 | 中国工程物理研究院激光聚变研究中心 | Preparation method of gold aerogel |
| CN112816111A (en) * | 2020-12-25 | 2021-05-18 | 哈尔滨工业大学（深圳） | Flexible touch sensor and manufacturing method thereof |
| CN112924906A (en) * | 2021-01-26 | 2021-06-08 | 西安交通大学 | Wireless flexible magnetic sensor based on magnetocaloric effect, and preparation method and detection method thereof |
| CN113341597A (en) * | 2021-06-17 | 2021-09-03 | 航天特种材料及工艺技术研究所 | Silicon dioxide aerogel with light transmittance changing along with ambient temperature, and preparation method and application thereof |
| CN113858742A (en) * | 2021-09-30 | 2021-12-31 | 南京恒电先进微波技术研究院有限公司 | Flexible electromagnetic shielding film and preparation method thereof |
| CN115124758A (en) * | 2022-08-17 | 2022-09-30 | 大连海洋大学 | Preparation process of aerogel composite material |
| CN115418029A (en) * | 2022-08-19 | 2022-12-02 | 东华大学 | Aerogel-based material for broadband electromagnetic wave management and preparation and application thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4319909A1 (en) * | 1993-06-16 | 1994-12-22 | Solvay Deutschland | Transition metal airgel-supported catalyst |
| CN101219360A (en) * | 2008-01-24 | 2008-07-16 | 同济大学 | Process for producing transition metal base silica aerogel, transition metal oxide silica aerogel, composite transition metal oxide silica aerogel |
| CN103073891A (en) * | 2013-01-15 | 2013-05-01 | 华东理工大学 | Preparation method of high-conductivity flexible conductive composite material |
| CN103288416A (en) * | 2013-05-27 | 2013-09-11 | 东华大学 | Modified three-dimensional fiber-based aerogel material and preparation method thereof |
| CN104801244A (en) * | 2015-04-09 | 2015-07-29 | 浙江理工大学 | Method for preparing three-dimensional graphene-copper nanowire composite aerogel |
| CN105032354A (en) * | 2015-07-29 | 2015-11-11 | 北京石油化工学院 | Silver nanowire/graphene composite elastic aerogel, and preparation method and application thereof |
| CN105251484A (en) * | 2015-11-20 | 2016-01-20 | 上海交通大学 | Reduction-oxidation graphene/nanometer metallic silver aerogel with three-dimensional structure and preparation method |
| CN105970193A (en) * | 2016-05-24 | 2016-09-28 | 中国工程物理研究院激光聚变研究中心 | Metal aerogel with high specific surface area and preparation method thereof |
| CN105970613A (en) * | 2016-06-24 | 2016-09-28 | 东华大学 | Method for preparing continuous cellulose/nano-metal aerogel fiber with catalytic performance from back-loaded nano-metal |
| CN108295778A (en) * | 2018-04-24 | 2018-07-20 | 中国工程物理研究院激光聚变研究中心 | A kind of noble metal aeroge and preparation method thereof |
| CN109400960A (en) * | 2018-08-28 | 2019-03-01 | 江苏理工学院 | A kind of graphene/nano silver polymer composites and preparation method thereof |
| CN110078031A (en) * | 2019-05-27 | 2019-08-02 | 中国科学技术大学 | A kind of Te nano wire three-dimensional aeroge, preparation method and its application |
| CN110639516A (en) * | 2019-10-16 | 2020-01-03 | 浙江大学台州研究院 | Graphene-loaded multi-metal nanowire aerogel composite material and preparation method thereof |
-
2020
- 2020-01-17 CN CN202010052115.0A patent/CN111250007B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4319909A1 (en) * | 1993-06-16 | 1994-12-22 | Solvay Deutschland | Transition metal airgel-supported catalyst |
| CN101219360A (en) * | 2008-01-24 | 2008-07-16 | 同济大学 | Process for producing transition metal base silica aerogel, transition metal oxide silica aerogel, composite transition metal oxide silica aerogel |
| CN103073891A (en) * | 2013-01-15 | 2013-05-01 | 华东理工大学 | Preparation method of high-conductivity flexible conductive composite material |
| CN103288416A (en) * | 2013-05-27 | 2013-09-11 | 东华大学 | Modified three-dimensional fiber-based aerogel material and preparation method thereof |
| CN104801244A (en) * | 2015-04-09 | 2015-07-29 | 浙江理工大学 | Method for preparing three-dimensional graphene-copper nanowire composite aerogel |
| CN105032354A (en) * | 2015-07-29 | 2015-11-11 | 北京石油化工学院 | Silver nanowire/graphene composite elastic aerogel, and preparation method and application thereof |
| CN105251484A (en) * | 2015-11-20 | 2016-01-20 | 上海交通大学 | Reduction-oxidation graphene/nanometer metallic silver aerogel with three-dimensional structure and preparation method |
| CN105970193A (en) * | 2016-05-24 | 2016-09-28 | 中国工程物理研究院激光聚变研究中心 | Metal aerogel with high specific surface area and preparation method thereof |
| CN105970613A (en) * | 2016-06-24 | 2016-09-28 | 东华大学 | Method for preparing continuous cellulose/nano-metal aerogel fiber with catalytic performance from back-loaded nano-metal |
| CN108295778A (en) * | 2018-04-24 | 2018-07-20 | 中国工程物理研究院激光聚变研究中心 | A kind of noble metal aeroge and preparation method thereof |
| CN109400960A (en) * | 2018-08-28 | 2019-03-01 | 江苏理工学院 | A kind of graphene/nano silver polymer composites and preparation method thereof |
| CN110078031A (en) * | 2019-05-27 | 2019-08-02 | 中国科学技术大学 | A kind of Te nano wire three-dimensional aeroge, preparation method and its application |
| CN110639516A (en) * | 2019-10-16 | 2020-01-03 | 浙江大学台州研究院 | Graphene-loaded multi-metal nanowire aerogel composite material and preparation method thereof |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111702368B (en) * | 2020-06-23 | 2022-04-22 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Preparation method and packaging method of metal aerogel-based preformed soldering lug |
| CN111702368A (en) * | 2020-06-23 | 2020-09-25 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Preparation method and packaging method of metal aerogel-based preformed soldering lug |
| CN111992149A (en) * | 2020-08-12 | 2020-11-27 | 中山大学 | Preparation method of porous carrier supported metal aerogel composite material |
| CN112222672A (en) * | 2020-10-09 | 2021-01-15 | 哈尔滨工业大学（深圳） | Composite material for low-temperature packaging, preparation method thereof and packaging method |
| CN112264628A (en) * | 2020-10-28 | 2021-01-26 | 中国工程物理研究院激光聚变研究中心 | Preparation method of gold aerogel |
| CN112264628B (en) * | 2020-10-28 | 2022-03-25 | 中国工程物理研究院激光聚变研究中心 | Preparation method of gold aerogel |
| CN112816111A (en) * | 2020-12-25 | 2021-05-18 | 哈尔滨工业大学（深圳） | Flexible touch sensor and manufacturing method thereof |
| CN112924906A (en) * | 2021-01-26 | 2021-06-08 | 西安交通大学 | Wireless flexible magnetic sensor based on magnetocaloric effect, and preparation method and detection method thereof |
| CN113341597A (en) * | 2021-06-17 | 2021-09-03 | 航天特种材料及工艺技术研究所 | Silicon dioxide aerogel with light transmittance changing along with ambient temperature, and preparation method and application thereof |
| CN113341597B (en) * | 2021-06-17 | 2023-06-09 | 航天特种材料及工艺技术研究所 | Silica aerogel with light transmittance changing along with ambient temperature, and preparation method and application thereof |
| CN113858742A (en) * | 2021-09-30 | 2021-12-31 | 南京恒电先进微波技术研究院有限公司 | Flexible electromagnetic shielding film and preparation method thereof |
| CN115124758A (en) * | 2022-08-17 | 2022-09-30 | 大连海洋大学 | Preparation process of aerogel composite material |
| CN115418029A (en) * | 2022-08-19 | 2022-12-02 | 东华大学 | Aerogel-based material for broadband electromagnetic wave management and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111250007B (en) | 2022-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111250007B (en) | Preparation method of pure metal aerogel and flexible composite material | |
| CN110628155B (en) | MXene/metal composite aerogel, preparation method and application thereof, and thermal interface material comprising MXene/metal composite aerogel | |
| Zhang | Interfacial assembly of two-dimensional MXenes | |
| CN108165018B (en) | Silicone rubber/graphene/silver nanowire nano composite material for electromagnetic shielding and preparation method thereof | |
| Yang et al. | Timesaving, high-efficiency approaches to fabricate aramid nanofibers | |
| CN108250677B (en) | Polymer-based composite material containing filler particle three-dimensional network and preparation method thereof | |
| Huang et al. | Super-stretchable and self-healing hydrogel with a three-dimensional silver nanowires network structure for wearable sensor and electromagnetic interference shielding | |
| CN103849008A (en) | Hybridized particle, polymer-based composite material, their preparation methods and use of polymer-based composite material | |
| CN105949512A (en) | Intercalation assembly based boron nitride-graphene composite material as well as application and preparation method thereof | |
| AU2011279530A1 (en) | Material and applications therefor | |
| CN108889959B (en) | rGO/Cu composite material and preparation method thereof | |
| CN105583408A (en) | Preparation method and application of Cu nanowire-reduced graphene oxide three-dimensional porous film | |
| JPWO2006043431A1 (en) | Composite metal body and method for producing the same | |
| CN111171362B (en) | Conductive silk material and preparation method and application thereof | |
| CN106832782A (en) | A kind of laminal filter particle/polymer composite and preparation method thereof | |
| CN109749441B (en) | Preparation method of conductive hydrogel based on one-dimensional nano polypyrrole | |
| CN111777841A (en) | Lamellar anisotropy-based graphene/epoxy resin composite material and preparation method thereof | |
| CN105602201B (en) | A kind of preparation method of high-strength conductive high molecule nano composite material | |
| CN112980182A (en) | COFs/nylon 6 composite material and preparation method thereof | |
| JP2008166641A (en) | Expanded carbon fiber composite material for electromagnetic shield with thermal conductivity and electric conductivity, and manufacturing method thereof | |
| CN110452494B (en) | Composite heat conduction material and preparation method thereof | |
| Yang et al. | Nanofibrous materials | |
| CN113289558B (en) | Discretization preparation method of two-dimensional material aerogel with designable three-dimensional structure | |
| CN101003088B (en) | Organism single layer protecting metal-group foam material, and its preparing method | |
| CN116535748A (en) | Thermal-conductivity-enhanced elastic thermal interface composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |