CN107617344B - Nanowire-loaded polymer microporous membrane and preparation method thereof - Google Patents
Nanowire-loaded polymer microporous membrane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polymer microporous membrane loaded with nanowires, wherein the surface of the polymer microporous membrane is loaded with a covering layer, the covering layer comprises a plurality of nanowires which are arranged in a disordered way and are crossed with each other, and a plurality of silver particles are attached to the crossed positions of adjacent nanowires, so that the nanowires form an integral cross-linked network structure. The invention also provides a preparation method of the polymer microporous membrane loaded with the nanowires.
Description
Technical Field
The invention relates to the field of polymer microporous membranes, in particular to a nanowire-loaded polymer microporous membrane and a preparation method thereof.
Background
Water shortage has become a huge crisis faced by mankind and the earth in the 21 st century. Currently, to address this severe water challenge, membrane separation technology is widely used in wastewater treatment and reuse. Meanwhile, with the continuous increase of application requirements, higher and higher requirements are also put forward on the membrane performance. And the polymer microporous membrane is functionally modified, so that multiple performances can be endowed to the polymer microporous membrane.
In the conventional modification method of the polymer microporous membrane, a new functional substance can be introduced. The functional substances are divided into organic and inorganic substances. Although the organic functional substance can provide abundant functionalization to the polymer microporous membrane, the physical and chemical damage resistance of the polymer microporous membrane cannot be improved. Therefore, organic/inorganic composite films have been prepared through a phase inversion process by introducing an inorganic medium such as inorganic nanoparticles directly into a polymer casting solution. However, due to the problem of interfacial compatibility between the polymer and the inorganic nanoparticles, the inorganic nanoparticles are not uniformly dispersed, and the mechanical properties of the polymer film are reduced. Therefore, there are also researchers to coat a layer of inorganic nano-materials on the surface of the polymer film by means of coating and loading. For example, Wang et al prepared polyethersulfone microporous membranes with nanosilver loaded on the surface by a nanosilver-containing chitosan solution deposition method, endowed with the membrane antibacterial and p-nitrophenol degrading functions (see references Rui W, Xin S, Tao X, eta1. Mussel-impregnated chip-polyurethane coatings for improving the antibacterial and antibacterial properties of polymeric membranes [ J ]. Carbohydrate Polymers, 2017, 168: 310.). Bear et al prepared polymer/Nanowire Films by coating polyethylene terephthalate treated Silver nanowires onto the surface of microporous Films (cf. Xiong, W., Liu, H., Chen, Y., Zheng, M., ZHao, Y., Kong, X., … & Jiang, L. (2016.). Highly Conductive, Air-Stable Silver Nanowire @ Iongel Composite Films heated Flexible Conductive electrodes, advanced Materials, 28(33), 7167-7172). However, in such methods, the inorganic nanomaterial is not stably loaded, and thus, poor exfoliation is likely to occur in separation applications.
Disclosure of Invention
In view of the above, the present invention provides a nanowire-loaded polymer microporous membrane with stable performance and a preparation method thereof.
The invention provides a polymer microporous membrane for loading nanowires, wherein a covering layer is loaded on the surface of the polymer microporous membrane, the covering layer comprises a plurality of nanowires which are arranged in a disordered way and are crossed with each other, and a plurality of silver particles are attached to the crossed positions of the adjacent nanowires, so that the nanowires form an integral cross-linked network structure.
The invention also provides a preparation method of the polymer microporous membrane loaded with the nanowires, which comprises the following steps:
(1) providing nanowires and a polymeric microporous membrane;
(2) loading the nano-wire on the surface of the polymer microporous membrane;
(3) providing a silver solution, wherein the silver solution is prepared from alkali, an ammonia water solution, silver nitrate and a saccharide compound;
(4) and (3) immersing the polymer microporous membrane obtained in the step (2) into the silver solution for a period of time, and taking out to obtain the polymer microporous membrane loaded with the nanowires.
Compared with the prior art, the nanowire-loaded polymer microporous membrane has the following advantages:
the plurality of nanowires are interdigitated with each other and the silver particles are coated at the intersections of the adjacent nanowires, which can be seen as "soldering" the adjacent nanowires together by the silver particles, so that the plurality of nanowires form an integral cross-linked network structure. At this time, the plurality of nanowires may be stably supported on the surface of the polymer microporous membrane. The cross-linked network structure formed by the nanowires can physically protect the polymer microporous membrane, and effectively reduce various physical and chemical damages and pollution to the polymer microporous membrane in the water treatment process, so that the obtained nanowire-loaded polymer microporous membrane has long-acting functional action and physical and chemical stability resistance in the practical application separation process.
Of course, by selecting different kinds of nanowires, abundant functions can be imparted to the polymer microporous membrane.
The preparation method of the polymer microporous membrane loaded with the nanowires has the following advantages:
compared with the existing method of loading inorganic matters on the surface of the polymer microporous membrane by coating, the method has the defect that inorganic matter particles are easy to fall off, and the nanowires loaded on the surface of the polymer microporous membrane obtained by the method disclosed by the application are in a cross-linked integral network structure, so that the nanowires can be firmly attached to the surface of the polymer microporous membrane.
In the preparation method, the silver solution is selected as a raw material to form the silver particles, considering that the formation of the silver solution (silver particles) can be realized at normal temperature, and the preparation and operation are easy without harsh reaction conditions such as high temperature and reaction equipment.
The preparation method has simple steps, is easy to operate and realize, and is easy for industrial production.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) cross-section photograph of a silver nanowire loaded polyvinylidene fluoride microporous membrane prepared in example 1;
FIG. 2 is a surface SEM photograph of a silver nanowire loaded polyvinylidene fluoride microporous membrane prepared in example 1;
fig. 3 is a surface photograph of the silver nanowire-loaded polyvinylidene fluoride microporous membrane prepared in example 1 after being washed with water at a pressure of 0.1MPa for 24 hours.
FIG. 4 is a photograph of the surface of the polyvinylidene fluoride microporous membrane of comparative example 1 after being washed with a water stream of 0.1MPa pressure for 24 hours.
Fig. 5 is a photograph showing the antibacterial effect of the microporous polylactic acid membrane of comparative example 2 and the microporous polylactic acid membrane supporting copper nanowires obtained in example 3 (wherein the left side corresponds to the microporous polylactic acid membrane of comparative example 2 and the right side corresponds to the microporous polylactic acid membrane supporting copper nanowires obtained in example 3).
Detailed Description
The nanowire-loaded polymer microporous membrane and the preparation method thereof provided by the present invention will be further described below.
The invention provides a preparation method of a polymer microporous membrane loaded with nanowires, which comprises the following steps:
s1, providing a nanowire and a polymer microporous membrane;
s2, loading the nanowires on the surface of the polymer microporous membrane;
s3, providing a silver solution, wherein the silver solution is prepared from alkali, an ammonia water solution, silver nitrate and a saccharide compound; and
and S4, immersing the polymer microporous membrane obtained in the step S2 into the silver solution for a period of time, and taking out to obtain the polymer microporous membrane loaded with the nanowires.
In step S1, the material and size of the nanowire are not limited. In practical applications, in order to endow the polymer microporous membrane with better performance, the nanowire can be at least one of silver nanowire, copper nanowire, gold nanowire, tungsten oxide nanowire and carbon nanotube. The diameter of the nano wire is 10-100 nanometers.
The material of the polymer microporous membrane is not limited, and the existing microporous membranes can be selected, such as: polyvinylidene fluoride microporous membranes, polysulfone microporous membranes, polylactic acid microporous membranes, polyether sulfone microporous membranes and the like. The surface of the polymer microporous membrane is provided with a plurality of open pores (see fig. 1), it should be noted that the nanowires loaded on the surface of the polymer microporous membrane do not block the open pores on the surface of the polymer microporous membrane, because the nanowires have a smaller diameter, and the cross-linked network structure formed by the multiple nanowires which are randomly arranged and crossed with each other includes a plurality of through holes, and the presence of the plurality of holes is also beneficial to the application of the polymer microporous membrane in membrane separation. In addition, the cross-linked network structure formed by the nanowires physically covers the surface of the polymer microporous membrane, namely a protective layer is formed on the surface of the polymer microporous membrane, the cross-linked network structure and the polymer microporous membrane are actually of a two-layer structure, and the nanowires do not enter the interior of the polymer microporous membrane.
In step S2, the method for loading the nanowires on the surface of the polymer microporous membrane can be spraying, spin coating, immersion, suction filtration, electrostatic spinning, blade coating, brush coating, and the like. For example, mixing the nanowires with a solvent to obtain a solution containing nanowires; and pouring the solution containing the nanowires to the polymer microporous membrane, and performing suction filtration to obtain the nano-wire-containing solution. It should be noted that the amount of the nanowires loaded on the polymer microporous membrane is not limited, as long as the loaded nanowires are located between adjacent nanowiresWith intersecting and through holes. Preferably, considering that the finally formed polymer microporous membrane loaded with nanowires still ensures the existence of surface open pores of the polymer microporous membrane, the nanowire concentration in the nanowire-containing solution is 0.01g/100 mL-0.05 g/100mL, and the ratio of the mass of the nanowire-containing solution to the area of the polymer microporous membrane is: 1g/cm2～5g/cm2。
In step S3, the silver solution may be prepared by alkali, ammonia solution, silver nitrate, and saccharide compound. The silver solution was the solution as prepared and was to be used immediately in step S4. In the silver solution, the mass fraction of the alkali is 0.01-0.1%, the mass fraction of the silver nitrate is 0.02-0.18%, the mass fraction of the saccharide compound is 0.1-1%, and the mass percentage of ammonia in the ammonia water solution in the silver solution is 0.01-0.15%. Wherein the alkali is at least one of sodium hydroxide and potassium hydroxide, and the saccharide compound is at least one of glucose, fructose and maltose. The mass fraction of ammonia in the ammonia water solution is 8-30%.
In step S4, the silver solution in step S3 undergoes a silver mirror-like reaction, except that silver is not supported on the surface of the glass, but on the nanowires. Because the plurality of nanowires are arranged in a disordered manner and cross with each other, the intersections of the adjacent nanowires are easier to deposit or cover with silver particles, and the silver particles are formed to enable the adjacent nanowires to be tightly connected to form an integral cross-linked network structure. This process, can be seen as: silver acts as a "solder" by which adjacent nanowires are "soldered" together by "electroless soldering" of the silver. Of course, the surface of the nanowires will also be coated with silver in this process.
And (4) immersing the polymer microporous membrane obtained in the step (S2) into the silver solution for 30 seconds to 10 minutes. The time for which the polymer microporous membrane is immersed in the silver solution is preferably 60 seconds to 5 minutes in consideration of the generation quality of silver and the efficiency of loading on the nanowire. The particle size of the formed silver particles is 10 nanometers to 1 micrometer.
The invention also provides a polymer microporous membrane loaded with the nanowire. The surface of the polymer microporous membrane is loaded with a covering layer. The cover layer includes a plurality of nanowires that are randomly arranged and cross each other. A plurality of silver particles overlie adjacent nanowire intersections such that the plurality of nanowires form an integral cross-linked network structure.
Wherein the thickness of the covering layer is 1-10 microns.
Compared with the prior art, the nanowire-loaded polymer microporous membrane has the following advantages:
the plurality of nanowires are interdigitated with each other and the silver particles are coated at the intersections of the adjacent nanowires, which can be seen as "soldering" the adjacent nanowires together by the silver particles, so that the plurality of nanowires form an integral cross-linked network structure. At this time, the plurality of nanowires may be stably supported on the surface of the polymer microporous membrane. The cross-linked network structure formed by the nanowires can physically protect the polymer microporous membrane, and effectively reduce various physical and chemical damages and pollution to the polymer microporous membrane in the water treatment process, so that the obtained nanowire-loaded polymer microporous membrane has long-acting functional action and physical and chemical stability resistance in the practical application separation process.
Of course, by selecting different kinds of nanowires, abundant functions can be imparted to the polymer microporous membrane.
The preparation method of the polymer microporous membrane loaded with the nanowires has the following advantages:
compared with the existing method of loading inorganic matters on the surface of the polymer microporous membrane by coating, the method has the defect that inorganic matter particles are easy to fall off, and the nanowires loaded on the surface of the polymer microporous membrane obtained by the method disclosed by the application are in a cross-linked integral network structure, so that the nanowires can be firmly attached to the surface of the polymer microporous membrane. The preparation method has simple steps, is easy to operate and realize, and is easy for industrial production.
Hereinafter, the nanowire-supported polymer microporous membrane and the method for preparing the same according to the present invention will be further described with reference to specific examples.
Example 1
Selecting silver nanowires with the diameter of 50 nanometers, preparing the silver nanowires into 0.05g/100mL of ethanol solution containing the silver nanowires, and performing suction filtration on 10g of ethanol solution containing the silver nanowires to the surface of a polyvinylidene fluoride microporous membrane with the square centimeter of the surface to obtain the prefabricated polyvinylidene fluoride microporous membrane.
And (2) preparing a silver solution, wherein the silver solution is an aqueous solution composed of 0.03% of sodium hydroxide, 0.05% of ammonia water, 0.1% of silver nitrate and 0.5% of maltose in mass fraction, the mass fraction is based on the total mass of the silver solution, and the mass fraction of each component is the same as that of the following embodiments and is not repeated.
And (3) placing the prepared polyvinylidene fluoride microporous membrane obtained in the step (1) in 20g of the silver solution for treating for 3 minutes.
And (4) placing the polyvinylidene fluoride microporous membrane treated in the step (3) in pure water, oscillating and cleaning for 3 minutes, and then drying to obtain the silver nanowire-loaded polyvinylidene fluoride microporous membrane.
And carrying out appearance characterization on the obtained polyvinylidene fluoride microporous membrane loaded with the silver nanowires. The results are shown in FIGS. 1 and 2.
As can be seen in fig. 1, the thickness of the silver nanowire layer on the surface of the silver nanowire-loaded polyvinylidene fluoride microporous membrane is about 2 micrometers.
As can be seen in fig. 2, silver particles are present at the silver nanowire intersections on the surface of the silver nanowire-loaded polyvinylidene fluoride microporous membrane.
To better illustrate the performance of the silver nanowire loaded polyvinylidene fluoride microporous membrane obtained in example 1, comparative example 1 is also provided.
Comparative example 1
Comparative example 1 is a control of example 1, i.e., consistent with the preformed polyvinylidene fluoride microporous membrane obtained in step (1) of example 1, without immersion in a silver solution.
And (3) carrying out stability performance test on the prefabricated polyvinylidene fluoride microporous membrane in the comparative example 1 and the silver nanowire-loaded polyvinylidene fluoride microporous membrane obtained in the example 1. The results are shown in FIGS. 3 and 4.
As can be seen from fig. 3 and 4, the silver nanowire layer on the surface of the silver nanowire-loaded polyvinylidene fluoride microporous membrane obtained in example 1 was maintained well after being washed with water, whereas the silver nanowire layer on the surface of the prefabricated polyvinylidene fluoride microporous membrane obtained in comparative example 1 was severely lost after being washed with water.
Example 2
Selecting gold nanowires with the diameter of 30 nanometers, preparing the gold nanowires into 0.01g/100mL of ethanol solution containing the gold nanowires, and depositing 15g of the ethanol solution containing the gold nanowires on the surface of a polysulfone microporous membrane with the thickness of 15 square centimeters to obtain a prefabricated polysulfone microporous membrane;
and (2) preparing a silver solution, wherein the silver solution is an aqueous solution consisting of 0.03% of sodium hydroxide, 0.01% of potassium hydroxide, 0.07% of ammonia water, 0.08% of silver nitrate and 0.4% of fructose in percentage by mass.
And (3) treating the preformed polysulfone microporous membrane obtained in the step (1) in 15g of the silver solution for 4 minutes.
And (4) placing the polysulfone microporous membrane treated in the step (3) in pure water, standing for 10 minutes, and then drying to obtain the gold nanowire-loaded polysulfone microporous membrane.
And performing morphology characterization and catalytic performance test on the obtained gold nanowire-loaded polysulfone microporous membrane. The result shows that the thickness of the gold nanowire layer on the surface of the gold nanowire-loaded polysulfone microporous membrane is about 3 microns. The gold nanowire-loaded polysulfone microporous membrane has a stable catalytic degradation effect on paranitrophenol.
Example 3
Step (1), selecting copper nanowires with the diameter of 70 nanometers, preparing the copper nanowires into 0.03g/100mL of ethanol solution containing the copper nanowires, and performing suction filtration on 25g of the ethanol solution containing the copper nanowires to the surface of a polylactic acid microporous membrane with the thickness of 20 square centimeters to obtain a prefabricated polylactic acid microporous membrane;
and (2) preparing a silver solution, wherein the silver solution is an aqueous solution composed of 0.01% of sodium hydroxide, 0.03% of ammonia water, 0.06% of silver nitrate and 0.2% of glucose in percentage by mass.
And (3) placing the preformed polylactic acid microporous membrane obtained in the step (1) in 20g of the silver solution for treating for 10 minutes.
And (4) placing the polylactic acid microporous membrane treated in the step (3) in pure water, standing for 10 minutes, and then drying to obtain the copper nanowire-loaded polylactic acid microporous membrane.
And carrying out appearance characterization on the obtained polylactic acid microporous membrane loaded with the copper nanowires. The results show that the thickness of the copper nanowire layer on the surface of the polylactic acid microporous membrane is about 1 micron.
To better illustrate the antibacterial effect of the copper nanowire-loaded polylactic acid microporous membrane obtained in example 3, comparative example 2 is also provided.
Comparative example 2
Comparative example 1 is a blank of example 3, a polylactic acid microporous membrane, not loaded with copper nanowires.
And (3) performing an antibacterial performance test on the polylactic acid microporous membrane in the comparative example 1 and the polylactic acid microporous membrane loaded with the copper nanowires obtained in the example 3 (the strain is escherichia coli). The results are shown in FIG. 5.
As can be seen from fig. 5, the surface of the polylactic acid microporous membrane of the comparative example 2 is full of escherichia coli, and no bacteriostatic zone appears, while the polylactic acid microporous membrane loaded with the copper nanowires obtained in example 3 has an obvious bacteriostatic zone, which indicates that the polylactic acid microporous membrane loaded with the copper nanowires obtained in example 3 has good antibacterial performance.
Example 4
Selecting a carbon nano tube with the diameter of 10 nanometers, preparing the carbon nano tube into 0.03g/100mL ethanol solution containing the carbon nano tube, and performing suction filtration on 15g of the ethanol solution containing the carbon nano tube to the surface of a polyether sulfone microporous membrane with the square centimeter of 10 to obtain the prefabricated polyether sulfone microporous membrane.
And (2) preparing a silver solution, wherein the silver solution is an aqueous solution composed of 0.08% of potassium hydroxide, 0.15% of ammonia water, 0.15% of silver nitrate and 0.8% of glucose in percentage by mass.
And (3) placing the prefabricated polyether sulfone microporous membrane obtained in the step (1) in 15g of the silver solution for treating for 8 minutes.
And (4) placing the polyether sulfone microporous membrane treated in the step (3) in pure water, standing for 10 minutes, and then drying to obtain the carbon nanotube-loaded polyether sulfone microporous membrane.
And performing morphology characterization on the obtained carbon nanotube-loaded polyethersulfone microporous membrane. The results show that the carbon nanotube wire layer thickness on the surface of the carbon nanotube-loaded polyethersulfone microporous membrane was about 7 microns.
Example 5
Step (1), selecting silver nanowires with the diameter of 50 nanometers and gold nanowires with the diameter of 30 nanometers, configuring the silver nanowires with the diameter of 0.02g/100mL and the gold nanowires with the diameter of 0.02g/100mL into ethanol solution, and immersing a polyvinylidene fluoride hollow fiber membrane with the length of 10 centimeters into 30g of ethanol solution containing the silver nanowires and the gold nanowires for 20 minutes to obtain the prefabricated polyvinylidene fluoride hollow fiber membrane.
And (2) preparing a silver solution, wherein the silver solution is an aqueous solution composed of 0.1% of sodium hydroxide, 0.1% of ammonia water, 0.18% of silver nitrate, 0.5% of fructose and 0.5% of glucose in percentage by mass.
And (3) placing the prefabricated polyvinylidene fluoride hollow fiber membrane obtained in the step (1) in 30g of the silver solution for treating for 30 seconds.
And (4) placing the polyvinylidene fluoride hollow fiber membrane treated in the step (3) in pure water, oscillating and cleaning for 3 minutes, and then drying to obtain the polyvinylidene fluoride hollow fiber membrane loaded with the silver nanowires and the gold nanowires.
And carrying out appearance characterization and catalytic performance test on the obtained polyvinylidene fluoride hollow fiber membrane loaded with the silver nanowires and the gold nanowires. The results show that the thickness of the carbon nano-tube line layer on the surface of the polyvinylidene fluoride hollow fiber membrane loaded with the silver nano-wires and the gold nano-wires is about 5 microns. The polysulfone microporous membrane loaded with the silver nanowires and the gold nanowires has good antibacterial performance on escherichia coli and catalytic degradation performance on methylene blue.
Example 6
Step (1), selecting tungsten oxide nanowires with the diameter of 100 nanometers, preparing the tungsten oxide nanowires into 0.05g/100mL of ethanol solution containing the tungsten oxide nanowires, and immersing a 30-centimeter-long polysulfone hollow fiber membrane into 50g of the ethanol solution containing the tungsten oxide nanowires for 30 minutes to obtain a prefabricated polysulfone hollow fiber membrane;
and (2) preparing a silver solution, wherein the silver solution is an aqueous solution composed of 0.05% of sodium hydroxide, 0.01% of ammonia water, 0.02% of silver nitrate and 0.1% of maltose in percentage by mass.
And (3) placing the prefabricated polysulfone hollow fiber membrane obtained in the step (1) in 50g of the silver solution for treating for 10 minutes.
And (4) placing the polysulfone hollow fiber membrane treated in the step (3) in pure water, standing for 10 minutes, and then drying to obtain the polysulfone hollow fiber membrane loaded with the tungsten oxide nanowires.
And performing morphology characterization and catalytic performance test on the obtained polysulfone hollow fiber membrane loaded with the tungsten oxide nanowires. The result shows that the thickness of the tungsten oxide nanowire layer on the surface of the polysulfone hollow fiber membrane loaded with the tungsten oxide nanowire is about 10 microns; the polysulfone hollow fiber membrane loaded with the tungsten oxide nanowires has good catalytic degradation performance on p-nitrophenol and methylene blue. .
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A preparation method of a polymer microporous membrane loaded with nanowires is characterized by comprising the following steps:
(1) providing nanowires and a polymeric microporous membrane;
(2) loading the nano-wire on the surface of the polymer microporous membrane;
(3) providing a silver solution, wherein the silver solution is prepared from alkali, an ammonia water solution, silver nitrate and a saccharide compound; and
(4) immersing the polymer microporous membrane obtained in the step (2) into the silver solution for a period of time, taking out to obtain the polymer microporous membrane loaded with the nanowires,
the surface of the polymer microporous membrane is loaded with a covering layer, the covering layer comprises a plurality of nanowires which are arranged in a disordered way and are crossed with each other, and a plurality of silver particles cover the crossed positions of the adjacent nanowires, so that a plurality of nanowires form an integral cross-linked network structure.
2. The method of preparing the nanowire-loaded polymer microporous membrane according to claim 1, wherein the mass fraction of the alkali in the silver solution is 0.01 to 0.1%, the mass fraction of the silver nitrate is 0.02 to 0.18%, the mass fraction of the saccharide compound is 0.1 to 1%, and the mass percentage of ammonia in the aqueous ammonia solution to the silver solution is 0.01 to 0.15%.
3. The method of preparing the nanowire-loaded polymer microporous membrane according to claim 2, wherein the base is at least one of sodium hydroxide and potassium hydroxide, and the saccharide compound is at least one of glucose, fructose, and maltose.
4. The method for preparing the nanowire-loaded polymer microporous membrane according to claim 1, wherein in the step (4), the polymer microporous membrane obtained in the step (2) is immersed in the silver solution for 30 seconds to 10 minutes.
5. A nanowire-supported polymer microporous membrane obtained by the preparation method according to any one of claims 1 to 4, wherein a covering layer is supported on the surface of the polymer microporous membrane, the covering layer comprises a plurality of nanowires which are randomly arranged and mutually crossed, and a plurality of silver particles cover the crossing positions of the adjacent nanowires, so that a plurality of nanowires form an integral cross-linked network structure.
6. The nanowire-loaded polymeric microporous membrane of claim 5, wherein the cover layer has a thickness of from 1 micron to 10 microns.
7. The nanowire-loaded polymeric microporous membrane of claim 5, wherein the nanowires have a diameter of 10 to 100 nanometers, and the nanowires are at least one of silver nanowires, copper nanowires, gold nanowires, and tungsten oxide nanowires.
8. The nanowire-loaded polymeric microporous membrane of claim 5, wherein the silver particles have a particle size of 10 nanometers to 1 micron.
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