CN113249876A - Ion conductor material and preparation method and application thereof - Google Patents
Ion conductor material and preparation method and application thereof Download PDFInfo
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- CN113249876A CN113249876A CN202110647100.3A CN202110647100A CN113249876A CN 113249876 A CN113249876 A CN 113249876A CN 202110647100 A CN202110647100 A CN 202110647100A CN 113249876 A CN113249876 A CN 113249876A
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- 238000000034 method Methods 0.000 claims abstract description 58
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- 239000012528 membrane Substances 0.000 claims abstract description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 42
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 17
- 235000019253 formic acid Nutrition 0.000 claims description 17
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- 239000002245 particle Substances 0.000 claims description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 claims description 2
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- 240000000249 Morus alba Species 0.000 description 8
- 241000382353 Pupa Species 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
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- 150000002500 ions Chemical class 0.000 description 3
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- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 229920001872 Spider silk Polymers 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
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Images
Classifications
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The invention provides an ion conductor material and a preparation method and application thereof, wherein the preparation method comprises the following steps: the solution containing metal ions and silk protein is used as spinning solution, a nanofiber membrane is formed through electrostatic spinning, and airflow is adopted in the electrostatic spinning process to assist spinning. In the preparation method of the nanofiber ionic conductor provided by the invention, airflow is used for carrying out auxiliary drafting and correction on jet flow of electrostatic spinning, so that stable and continuous preparation of ionic conductor materials with uniform diameters is realized. In addition, the metal ions in the nano-fibers in the ion conductor material prepared by the technical means of the invention are uniformly distributed, which is beneficial to improving the performance stability of the ion conductor material.
Description
Technical Field
The invention relates to the field of ionic conductors, in particular to an ionic conductor and a preparation method and application thereof.
Background
With the advent of the 5G era and the rise of flexible wearable technology, flexible electronic devices have received much attention as core materials of wearable technology.
The stretchable flexible electronic device can meet the functions of the conventional rigid electronic device, and can also adapt to the mechanical deformation of electronic equipment in the using process, so that the stretchable flexible electronic device has good application potential in the field of flexible electronic skin. The ion conductor material based on the nano-fibers has the characteristics of good flexibility, excellent air permeability, good adhesion and the like, and has good application prospects in the aspects of human-computer interaction and comfortable artificial skin.
The current methods for preparing ion conductor nanofiber/nanofiber membranes are mainly of two types, the first method is that prepared nanofiber/nanofiber membranes are usually immersed in a salt solution, the method has the problems of uneven distribution in an ion permeation process and the post-treatment is easy to cause the change of fiber morphology, so that the usability of materials is poor. Another method is to use a solution spinning method, mix salt ions with a polymer for dissolution, and then spin the solution by an electrostatic spinning method to obtain the ion conductor nanofiber, however, this method has a great problem: the electrostatic spinning method is seriously influenced by the conductivity of a spinning solution, and after conductive ions are doped into the spinning solution, the spinnability of the spinning solution is seriously deteriorated, which is specifically shown in that jet flow shakes seriously in the spinning process, so that the spinning solution splashes to cause fiber membrane defects.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide an ion conductor material, a method for preparing the same, and a use thereof, which solve the problems of the prior art.
To achieve the above objects and other related objects, the present invention is achieved by the following technical solutions.
The invention provides a preparation method of an ion conductor material, which comprises the following steps: the solution containing metal ions and silk protein is used as spinning solution, a nanofiber membrane is formed through electrostatic spinning, and airflow is adopted in the electrostatic spinning process to assist spinning.
Preferably, the metal ion is selected from Ca2+、Li+、Mg2+、Na+And K+One or more of them.
Preferably, the silk protein is silk and/or spider silk.
Preferably, the spinning solution is further added with an additive, and the additive is one or more selected from graphene, graphene oxide, boron nitride, metal organic framework materials (MOF for short), covalent organic framework materials (COF for short), nano silver particles and nano copper particles.
Preferably, the mass ratio of the additive to the fibroin is (0.1-100): 100.
preferably, the solvent in the solution is one or more selected from water, ethanol, formic acid, acetic acid and hexafluoroisopropanol. Preferably, the mass ratio of the metal salt for providing metal ions to the silk protein is (0.1-100): 100.
preferably, the process conditions in electrospinning include: the power voltage is 10-60 kV, the temperature of the spinning environment is 15-40 ℃, the relative humidity of the spinning environment is 20-80%, and the receiving distance is 10-70 cm.
Preferably, the pressure of the gas flow is 5 psi-50 psi, and the direction of movement of the gas flow is along the direction from the showerhead to the receiving surface.
The invention also discloses the ion conductor material formed by the preparation method.
The invention also discloses the application of the ionic conductor material as the electronic skin.
In the preparation method of the nanofiber ionic conductor provided by the invention, airflow is used for carrying out auxiliary drafting and correction on jet flow of electrostatic spinning, so that stable and continuous preparation of ionic conductor materials with uniform diameters is realized. In addition, the metal ions in the nano-fibers in the ion conductor material prepared by the technical means of the invention are uniformly distributed, which is beneficial to improving the performance stability of the ion conductor material.
Drawings
FIG. 1 is a schematic view showing the structure of a spinneret in which air nozzles and spinning nozzles are coaxially arranged, which is used in the spinneret of the present invention.
FIG. 2 is a schematic view of a spinneret in which a plurality of air nozzles are circumferentially arranged around the periphery of the spinneret according to an embodiment of the present invention.
Fig. 3 is an SEM image of the ion conductor material formed in example 1 of the present invention.
Fig. 4 is an SEM image of the ion conductor material formed in example 4 of the present invention.
Fig. 5 is a graph showing the effect of the electronic skin formed in example 4 of the present invention.
Fig. 6 is a graph showing the flame retardant effect of the electronic skin formed in example 4 of the present invention.
Fig. 7 is a graph showing the trend of the change in the electrical resistance of the electronic skin formed in example 4 of the present invention after contacting a flame.
FIG. 8 is a schematic diagram showing the conductivity of the nanofiber ionic conductor in example 5 at different temperatures
The reference numerals in fig. 1 and 2 are described as follows, 1 being a spinning nozzle and 2 being an air nozzle.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
The application provides an ion conductor material, a preparation method and application thereof. The preparation method of the ionic conductor material comprises the following steps: the solution containing metal ions and silk protein is used as spinning solution, a nanofiber membrane is formed through electrostatic spinning, and airflow is adopted in the electrostatic spinning process to assist spinning.
The invention uses the airflow-assisted electrostatic spinning technology to perform auxiliary drafting and correction on spinning jet flow, can effectively reduce the electric field interference on the spinning solution, can overcome the problem that the high-ion-content spinning solution cannot be normally spun due to jet flow disorder when the traditional electrostatic spinning method is used, can solve the problem that the jet flow disorder collection and control are difficult when the solution air-jet spinning method is used singly, and is beneficial to the stability of spinning jet flow and the smooth running of the spinning process. Is beneficial to the high-efficiency preparation of the nanofiber ionic conductor. The silk protein nanofiber ionic conductor film is prepared by adopting an airflow-assisted electrostatic spinning method and can be used for preparing electronic skins.
In a preferred embodiment, the metal ion is selected from Ca2+、Li+、Mg2+、Na+And K+One or more of them. The source of the metal ions may be a source containing metal salts corresponding to these metal ions. The metal salt is capable of dissolving in the spinning solution.
In a preferred embodiment, the silk protein is silk and/or spider silk.
In a preferred embodiment, one or more of graphene, graphene oxide, boron nitride, metal organic framework material (MOF for short), covalent organic framework material (COF for short), silver nanoparticles and copper nanoparticles are further added into the spinning solution.
In a preferred embodiment, the mass ratio of the admixture to the fibroin is (0.1-100): 100. such as 0.1:100, 0.5:100, 1:100, 5:100, 10:100, 15:100, 20:100, 25:100, 30:100, 35:100, 40:100, 45:100, 50:100, 55:100, 60:100, 65:100, 70:100, 75:100, 80:100, 85:100, 90:100, 95:100, or 100: 100.
In a preferred embodiment, the solvent in the solution is one or more selected from the group consisting of water, ethanol, formic acid, acetic acid and hexafluoroisopropanol.
In order to ensure that the spinning solution is uniform and stable, the preparation process of the spinning solution can be realized by stirring or ultrasonic dispersion. The ambient temperature for forming the spinning solution can be room temperature, and can also be reasonably selected according to the conditions of solutes and other raw materials.
In a preferred embodiment, the silk protein is 5 to 30 wt% based on the mass of the solvent and the silk protein.
In a preferred embodiment, the mass ratio of the metal salt for providing metal ions to the silk protein is (0.1-100): 100. such as 0.1:100, 0.5:100, 1:100, 5:100, 10:100, 15:100, 20:100, 25:100, 30:100, 35:100, 40:100, 45:100, 50:100, 55:100, 60:100, 65:100, 70:100, 75:100, 80:100, 85:100, 90:100, 95:100, or 100: 100.
Generally, the preparation method in the prior art has strict requirements on the amount of entering metal ions and the amount of the additive, such as 0.01 wt% -1 wt%, otherwise, the spinnability of the spinning solution is affected, and the continuous large-scale production is not facilitated. In the method, the airflow is adopted to assist spinning, so that the content of metal ions in the spinning is greatly improved, the addition amount of the metal salt can be the same as the usage amount of fibroin, and the formed spinning solution still has good spinnability under the condition of high content of the metal salt, so that the conductivity of the formed nanofiber membrane is further ensured. The airflow can assist the forming of the nano-fiber, and can control the air flow in the motion path of the nano-fiber jet flow so as to control and avoid the vibration of the nano-fiber jet flow, thereby forming a flawless nano-fiber film, further improving the stability of producing the nano-fiber containing metal ions under the condition of not influencing the production speed of the nano-fiber film, and being convenient for preparing ion conductor materials on a large scale.
In the preparation method, the process conditions during electrostatic spinning are as follows: the power voltage is 10-60 kV, the temperature of the spinning environment is 15-40 ℃, the relative humidity of the spinning environment is 20-80%, the pressure of the air flow is 5-50 psi, the moving direction of the air flow is along the direction from the spray head to the receiving surface, and the receiving distance is 10-70 cm. The advancing speed of the spinning solution is 1-10 mL/h.
In a particular embodiment, applicants also provide a gas-assisted electrospinning apparatus comprising an electrospinning apparatus and a gas flow supplying apparatus; the electrostatic spinning device comprises a liquid supply part, a spinning spray head, a high-voltage power supply and a nanofiber receiving part; the airflow supply device includes an airflow source and an airflow channel. During operation, the high voltage supplied by the power supply and the airflow are simultaneously applied to the spinning nozzle, and the continuous forming process of the nano-fibers is regulated and controlled through the voltage, the airflow and the size.
The nanofiber receiving part can be flat plate type, drum type or net bag type, and the nanofiber receiving part can be made of metal or nonmetal.
In a more specific embodiment, the spinning nozzle is provided with a spinning nozzle and an air nozzle. The spinning nozzle and the gas nozzle may be arranged coaxially, as shown in fig. 1. Or, in another more specific embodiment, the plurality of air nozzles are arranged around the periphery of the spinneret orifice, and the plurality of air nozzles are symmetrically arranged, specifically as shown in fig. 2, the number of the air nozzles is four, and the four air nozzles are symmetrically arranged around the periphery of the spinneret orifice.
The nanofiber ion conductor electronic skin with good mechanical property, conductivity and wearing comfort can be obtained by adding soluble conductive ions or other additives into the spinning solute listed in the invention. In the technical scheme of the application, different additives have different influences on the performance and the function of the ionic conductor material. Such as: the addition of graphene and graphene oxide helps to enhance the electrical conductivity, flame retardancy and alarm responsiveness of the ionic conductor material when applied to electronic skin, as in example 4. For another example: the addition of boron nitride helps to enhance the flame retardancy, thermal conductivity and heat dissipation of the ionic conductor material when used on electronic skin, as in example 5. Moreover, the applicant proves through practical tests and effects of examples 4 and 5 that the addition of the additives such as graphene does not affect the spinning forming process of the nanofiber membrane, and by adopting the air flow assisted electrostatic spinning technology, the spinning solution containing the additives still has good spinnability, the continuous spinning stability is good, and the spinning speed is high, so that the spinning process and the spinning quality are not affected.
Example 1
Preparing degummed mulberry silk according to the existing method: removing pupa bombycis from Bombyx Bombycis, cutting into small pieces with length of 1-2cm, adding 0.5 wt% NaHCO3Degumming in water solution (bath ratio 1: 200g/mL) at 100 deg.C for 30min, and replacing NaHCO under the same conditions3Continuously degumming the aqueous solution for 30min, soaking and washing with hot water after degumming, washing with deionized water, and drying to obtain degummed silk fiber.
Preparing an ionic conductor spinning solution: 0.33g of CaCl2Dissolving in formic acid, stirring to dissolve CaCl completely2Formic acid solution of (1). Subsequently, 1g of degummed silk was added to the above-mentioned dissolved CaCl2Stirring the solution for 30 minutes to obtain an ion conductor spinning solution.
Preparing a nanofiber ionic conductor: the air flow assisted electrostatic spinning method stated in the patent is used for spinning, and the process conditions are as follows: the power voltage is 25kV, the spinning environment temperature is 25 ℃, the relative humidity is 25%, the spinning solution perfusion speed is 5mL/h, the air flow pressure is 20psi, a metal roller with the surface covered with non-woven fabric is used for receiving, the receiving distance is 30cm, and the nanofiber ionic conductor is obtained through spinning, as shown in figure 3.
Example 2
Preparing degummed mulberry silk according to the existing method: removing pupa bombycis from Bombyx Bombycis, cutting into small pieces with length of 1-2cm, adding 0.5 wt% NaHCO3Degumming in water solution (bath ratio 1: 200g/mL) at 100 deg.C for 30min, and replacing NaHCO under the same conditions3Continuously degumming the aqueous solution for 30min, soaking and washing with hot water after degumming, washing with deionized water, and drying to obtain degummed silk fiber.
Preparing an ionic conductor spinning solution: first, 0.3g LiCl was dissolved in formic acid, and the solution was fully stirred to dissolve LiCl completely to obtain a solution in which LiCl was dissolved2Formic acid solution of (1). Subsequently, 1g of degummed silk was added to the above LiCl-dissolved silk2Stirring the solution for 30 minutes to obtain an ion conductor spinning solution.
Preparing a nanofiber ionic conductor: the air flow assisted electrostatic spinning method stated in the patent is used for spinning, and the process conditions are as follows: the power voltage is 30kV, the spinning environment temperature is 26 ℃, the relative humidity is 20%, the spinning solution filling speed is 1mL/h, the airflow pressure is 10psi, a metal roller with the surface covered with non-woven fabric is used for receiving, the receiving distance is 10cm, and the nanofiber ionic conductor is obtained through spinning.
Example 3
Preparing degummed mulberry silk according to the existing method: removing pupa bombycis from Bombyx Bombycis, cutting into small pieces with length of 1-2cm, adding 0.5 wt% NaHCO3Degumming in water solution (bath ratio 1: 200g/mL) at 100 deg.C for 30min, and replacing NaHCO under the same conditions3Continuously degumming the aqueous solution for 30min, soaking and washing with hot water after degumming, washing with deionized water, and drying to obtain degummed silk fiber.
Preparing an ionic conductor spinning solution: first, 0.3g of LiCl was dissolved in formic acid, and the solution was thoroughly stirred to obtain a solution of LiCl-dissolved formic acid. Subsequently, 1g of degummed silk was added to the above formic acid solution in which LiCl was dissolved, and stirred for 30 minutes to obtain an ion conductor spinning solution.
Preparing a nanofiber ionic conductor: the air flow assisted electrostatic spinning method stated in the patent is used for spinning, and the process conditions are as follows: the power voltage is 60kV, the spinning environment temperature is 26 ℃, the relative humidity is 20%, the spinning solution filling speed is 10mL/h, the airflow pressure is 50psi, a metal roller with the surface covered with non-woven fabric is used for receiving, the receiving distance is 70cm, and the nanofiber ionic conductor is obtained through spinning.
Example 4
Preparing degummed mulberry silk according to the existing method: removing pupa bombycis from Bombyx Bombycis, cutting into small pieces with length of 1-2cm, adding 0.5 wt% NaHCO3Degumming in water solution (bath ratio 1: 200g/mL) at 100 deg.C for 30min, and replacing NaHCO under the same conditions3Continuously degumming the aqueous solution for 30min, soaking and washing with hot water after degumming, washing with deionized water, and drying to obtain degummed silk fiber.
Preparing an ionic conductor spinning solution: 0.33g of CaCl2Dissolving in formic acid, stirring to dissolve CaCl completely2Formic acid solution of (1). Subsequently dissolve CaCl2Adding 0.1g of graphene into the formic acid solution, and performing ultrasonic treatment for 30 minutes to obtain uniformly dispersed CaCl2Graphene/formic acid dispersion, then 1g degummed silk was added to the above CaCl2And stirring the graphene/formic acid dispersion liquid for 30 minutes to obtain the ionic conductor spinning solution.
Preparing a nanofiber ionic conductor: the air flow assisted electrostatic spinning method stated in the patent is used for spinning, and the process conditions are as follows: the power voltage is 23kV, the spinning environment temperature is 26 ℃, the relative humidity is 30%, the spinning solution perfusion speed is 3mL/h, the airflow pressure is 15psi, a metal roller with the surface covered with non-woven fabric is used for receiving, the receiving distance is 35cm, and the nanofiber ionic conductor is obtained through spinning, as shown in figure 4.
The prepared nanofiber ionic conductor has self-contraction performance of humidity response, can be coated on the surface of an irregular object in a self-adaptive manner, as shown in fig. 5, and can be used as electronic skin to capture actions. In addition, the prepared electronic skin also has flame retardant property, can be used as protective skin to play a role of fire prevention and flame retardance, does not burn when meeting flame, and does not continue to burn when the flame leaves, as shown in figure 6. The prepared electronic skin also has temperature sensitivity, can be used together with an electric signal monitoring system to realize the functions of fire protection and early warning, the resistance reduction amplitude is rapidly larger than 80% of the initial value within 4 seconds after the electronic skin is contacted with flame, so that an early-warning characteristic signal peak appears, and a continuous alarm signal is triggered after 20 seconds, as shown in figure 7.
Example 5
Preparing degummed mulberry silk according to the existing method: removing pupa bombycis from Bombyx Bombycis, cutting into small pieces with length of 1-2cm, adding 0.5 wt% NaHCO3Degumming in water solution (bath ratio 1: 200g/mL) at 100 deg.C for 30min, and replacing NaHCO under the same conditions3Continuously degumming the aqueous solution for 30min, soaking and washing with hot water after degumming, washing with deionized water, and drying to obtain degummed silk fiber.
Preparing an ionic conductor spinning solution: first 0.5g of CaCl2Dissolving in formic acid, stirring to dissolve CaCl completely2Formic acid solution of (1). Subsequently dissolve CaCl2Adding 0.5g of boron nitride into the formic acid solution, and performing ultrasonic treatment for 30 minutes to obtain uniformly dispersed CaCl2Boron nitride/formic acid dispersion, 1.5g degummed silk was added to the above CaCl2Stirring the boron nitride/formic acid dispersion liquid for 40 minutes to obtain the ion conductor spinning solution.
Preparing a nanofiber ionic conductor: the air flow assisted electrostatic spinning method stated in the patent is used for spinning, and the process conditions are as follows: the power voltage is 60kV, the spinning environment temperature is 20 ℃, the relative humidity is 80%, the spinning solution filling speed is 3mL/h, the airflow pressure is 50psi, a metal roller with the surface covered with non-woven fabric is used for receiving, the receiving distance is 70cm, and the nanofiber ionic conductor is obtained through spinning.
The prepared nanofiber ionic conductor can be pasted on the surface of an object to be used as a heat dissipation type electronic skin, has good stress sensing and flame retardant properties, does not burn when meeting flame, and does not continue to burn when the flame leaves. The prepared electronic skin also has temperature sensitivity, can be used together with an electric signal monitoring system to realize temperature monitoring and early warning functions, as shown in figure 8, the material is hermetically packaged, has different conductivities at different temperatures, and when the temperature is higher than 100 ℃, the resistance is increased due to the separation of water and the material, and an alarm characteristic peak appears.
Example 6
Preparing the mulberry silk aqueous solution according to the existing method: removing silkworm pupa from silkworm cocoon, cutting into pieces with length of 1-2cm, adding into 9.3mol/L LiBr solution, and heating at 60 deg.C for 1 hr for dissolving. And dialyzing the obtained silk solution in deionized water to remove LiBr, and then concentrating to obtain silk protein solution with the concentration of 30 wt%.
Preparation of a dispersion solution of salt ions and additives: the metal salt is MgCl2And other additives are graphene oxide, and water is selected as a solvent. Wherein, MgCl2The mass ratio of the graphene oxide to the silk protein is 15:100, and the mass ratio of the graphene oxide to the silk protein is 5:100, the total mass of salt and additives and water is the same as the silk aqueous solution. Dissolving metal salt in water, and stirring to dissolve completely to obtain water solution containing metal salt. And then adding graphene oxide into the solution containing the metal salt, and performing ultrasonic treatment for 30 minutes to obtain a uniform dispersion liquid.
Preparing a spinning solution: and (3) mixing the silk aqueous solution with the dispersion liquid of the salt ions and the additives, and uniformly stirring to obtain the spinning solution.
Preparing a nanofiber ionic conductor: the air flow assisted electrostatic spinning method stated in the patent is used for spinning, and the process conditions are as follows: the power voltage is 40kV, the spinning environment temperature is 40 ℃, the relative humidity is 50%, the spinning solution perfusion speed is 5mL/h, the airflow pressure is 50psi, a metal roller with the surface covered with non-woven fabrics is used for receiving, the receiving distance is 70cm, and the nanofiber ionic conductor is obtained through spinning.
Example 7
Preparing the mulberry silk aqueous solution according to the existing method: removing silkworm pupa from silkworm cocoon, cutting into pieces with length of 1-2cm, adding into 9.3mol/L LiBr solution, and heating at 60 deg.C for 1 hr for dissolving. And dialyzing the obtained silk solution in deionized water to remove LiBr, and then concentrating to obtain silk protein solution with the concentration of 30 wt%.
Preparation of a dispersion solution of salt ions and additives: the metal salt is NaCl, other additives are graphene oxide, and water is selected as a solvent. Wherein the mass ratio of NaCl to silk protein is 100:100, and the mass ratio of graphene oxide to silk protein is 1:100, the total mass of salt and additives and water is the same as the silk aqueous solution. Dissolving metal salt in water, and stirring to dissolve completely to obtain water solution containing metal salt. And then adding graphene oxide into the solution containing the metal salt, and performing ultrasonic treatment for 30 minutes to obtain a uniform dispersion liquid.
Preparing a spinning solution: and (3) mixing the silk aqueous solution with the dispersion liquid of the salt ions and the additives, and uniformly stirring to obtain the spinning solution.
Preparing a nanofiber ionic conductor: the air flow assisted electrostatic spinning method stated in the patent is used for spinning, and the process conditions are as follows: the power voltage is 10kV, the spinning environment temperature is 15 ℃, the relative humidity is 60%, the spinning solution filling speed is 2mL/h, the airflow pressure is 30psi, a metal roller with the surface covered with non-woven fabric is used for receiving, the receiving distance is 50cm, and the nanofiber ionic conductor is obtained through spinning.
Example 8
Preparing degummed mulberry silk according to the existing method: removing pupa bombycis from Bombyx Bombycis, cutting into small pieces with length of 1-2cm, adding 0.5 wt% NaHCO3Degumming in water solution (bath ratio 1: 200g/mL) at 100 deg.C for 30min, and replacing NaHCO under the same conditions3Continuously degumming the aqueous solution for 30min, soaking and washing with hot water after degumming, washing with deionized water, and drying to obtain degummed silk fiber.
Preparing an ionic conductor spinning solution: firstly, degummed silk, metal salt and other additives are prepared, wherein the metal salt is LiCl, the other additives are MOF, and formic acid is selected as a solvent. Wherein the mass ratio of LiCl to silk protein is 30:100, the mass ratio of MOF to silk protein is 10:100, the silk protein accounts for 5 wt% of all solutes and solvents. The metal salt is dissolved in a solvent, and the solution containing the metal salt is obtained by completely dissolving the metal salt by stirring. And then adding other additives into the solution containing the metal salt, carrying out ultrasonic treatment for 30 minutes to obtain uniform dispersion liquid, then adding the degummed silk into the dispersion liquid, and stirring for 30 minutes to obtain the ion conductor spinning solution.
Preparing a nanofiber ionic conductor: the air flow assisted electrostatic spinning method stated in the patent is used for spinning, and the process conditions are as follows: the power voltage is 20kV, the spinning environment temperature is 20 ℃, the relative humidity is 20%, the spinning solution filling speed is 1mL/h, the airflow pressure is 15psi, a metal roller with the surface covered with non-woven fabric is used for receiving, the receiving distance is 40cm, and the nanofiber ionic conductor is obtained through spinning.
Examples 9-15 the procedure was the same as in example 8, wherein the solution parameters and process parameters are shown in Table 1.
TABLE 1
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A method for preparing an ionic conductor material, comprising: the solution containing metal ions and silk protein is used as spinning solution, a nanofiber membrane is formed through electrostatic spinning, and airflow is adopted in the electrostatic spinning process to assist spinning.
2. The method according to claim 1, wherein the metal ion is Ca2+、Li+、Mg2+、Na+And K+One or more of (a).
3. The preparation method according to claim 1, wherein the spinning solution is further added with an additive, and the additive is one or more selected from graphene, graphene oxide, boron nitride, a metal organic framework material, a covalent organic framework material, nano silver particles and nano copper particles.
4. The preparation method according to claim 3, wherein the mass ratio of the admixture to the fibroin is (0.1-100): 100.
5. the method according to claim 1, wherein the solvent in the solution is one or more selected from the group consisting of water, ethanol, formic acid, acetic acid, and hexafluoroisopropanol.
6. The method according to claim 1, wherein the mass ratio of the metal salt for providing metal ions to the silk protein is (0.1-100): 100.
7. the preparation method according to claim 1, wherein the process conditions in the electrospinning include: the power voltage is 10-60 kV, the temperature of the spinning environment is 15-40 ℃, the relative humidity of the spinning environment is 20-80%, and the receiving distance is 10-70 cm.
8. The method of claim 1, wherein the pressure of the gas stream is 5psi to 50psi and the direction of movement of the gas stream is along the spinneret to the nanofiber-receiving face.
9. An ion conductor material formed by the production method as claimed in any one of claims 1 to 8.
10. Use of the ionic conductor material of claim 9 as an electronic skin.
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