CN109847594B - Asymmetric nano-pore composite membrane and preparation method and application thereof - Google Patents
Asymmetric nano-pore composite membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an asymmetric nano-pore composite membrane based on a mesoporous-macroporous material, a preparation method and application thereof, wherein the composite membrane comprises a silk membrane with a mesoporous structure and a membrane material with a macroporous structure; the asymmetric nanometer pore channel means that part of mesopores in the silk membrane with the mesoporous structure are correspondingly communicated with part of macropores in the membrane material with the macroporous structure. The invention takes the silk membrane as the mesoporous material for the first time and is used for manufacturing the asymmetric nano-pore composite membrane, and the silk membrane has stable performance, rich raw materials, low price, mild preparation conditions and simple operation. In addition, the asymmetric nano-pore composite membrane prepared by the invention can be used as a salt difference battery diaphragm to be applied to a salt difference energy power generation system, and has the advantages of long-time current output, wide pH range application, stable performance, high conversion efficiency and wide application range.
Description
Technical Field
The invention relates to the field of a nano-pore composite membrane, in particular to an asymmetric nano-pore composite membrane and a preparation method and application thereof.
Background
With the continuous consumption of traditional energy sources such as petroleum, coal mines, natural gas and the like and the rapid increase of energy demand in social development, the exploitation of novel renewable and sustainable energy sources from the nature has become the primary means for solving the energy demand of human beings. Under the background, the salt tolerance energy existing in the boundary water area of river water and seawater is beneficial to relieving the crisis of energy exhaustion to a certain extent due to the characteristics of large reserve, easy acquisition, wide distribution and the like. In order to capture such clean energy, researchers have designed a large number of energy conversion devices to convert such salt difference energy into electrical energy.
In such systems for converting salt difference energy into electrical energy, nanoporous membrane materials have been extensively studied as one of the most important components. The existing membrane material faces the problems of expensive raw materials, complex preparation process and the like, for example, the synthesis yield of the block copolymer membrane is low, and the related organic reaction needs to control the harsh preparation conditions; the channel etching of inorganic films such as molybdenum disulfide and the like has high technical requirements, and processes such as ion bombardment, focused ion beams and the like are needed; the polymer film such as PET film has poor control capability of etching technology, high cost, and a large amount of strong acid and strong base waste liquid and the like can be generated in the etching process. Therefore, it is necessary to develop a nanopore membrane with a mild preparation process, abundant and cheap raw materials, mature technology, large-scale popularization and wide applicability to solve the defects of the prior art.
Disclosure of Invention
The invention aims to provide an asymmetric nanopore composite membrane based on a mesoporous-macroporous material, which comprises a silk membrane with a mesoporous structure, wherein the silk membrane is stable in performance, rich in raw materials and low in price.
The second purpose of the invention is to provide a preparation method of the asymmetric nano-pore composite membrane based on the mesoporous-macroporous material, which has mild conditions and simple operation.
The third purpose of the invention is to provide an application of the asymmetric nano-pore composite membrane based on the mesoporous-macroporous material in the salt difference battery diaphragm.
The fourth purpose of the invention is to provide an application of the asymmetric nano-pore composite membrane based on the mesoporous-macroporous material in a salt energy difference power generation system, wherein the asymmetric nano-pore composite membrane can be used for a reverse electrodialysis technology to capture salt difference energy and has the advantages of stable output electric power, high efficiency and wide application range.
In order to achieve the first object of the present invention, the asymmetric nanopore composite membrane based on the mesoporous-macroporous material provided by the present invention has the following characteristics:
the composite membrane comprises a silk membrane with a mesoporous structure and a membrane material with a macroporous structure; the asymmetric nanometer pore channel means that part of mesopores in the silk membrane with the mesoporous structure are correspondingly communicated with part of macropores in the membrane material with the macroporous structure.
Preferably, the membrane material with a macroporous structure is one selected from an anodic aluminum oxide membrane, a polycarbonate membrane, a cellulose membrane, a polytetrafluoroethylene membrane or a polyvinylidene fluoride membrane.
Preferably, the membrane material having a macroporous structure is an anodic aluminum oxide membrane.
Preferably, the aperture of the mesopores on the silk membrane is 15-25 nm; the pore diameter of the macropores on the membrane material is 20-200 nm. .
Preferably, the thickness of the silk membrane is 5 to 80 μm.
The present invention achieves the second technical object of the present invention by implementing the following technical means.
A preparation method of an asymmetric nanometer pore channel composite membrane based on a mesoporous-macroporous material comprises the following steps: placing the silk nanofiber in a vacuum filtration device, fixing a membrane material with a macroporous structure on a sand core funnel of the vacuum filtration device, and adsorbing the silk nanofiber to the surface of the membrane material with the macroporous structure after vacuum filtration to obtain the composite membrane.
The invention also provides application of the asymmetric nano-pore composite membrane as a salt difference battery diaphragm.
The fourth purpose of the invention is to provide the application of the asymmetric nano-pore composite membrane in a salt-difference energy power generation system.
Preferably, in the application process of the asymmetric nanopore composite membrane in the salt difference energy power generation system, the pore diameter of a mesopore on a silk membrane in the asymmetric nanopore composite membrane is 15-25 nm; the pore diameter of the macropores on the membrane material is 80-100 nm.
Preferably, in the application process of the asymmetric nanopore composite membrane in the salt difference energy power generation system, the thickness of a silk membrane in the asymmetric nanopore composite membrane is 10-20 μm.
The invention has the following beneficial effects:
the invention provides an asymmetric nanopore composite membrane based on a mesoporous-macroporous material, which comprises a silk membrane with a mesoporous structure, wherein the silk membrane is stable in performance, rich in raw materials, low in price, mild in preparation condition and simple in operation, and can be prepared only by vacuum filtration, and the defects of complex process, high cost and poor controllability in the prior art are overcome.
In addition, the application of the asymmetric nano-pore composite membrane as a salt difference battery diaphragm and a salt difference energy power generation system has obvious advantages:
1, positive ions and negative ions are allowed to pass through, so that the concentration polarization effect caused by selective passing of single ions is weakened, and the improvement of the ion transmission efficiency is facilitated;
2, the asymmetric nano-pore structure has advantages in adjusting the ion diffusion;
3, high energy conversion efficiency: successfully converts the salt difference energy into electric energy, and the maximum output energy density reaches 2.86W/M in a salt difference energy power generation system simulating and utilizing seawater (0.5M NaCl) and river water (0.01M NaCl)2；
4, wide application range: the silk film can be used in an electrolyte solution with pH value of 3-11, and the thickness of the silk film can be adjusted according to the pH value during use, so that the maximization of energy conversion efficiency is realized;
5, stable performance: the salt difference energy power generation system comprising the composite membrane also has good stability, and the power generation efficiency is only declined by 10% after 3-month continuous tests.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 shows a schematic diagram of the preparation process of the silk fiber and asymmetric nanopore composite membrane of example 1.
Fig. 2 shows a scanning electron micrograph (a) of a cross section of the asymmetric nanopore composite membrane and a scanning electron micrograph (b) of the surface of the silk membrane in example 1.
FIG. 3 shows transmission electron micrographs of silk film fibers in example 1.
Figure 4 shows the system setup diagram for the conversion of salt difference energy to electrical energy in example 11.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides an asymmetric nano-pore composite membrane based on a mesoporous-macroporous material, which comprises a silk membrane with a mesoporous structure and a membrane material with a macroporous structure; the asymmetric nanometer pore channel means that part of mesopores in the silk membrane with the mesoporous structure are correspondingly communicated with part of macropores in the membrane material with the macroporous structure.
The invention solves the problems in the prior art by providing the silk membrane as the mesoporous material aiming at the problems of expensive raw materials, high cost, complex process and high technical requirement of membrane material preparation in the prior art. The silk nanofiber is used as a porous protein fiber, a silk membrane formed by the silk nanofiber has good adhesive force with a macroporous structure, and the silk membrane has a mesoporous structure and can form an asymmetric nanopore with macropores. In addition, the silk membrane material has rich and cheap raw materials and good stability.
The membrane material with the macroporous structure provided by the invention is one selected from an anodic aluminum oxide membrane, a polycarbonate membrane, a cellulose membrane, a polytetrafluoroethylene membrane or a polyvinylidene fluoride membrane.
According to some preferred embodiments, the membrane material with a macroporous structure provided by the invention is an anodic aluminum oxide membrane.
In the invention, the anodic aluminum oxide film has good hardness, wear resistance and corrosion resistance, and can effectively protect the aluminum matrix from abrasion and corrosion; in addition, the porosity of the anodic aluminum oxide film is beneficial to the attachment of the silk nanofibers on the surface of the silk film to form the silk film with a mesoporous structure, and the macroporous structure is provided to be matched with the structure in the silk film to form an asymmetric nanopore channel.
In the invention, the aperture of the mesopore on the silk membrane is 15-25 nm; the pore diameter of the macropores on the membrane material is 20-200 nm.
According to some preferred embodiments, for example, the pore size of the mesopores on the silk membrane can also be, but not limited to, 16-24nm, 17-23nm, 18-22nm, 19-21nm, or the like; the pore diameter of the macropores on the membrane material can also be, but not limited to, 30-180nm, 40-160nm, 50-140nm, 60-120nm or 70-100nm and the like.
In the present invention, the thickness of the silk film is 5 to 80 μm.
According to some preferred embodiments, for example, the silk membrane may also have a thickness of, but not limited to, 10-65 μm, 15-60 μm, 20-55 μm, 25-50 μm, or 30-45 μm, etc.
The thickness of the silk membrane mainly influences the electrification amount and the pore canal resistance.
The invention also provides a preparation method of the asymmetric nano-pore composite membrane based on the mesoporous-macroporous material, which comprises the following steps: placing the silk nanofiber in a vacuum filtration device, fixing a membrane material with a macroporous structure on a sand core funnel of the vacuum filtration device, and adsorbing the silk nanofiber to the surface of the membrane material with the macroporous structure after vacuum filtration to obtain the composite membrane.
The silk shells used in the preparation process of the composite membrane provided by the present invention are commercially available, and the present invention is not limited thereto. The invention provides a preparation method of the silk nanofiber, which comprises the following steps:
(1) degumming silk: adding 1 part of silk into 400 parts of sodium bicarbonate solution with the mass fraction of 0.5%, boiling for 1h, washing with cold water to be neutral, and drying to obtain degumming silk fiber;
(2) preparing silk microfiber: soaking 1 part of degumming silk fiber into 30 parts of hexafluoroisopropanol solution, hermetically storing at a constant temperature of 60 ℃ for 24 hours, and naturally evaporating hexafluoroisopropanol at normal temperature and normal pressure for 5 hours to obtain silk microfiber;
(3) preparing a silk nanofiber solution: dissolving 1 part of silk microfiber in 400 parts of water, filtering, performing ultrasonic treatment for 30 minutes and centrifugal treatment for 20 minutes on the filtrate, and filtering to obtain a silk nanofiber solution, wherein the mass percentage of the silk nanofiber contained in the silk nanofiber solution is about 0.05%.
The silk nano-fiber provided by the invention has the size that the diameter is distributed between 15 nm and 20nm, and the length is between 200nm and 500 nm.
The preparation method of the asymmetric nanopore composite membrane provided by the invention only adopts a vacuum filtration mode, is simple to operate, and avoids the defects of complex preparation process, high cost and poor controllability in the prior art.
The invention also provides application of the asymmetric nano-pore composite membrane as a salt difference battery diaphragm.
According to the asymmetric nanopore composite membrane provided by the invention, under different pH conditions, the composite membrane can selectively allow more positive ions to pass through. In addition, in the use process, the macropores of the composite membrane face to a high-concentration solution, the mesopores face to a low-concentration solution, and ions are diffused from the high-concentration solution to the low-concentration solution under the combined action of concentration difference and an asymmetric pore channel structure.
The fourth aspect of the invention provides an application of the asymmetric nano-pore composite membrane in a salt-difference energy power generation system.
As described above, the asymmetric nanopore composite membrane provided by the invention can be used as a salt difference battery membrane, so that in a power generation system utilizing salt difference energy, the composite membrane can be arranged between electrolyte solutions with different concentrations as the salt difference battery membrane. Ions are diffused to low-concentration solution from high-concentration solution through an asymmetric ion channel on the composite membrane, and form a loop with an ammeter and a load resistor which are externally connected between electrolyte solutions with different concentrations, so that the process of converting salt difference energy into electric energy is realized.
The asymmetric nano-pore composite membrane provided by the invention successfully converts the salt difference energy into electric energy in a salt difference energy power generation system simulating and utilizing seawater (0.5M NaCl) and river water (0.01M NaCl), and the maximum output energy density of the asymmetric nano-pore composite membrane is 2.86W/M2。
Tests show that the salt difference energy power generation system comprising the composite membrane has stable current output performance in an environment with the pH value of 3-11; in the actual operation process, the thickness of the silk membrane in the composite membrane can be adjusted according to different pH values, so that the balance between resistance and pushing force is realized, and the maximization of energy conversion efficiency is realized.
In addition, the salt difference energy power generation system comprising the composite membrane also has good stability, and the power generation efficiency is only declined by 10% after continuous tests for 3 months.
According to some preferred embodiments, in the application process of the asymmetric nanopore composite membrane in the salt difference energy power generation system, the pore diameter of the mesopores on the silk membrane in the asymmetric nanopore composite membrane is 15-25 nm; the pore diameter of the macropores on the membrane material is 80-100 nm.
According to some preferred embodiments, the asymmetric nanopore composite membrane has a thickness of a silk membrane of 10 to 20 μm in a silk membrane of the asymmetric nanopore composite membrane during use of the asymmetric nanopore composite membrane in a salt difference energy generation system.
The invention will be further illustrated by way of example, but the scope of protection is not limited to these examples.
Example 1
Preparation of asymmetric nano-pore composite membrane
As shown in fig. 1, the preparation of the asymmetric nanopore composite membrane comprises the following steps:
(1) cutting silkworm cocoons into pieces with the size of fingernails, adding 1 part of silk into 400 parts of sodium bicarbonate solution with the mass fraction of 0.5%, boiling for 1h, then cleaning with cold distilled water to be neutral, then squeezing the silk, then laying the silk on a clean aluminum foil, and allowing the silk to air at room temperature overnight to obtain the degumming silk fiber.
(2) And then soaking 1 part of the degumming silk fiber into 30 parts of hexafluoroisopropanol solution, fully stirring, hermetically storing at a constant temperature of 60 ℃ for 24 hours, then transferring the solution into an air cabinet, and naturally evaporating hexafluoroisopropanol for 5 hours at normal temperature and normal pressure to obtain the silk microfiber. (3) Dissolving 1 part of silk microfiber in 400 parts of distilled water, filtering, and performing ultrasonic treatment on the filtrate at the frequency of 40kHz for 1h, wherein an ice bag can be arranged in an ultrasonic instrument during the ultrasonic treatment process to prevent the high temperature generated by ultrasonic from generating adverse effect on silk. And centrifuging at 10000rpm for 30 min by using a centrifuge to obtain the silk nanofiber solution with the mass percent of about 0.05%, wherein the transmission electron microscope image is shown in FIG. 3. (4) And (3) after filtering, transferring the supernatant into a vacuum filtration device, fixing an anodic alumina membrane with the aperture of 80-100nm on a sand core of the filtration device, and performing filtration to obtain the asymmetric nanopore composite membrane comprising the silk membrane and the anodic alumina membrane, wherein a section scanning electron microscope image of the asymmetric nanopore composite membrane is shown in figure 2(a), and a surface scanning electron microscope image of one side of the silk membrane is shown in figure 2 (b). The thickness of the silk membrane is 10 mu m, the aperture of the silk membrane is 15-25nm, and the aperture of the anodic aluminum oxide membrane is 80-100 nm.
Examples 2 to 5
Preparation of composite membranes with different silk film thicknesses
Compared with the embodiment 1, by changing the using amount of the silk fiber solution in the step (4), the asymmetric nanopore composite membrane with the anodic alumina membrane with the pore diameter of 80-100nm, the silk membrane with the pore diameter of 15-25nm and the silk membrane thickness of 5 microns, 15 microns, 40 microns and 80 microns can be obtained.
Examples 6 to 9
Preparation of composite membranes with different macropore diameters
Compared with the embodiment 1, the asymmetric nanopore composite membrane with the silk membrane thickness of 10 microns, the silk membrane aperture of 15-25nm, the anodic aluminum oxide membrane aperture of 20-30nm, 40-70nm, 110-150nm and 160-200nm can be obtained by changing the aperture of the anodic aluminum oxide membrane fixed on the sand core of the suction filtration device in the step (4).
Example 10
Preparation of composite membrane with polycarbonate macroporous membrane material
The preparation process comprises the following steps: (1) cutting silkworm cocoons into pieces with the size of fingernails, adding 1 part of silk into 400 parts of sodium bicarbonate solution with the mass fraction of 0.5%, boiling for 1h, then cleaning with cold distilled water to be neutral, then squeezing the silk, then laying the silk on a clean aluminum foil, and allowing the silk to air at room temperature overnight to obtain the degumming silk fiber. (2) And then soaking 1 part of the degumming silk fiber into 30 parts of hexafluoroisopropanol solution, fully stirring, hermetically storing at a constant temperature of 60 ℃ for 24 hours, then transferring the solution into an air cabinet, and naturally evaporating hexafluoroisopropanol for 5 hours at normal temperature and normal pressure to obtain the silk microfiber. (3) Dissolving 1 part of silk microfiber in 400 parts of distilled water, filtering, and performing ultrasonic treatment on the filtrate at the frequency of 40kHz for 1h, wherein an ice bag can be arranged in an ultrasonic instrument during the ultrasonic treatment process to prevent the high temperature generated by ultrasonic from generating adverse effect on silk. And centrifuging the solution for 30 minutes by using a centrifuge at 10000rpm to obtain the silk nanofiber solution with the mass percent of about 0.05 percent. (4) And (3) after filtering, transferring the supernatant into a vacuum filtration device, fixing a polycarbonate membrane with the aperture of 200nm on a sand core of the filtration device, and then carrying out filtration to obtain the asymmetric nanopore composite membrane comprising the silk membrane and the polycarbonate membrane. The thickness of the silk membrane is 10 μm, the aperture of the silk membrane is 20nm, and the aperture of the polycarbonate membrane is 200 nm.
Example 11
Conversion of salt difference energy into electric energy
As shown in FIG. 4, the device for converting the salt difference energy into the electric energy is a closed system, and the left container is filled with 0.5M NaCl electrolyte solution, which corresponds to the right container filled with 0.1M NaCl electrolyte solution. There is a groove in each of the left and right containers for injecting the solution and inserting the electrodes. The composite film prepared in example 1 was mounted between two containers and fixed with a screw. The small pore end of the composite membrane, namely the silk membrane, faces to the low-concentration solution side, and the large pore end, namely the anodic aluminum oxide membrane, faces to the high-concentration side. The two electrolyte solutions are communicated with the circuit through an external ammeter and a load resistor. The pH of the electrolyte solution was adjusted to 11, at which time the energy density in the external circuit was measured to be 2.86W/m2。
Examples 12 to 15
Composite membranes with different alumina membrane apertures convert salt difference energy into electric energy
The asymmetric nano-porous composite membrane prepared in the examples 6 to 9 is used for replacing the composite membrane in the example 11, the condition is not changed, and the influence of the aperture of the anodic aluminum oxide membrane on the energy density in an external circuit can be testedIt is found that when the pore diameters of the anodic aluminum oxide film are 20-30nm, 40-70nm, 110-150nm and 160-200nm, the corresponding external circuit energy densities are: 1.88W/m2、2.02W/m2、1.79W/m2And 1.24W/m2。
In combination with the results of examples 11 to 15, it was found that the conversion efficiency of the salt energy difference into electric energy was the highest when the pore diameter of the anodized aluminum film was 80 to 100 nm.
Examples 16 to 17
Converting salt difference energy into electric energy by using composite membrane under different pH values
As a result of adjusting the pH of the electrolyte solution to 3 and 6.1, respectively, as compared with example 11, it was found that the energy densities in the external circuits at this time were 1.55W/m, respectively2And 2.22W/m2。
Examples 18 to 21
Composite membrane with different silk membrane thicknesses converts salt difference energy into electric energy
The asymmetric nanopore composite membranes prepared in examples 2-5 were used in place of the composite membrane in example 11 under the same conditions, and the effect of the thickness of the silk membrane on the energy density in the external circuit was measured, and it was found that when the silk membrane thickness was 5 μm, 15 μm, 40 μm and 80 μm, respectively, the corresponding energy density in the external circuit was: 1.26W/m2、1.97W/m2、1.91W/m2And 1.66W/m2。
The results of examples 11, 18-21 show that the silk film thickness of 10 μm has the maximum energy conversion efficiency at pH 11 of the electrolyte solution and the energy density of the external circuit of 2.86W/m2。
Examples 22 to 25
Composite membrane with different silk membrane thicknesses converts salt difference energy into electric energy
By adjusting the pH of the electrolyte solution to 6.1 in comparison with examples 18-21, it was found that when the silk film thicknesses were 5 μm, 15 μm, 40 μm and 80 μm, respectively, the external circuit energy densities were: 1.21W/m2、1.84W/m2、1.89W/m2And 1.39W/m2。
As demonstrated by the results of examples 17 and 22 to 25,when the pH value of the electrolyte solution is 6.1, the silk film thickness is 10 mu m, the maximum energy conversion efficiency is achieved, and the external circuit energy density is 2.86W/m2。
Examples 26 to 29
Composite membrane with different silk membrane thicknesses converts salt difference energy into electric energy
By adjusting the pH of the electrolyte solution to 3 in comparison with examples 14-17, it was found that when the silk film thicknesses were 5 μm, 15 μm, 40 μm and 80 μm, respectively, the external circuit energy densities were: 0.95W/m2、1.64W/m2、1.32W/m2And 1.12W/m2。
The results of examples 16 and 26 to 29 show that the silk film thickness of 15 μm has the maximum energy conversion efficiency and the external circuit energy density of 1.64W/m at pH 3 of the electrolyte solution2。
The results of examples 11, 16-29 show that the silk film thickness with the maximum energy conversion efficiency varies when the electrolyte solution concentration varies. In the electrolyte solution with pH 11, the silk film thickness of 10 μm has the maximum energy conversion efficiency; in an electrolyte solution with pH of 6.1, the silk film thickness of 10 μm has the maximum energy conversion efficiency; the silk film thickness of 15 μm has the greatest energy conversion efficiency in an electrolyte solution with a pH of 3. Therefore, in the actual use process, composite membranes with different silk membrane thicknesses can be manufactured according to the pH value of the electrolyte solution, and further the maximization of energy conversion is realized.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. An asymmetric nano-pore composite membrane based on a mesoporous-macroporous material is characterized in that the composite membrane comprises a silk membrane with a mesoporous structure and a membrane material with a macroporous structure; the asymmetric nanometer pore channel means that part of mesopores in the silk membrane with the mesoporous structure are correspondingly communicated with part of macropores in the membrane material with the macroporous structure.
2. The composite membrane according to claim 1, wherein the membrane material having a macroporous structure is one selected from an anodized aluminum membrane, a polycarbonate membrane, a cellulose membrane, a polytetrafluoroethylene membrane, and a polyvinylidene fluoride membrane.
3. The composite membrane according to claim 1, wherein the membrane material having a macroporous structure is an anodic aluminum oxide membrane.
4. The composite membrane according to claim 1, wherein the pore size of the mesopores on the silk membrane is 15 to 25 nm; the pore diameter of the macropores on the membrane material is 50-200 nm.
5. The composite membrane according to claim 1, wherein the thickness of the silk membrane is 5-80 μm.
6. A method for preparing the asymmetric nano-pore composite membrane based on the mesoporous-macroporous material as in any one of claims 1 to 5, wherein silk nano-fibers are placed in a vacuum filtration device, membrane materials with macroporous structures are fixed on sand core funnels of the vacuum filtration device, and after vacuum filtration, the silk nano-fibers are adsorbed to the surfaces of the membrane materials with macroporous structures to obtain the composite membrane;
the preparation method of the silk nanofiber comprises the following steps:
(1) degumming silk: adding 1 part of silk into 400 parts of sodium bicarbonate solution with the mass fraction of 0.5%, boiling for 1h, washing with cold water to be neutral, and drying to obtain degumming silk fiber;
(2) preparing silk microfiber: soaking 1 part of degumming silk fiber into 30 parts of hexafluoroisopropanol solution, hermetically storing at a constant temperature of 60 ℃ for 24 hours, and naturally evaporating hexafluoroisopropanol at normal temperature and normal pressure for 5 hours to obtain silk microfiber;
(3) preparing a silk nanofiber solution: dissolving 1 part of silk microfiber in 400 parts of water, filtering, performing ultrasonic treatment for 30 minutes and centrifugal treatment for 20 minutes on the filtrate, and filtering to obtain a silk nanofiber solution, wherein the mass percentage of the silk nanofiber contained in the silk nanofiber solution is 0.05%.
7. The application of the asymmetric nano-pore composite membrane as claimed in any one of claims 1 to 5 as a salt difference battery diaphragm, wherein when the asymmetric nano-pore composite membrane is used as the salt difference battery diaphragm, the macroporous base membrane is an anodic aluminum oxide membrane.
8. The application of the asymmetric nano-pore composite membrane as claimed in any one of claims 1 to 5 in a salt-difference energy power generation system, wherein when the asymmetric nano-pore composite membrane is used as a salt-difference battery diaphragm, a macroporous base membrane is an anodic aluminum oxide membrane.
9. The use according to claim 8, wherein during use, the pore size of the nanopores in the silk membrane is from 15 to 25 nm; the pore diameter of the macropores on the membrane material is 80-100 nm.
10. The use according to claim 8, characterized in that the thickness of the silk film is 10-20 μm during the use.
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| CN108022761A (en) * | 2017-12-28 | 2018-05-11 | 中国人民大学 | A kind of silk nano fibrous membrane and preparation method thereof and the application in ultracapacitor |
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| CN109847594A (en) | 2019-06-07 |
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