CN110480028B - Method for preparing silver nano-fibers by using organic halide as auxiliary material and application thereof - Google Patents
Method for preparing silver nano-fibers by using organic halide as auxiliary material and application thereof Download PDFInfo
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- CN110480028B CN110480028B CN201910906016.1A CN201910906016A CN110480028B CN 110480028 B CN110480028 B CN 110480028B CN 201910906016 A CN201910906016 A CN 201910906016A CN 110480028 B CN110480028 B CN 110480028B
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Abstract
The invention discloses a method for preparing silver nanofibers by using organic halides for assistance and application, and belongs to the field of preparation of one-dimensional nanomaterials. The preparation method specifically comprises the following steps: respectively dissolving a silver salt, an organic protective agent and an organic halide in a condensed polyol or a condensed polyol to form a solution; then, uniformly mixing the solutions and reacting for a period of time at a fixed temperature to finally obtain a silver nanofiber solution; after the silver nano-fiber solution is separated and purified, the silver nano-fiber with the average diameter of 5-50nm and the average length of 5-100 mu m is obtained. The preparation method does not need high temperature/high pressure and extra protective gas, the whole process flow is easy to operate, the reaction condition is relatively mild, and batch production is easy to realize; and the prepared silver nanofiber has small diameter, high length-diameter ratio and good uniformity, and can be used as a key conductive material for preparing a flexible transparent conductive film.
Description
Technical Field
The invention belongs to the field of preparation of one-dimensional nano materials, relates to a method for preparing silver nano fibers by using organic halides in an auxiliary manner, and also relates to application of silver nano fibers prepared by using organic halides in preparation of a flexible transparent conductive film.
Background
Currently, indium Tin Oxide (ITO) sputtered plastic films are most widely used in highly transparent conductive electronic components, although these films have relatively low resistivity. However, it has high brittleness and poor flexibility, and thus is easily damaged by bending force applied from the outside, and indium in the ITO thin film is a scarce metal, has a small amount of global reserves, and has a high development and purification cost, resulting in a rapid rise in its price. Along with the development of science and technology and society, the ITO film is owing to exist more than not enough, can't satisfy people to the touch-sensitive screen of can buckling, flexible electronic components's such as wearable equipment demand. Therefore, research and preparation of ITO film substitute materials with practical application prospects are important, and the materials are expected to become main raw materials for flexible electronic component production in the future.
With the development, many materials to replace ITO thin films have been derived, such as: nano silver wire, carbon nanotube, metal mesh, graphene, etc. The industrial production technology of carbon nanotubes still needs to be improved, and the performance of the transparent conductive film made of the carbon nanotubes cannot be comparable to that of the existing ITO film; and although the metal grid has low sheet resistance, high transparency and high flexibility, the metal grid can cause serious Moore interference fringes and cannot be used as a substitute material of a mainstream ITO (indium tin oxide) film in a touch screen scene used at a short distance.
Although graphene has high light transmittance and low resistivity, in an actual production process, extremely severe conditions such as high pressure, high temperature and vacuum are required, so that the production cost is greatly increased, and the conditions for realizing industrial production are difficult to be met in a short time. In comparison, silver is more in the earth crust, is widely distributed and is lower in price; in addition, the transparent conductive film made of the silver nanofibers has more excellent light transmittance, conductivity and bending resistance, so that the application of the silver nanofibers in flexible display electronic devices is more competitive. More importantly, the conditions for preparing the silver nano-fiber are generally mild, severe conditions such as high temperature and high pressure are not needed, the operation process is simple, the danger is low, the production cost is low, the environmental pollution is light, and the industrial production is easy to realize. Therefore, the ITO material is considered to be the ITO substitute material with the highest application potential at present, and is expected to become the mainstream material for manufacturing flexible electronic components in the future.
However, the film is prone to severe diffuse reflection due to the irregularity of the distribution of silver nanofibers on the surface of the film. This results in the light reflected from the surface of the film when the film is exposed to intense light, which makes the content invisible. It has been proved by the existing research that when the wire diameter of the silver nano fiber is smaller and the length-diameter ratio is higher, the haze of the film is lower, the light transmittance is higher and the resistance is lower. Therefore, in order to improve the light transmittance and the electrical conductivity of the silver nanofiber film, effectively reduce the haze and solve the practical application problem, the silver nanofiber with small wire diameter and high length-diameter ratio needs to be prepared.
Among the many processes for preparing silver nanofibers, the most widely used and technically mature process to date is the polyol reduction process. For example, lee et al (APL Materials,1 (2013): 042118/1-6) produced ultra-fine nano silver wires with a wire diameter of 15nm using sodium chloride and potassium bromide as additive aids, but this method required two kinds of aids and was carried out under high pressure reaction conditions. You et al (Materials Letters,63 (2009): 920-922) prepared ultra-fine silver nanowires with a wire diameter of 20nm by reducing silver nitrate in ethanol solution with dodecylamine. However, the preparation method is long in time, time-consuming, labor-consuming and not beneficial to industrial production.
Therefore, how to prepare silver nanofibers with small wire diameter, high aspect ratio, good uniformity and easy realization of industrial production is a technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
The invention aims to provide a method for preparing silver nanofibers by using organic halides, the silver nanofibers prepared by the method have small wire diameter, high length-diameter ratio, few particles and other nonlinear substances, the process flow is simple, and the industrial production is easy to realize.
In order to achieve the above results, the present invention needs to adopt the following process technologies:
the invention provides a method for preparing silver nano-fibers by using organic halides for assistance, which comprises the following specific steps:
(1) Respectively dissolving silver salt, organic protective agent and organic halide in mono-condensed or poly-condensed polyol to form solution a, solution b and solution c;
(2) Uniformly stirring and mixing the solution a, the solution b and the solution c to obtain a solution d;
(3) Standing the solution d at room temperature for reaction for a period of time; obtaining a reaction solution e;
(4) Keeping the solution e at a set temperature for a period of time to obtain a silver nanofiber solution f;
(5) And (3) carrying out multiple separation and purification treatments on the silver nanofiber solution f to finally prepare the silver nanofiber.
Preferably, the silver salt is selected from one or more of silver acetate, silver carboxylate, silver acetylacetonate and other silver salt compounds with organic anions; the polyhydric alcohol is selected from one or more of diethylene glycol, dipropylene glycol, diglycerol, triethylene glycol, tripropylene glycol and other polyhydric alcohols or derivatives thereof; the organic protective agent is selected from one or more of a multi-block copolymer of polyvinylpyrrolidone and polyethylene glycol and derivatives thereof.
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Preferably, the molar ratio of the organic protective agent to the silver salt in the solution d is 0.1.
Preferably, the molar volume concentration of the silver salt in the solution a is 0.001 mol/L-2.00 mol/L, the molar volume concentration of the organic protective agent in the solution b is 0.001 mol/L-20 mol/L, and the molar volume concentration of the organic halide in the solution c is 0.0001 mol/L-0.020 mol/L.
Preferably, the molecular weight Mw of the organic protective agent is 30000-3000000.
Preferably, the stirring temperature of the solution a-c is 0-30 ℃, the stirring speed is 0-100 r/s, and the stirring time is 1-120 min.
Preferably, the room temperature of the solution d is 0-30 ℃, and the standing time is 1-1440 min.
Preferably, the reaction temperature of the solution e is 80-250 ℃, and the heat preservation time is 10-1440 min.
The invention also discloses an application of the silver nano-fiber prepared by the aid of the organic halide in preparation of the flexible transparent conductive film.
According to the technical scheme, compared with the prior art, the method for preparing the silver nano-fibers by using the organic halide and the application thereof disclosed by the invention have the following excellent effects:
(1) The invention does not need high pressure, high temperature and extra protective gas, has simple whole process flow, is easy to operate and is easy to realize industrial production.
(2) The silver nano-fiber prepared by the method has the average diameter of 5-50nm, the average length of 5-100 mu m, almost no nano-particles, nano-rods and the like, and good uniformity.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings required for the embodiments will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and it is also possible for those skilled in the art to obtain other drawings based on the provided drawings without inventive effort.
FIG. 1 is a process flow diagram of the method for preparing silver nano-fibers with the aid of organic halides.
Fig. 2 is a scanning electron microscope image of the silver nanofibers prepared in example 1 of the present invention.
Fig. 3 is a scanning electron microscope image of the silver nanofiber prepared in example 2 of the present invention.
Fig. 4 is a scanning electron microscope image of silver nanofibers prepared in example 3 of the present invention.
Fig. 5 is a scanning electron microscope image of silver nanofibers prepared in example 4 of the present invention.
Fig. 6 is a scanning electron microscope image of silver nanofibers prepared in example 5 of the present invention.
Fig. 7 is a scanning electron microscope image of silver nanofibers prepared in example 6 of the present invention.
Fig. 8 is a scanning electron microscope photograph of silver nanofibers prepared according to example 7 of the present invention.
Fig. 9 is a scanning electron microscope photograph of silver nanofibers prepared according to example 8 of the present invention.
Fig. 10 is a scanning electron microscope image of silver nanofibers prepared in example 9 of the present invention.
Fig. 11 is a scanning electron microscope photograph of silver nanofibers prepared in example 10 of the present invention.
Fig. 12 is a scanning electron microscope photograph of silver nanofibers prepared in example 11 of the present invention.
Fig. 13 is a scanning electron microscope photograph of silver nanofibers prepared according to comparative example 1 of the present invention.
Fig. 14 is a scanning electron microscope photograph of silver nanofibers prepared according to comparative example 2 of the present invention.
Fig. 15 is a scanning electron microscope image of silver nanofibers prepared in comparative example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings of the specification, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to the attached drawing 1 of the specification, the invention discloses and protects a method for preparing silver nano-fibers by using organic halides, which specifically comprises the following steps:
(1) Respectively dissolving silver salt, organic protective agent and organic halide in mono-condensed or poly-condensed polyol to form solution a, solution b and solution c;
(2) Uniformly stirring and mixing the solution a, the solution b and the solution c to obtain a solution d;
(3) Standing the solution d at room temperature for reaction for a period of time to obtain a reaction solution e;
(4) Keeping the solution e at a set temperature for a period of time to obtain a silver nanofiber solution f;
(5) And (4) carrying out multiple separation and purification treatments on the silver nanofiber solution f to finally obtain the silver nanofiber.
In order to further optimize the technical scheme, the silver salt is selected from one or more of silver acetate, silver carboxylate, silver acetylacetonate and other silver salt compounds with organic anions; the polyhydric alcohol is one or more selected from diethylene glycol, dipropylene glycol, diglycerol, triethylene glycol, tripropylene glycol and other polyhydric alcohols or derivatives thereof; the organic protective agent is selected from one or more of a multi-block copolymer of polyvinylpyrrolidone and polyethylene glycol and derivatives thereof.
In order to further optimize the above technical solution, the organic halide is selected from one or more of methyl magnesium bromide, 6-bromohexyltriethylammonium bromide, 6-bromohexyltrimethylammonium bromide, hexylmagnesium bromide, n-pentylmagnesium bromide, 5-chloropentylzinc bromide, 6-chlorohexylzinc bromide, 5-bromopentyltrimethylammonium bromide, 1-methylpentylzinc bromide, 3-bromopropyltrimethylammonium bromide, 3-methylpropylammonium bromide, 2-bromoethyltrimethylammonium bromide, tetra-n-butylammonium dichlorobromide, tetra-n-butylammonium dibromochloride, tetra-n-butylammonium dibromoiodide, tetra-n-butylammonium diiodobromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetraheptylammonium bromide, tetraoctylammonium bromide, tetramethyltrimethylammonium bromide, tetrabutylammonium tribromide, tetrabutyltrimethylammonium iodide, decaalkyltrimethylammonium bromide, didodecyldimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, dihexadecyldimethylammonium bromide, dioctadecyldimethylammonium bromide, and similar or more organic derivatives thereof.
In order to further optimize the technical scheme, the molar ratio of the organic protective agent to the silver salt in the solution d is 0.1 to 20.
In order to further optimize the technical scheme, the molar volume concentration of the silver salt in the solution a is 0.001-2.00 mol/L, the molar volume concentration of the organic protective agent in the solution b is 0.001-20 mol/L, and the molar volume concentration of the organic halide in the solution c is 0.0001-0.020 mol/L.
In order to further optimize the technical scheme, the molecular weight Mw of the organic protective agent is 30000-3000000.
In order to further optimize the technical scheme, the stirring temperature is 0-30 ℃ when the solution a is mixed with the solution b and the solution c, the stirring speed is 0-100 r/s, and the stirring time is 1-120 min.
In order to further optimize the technical scheme, the standing temperature of the solution d is 0-30 ℃, and the standing time is 1-1440 min.
In order to further optimize the technical scheme, the reaction temperature of the solution e is 80-250 ℃, and the heat preservation time is 10-1440 min.
The preparation process and the excellent results of the present invention will be further illustrated with reference to specific examples, but the present invention is not limited to the following examples.
Example 1
A method for preparing silver nano-fibers by using organic halides for assistance specifically comprises the following steps:
(1) 1.122g of silver acetate and 0.075g of polyvinylpyrrolidone-polyethylene glycol diblock copolymer (molecular weight M) w = 30000) and 0.025g 6-bromohexyltriethylammonium bromide are respectively dissolved in diethylene glycol to form solutions a, b and c in sequence for standby;
(2) Uniformly mixing the solutions a-c under the condition of stirring at 0 ℃, wherein the stirring speed is 100r/s, and the stirring time is 30min, so as to obtain a solution d for later use;
(3) Standing the solution d at room temperature of 25 ℃ for reaction for 1min; obtaining a reaction solution e for later use;
(4) Setting the reaction temperature of the solution e to 180 ℃, and preserving the heat for 20min at the temperature to obtain a silver nanofiber solution f;
(5) And (4) carrying out multiple times of centrifugal washing and purification treatment on the solution f by using deionized water and absolute ethyl alcohol, and finally preparing the silver nano fiber. And it is known from the scanning electron microscope picture (figure 2) of the silver nanofiber prepared in example 1 of the present invention that the wire diameter of the silver nanofiber is-10 nm and the length is 40 μm, and the wire diameter and the length of the silver nanofiber are uniform and almost no particles are present.
Example 2
A method for preparing silver nano-fibers by using organic halides for assistance specifically comprises the following steps:
(1) 1.132g of silver carboxylate and 14.915g of polyvinylpyrrolidone-polyethylene glycol diblock copolymer (molecular weight M) w = 3000000) and 0.125g 3-methylpropyl ammonium bromide are respectively dissolved in diglycerol to form solutions a, b and c in sequence for standby;
(2) Uniformly mixing the solutions a-c under the condition of stirring at 25 ℃, wherein the stirring speed is 40r/s, and the stirring time is 120min, so as to obtain a solution d for later use;
(3) Standing the solution d at room temperature of 30 ℃ for reaction for 0.5h; obtaining a reaction solution e for later use;
(4) Setting the reaction temperature of the solution e to 160 ℃, and preserving the heat for 70min at the temperature to obtain a silver nanofiber solution f;
(5) And (4) carrying out multiple centrifugal washing and purification treatments on the solution f through deionized water and absolute ethyl alcohol, and finally preparing the silver nano fiber. And from the scanning electron micrograph (fig. 3) of the silver nanofiber prepared in example 2 of the present invention, it was found that the silver nanofiber has a wire diameter of-5 nm and a length of 50 μm, and the wire diameter and length of the silver nanofiber are uniform and almost free of particles.
Example 3
A method for preparing silver nano-fibers by using organic halides in an auxiliary manner specifically comprises the following steps:
(1) Will be provided with1.232g of silver acetylacetonate and 1.263g of polyvinylpyrrolidone-polyethylene glycol diblock copolymer (molecular weight M) w = 90000) and 0.120g of 1-methyl amyl zinc bromide are respectively dissolved in dipropylene glycol to form solutions a, b and c in sequence for later use;
(2) Uniformly mixing the solutions a-c under the stirring condition of 30 ℃, wherein the stirring speed is 50r/s, and the stirring time is 1min, so as to obtain a solution d for later use;
(3) Standing the solution d at 0 ℃ for reaction for 24 hours; obtaining a reaction solution e for later use;
(4) Setting the reaction temperature of the solution e to 250 ℃, and preserving the heat for 10min at the temperature to obtain a silver nanofiber solution f;
(5) And (4) carrying out multiple times of centrifugal washing and purification treatment on the solution f by using deionized water and absolute ethyl alcohol, and finally preparing the silver nano fiber. And from the scanning electron micrograph (fig. 4) of the silver nanofiber prepared in example 3 of the present invention, it was found that the silver nanofiber had a wire diameter of-10 nm and a length of 40 μm, and the wire diameter of the silver nanofiber had high uniformity and almost no particles.
Example 4
A method for preparing silver nano-fibers by using organic halides in an auxiliary manner specifically comprises the following steps:
(1) 1.032g of silver acetate and 1.263g of polyvinylpyrrolidone-polyethylene glycol diblock copolymer (molecular weight M) w = 60000) and 0.0001g of 1-methylpentyl zinc bromide are respectively dissolved in tripropylene glycol to form solutions a, b and c in turn for later use;
(2) Uniformly mixing the solutions a-c under the condition of stirring at 10 ℃, wherein the stirring speed is 0r/s, and the stirring time is 70min, so as to obtain a solution d for later use;
(3) Standing the solution d at room temperature of 25 ℃ for reaction for 1.5h; obtaining a reaction solution e for later use;
(4) Setting the reaction temperature of the solution e to 170 ℃, and preserving the heat for 100min at the temperature to obtain a silver nanofiber solution f;
(5) And (4) carrying out multiple times of centrifugal washing and purification treatment on the solution f by using deionized water and absolute ethyl alcohol, and finally preparing the silver nano fiber. And from the scanning electron micrograph (fig. 5) of the silver nanofiber prepared in example 4 of the present invention, it was found that the silver nanofiber had a wire diameter of-10 nm and a length of 40 μm, and the wire diameter of the silver nanofiber had high uniformity and almost no particles.
Example 5
A method for preparing silver nano-fibers by using organic halides in an auxiliary manner specifically comprises the following steps:
(1) 1.262g of silver carboxylate and 1.263g of polyvinylpyrrolidone-polyethylene glycol diblock copolymer (molecular weight M) w = 60000) and 0.335g didodecyldimethylammonium bromide are respectively dissolved in tripropylene glycol to form solutions a, b and c in sequence for later use;
(2) Uniformly mixing the solutions a-c under the condition of stirring at 25 ℃, wherein the stirring speed is 100r/s, and the stirring time is 120min, so as to obtain a solution d for later use;
(3) Standing the solution d at room temperature of 25 ℃ for reaction for 2h; obtaining a reaction solution e for later use;
(4) Setting the reaction temperature of the solution e to 80 ℃, and preserving the heat for 24 hours at the temperature to obtain a silver nanofiber solution f;
(5) And (4) carrying out multiple times of centrifugal washing and purification treatment on the solution f by using deionized water and absolute ethyl alcohol, and finally preparing the silver nano fiber. And from the scanning electron micrograph (fig. 6) of the silver nanofiber prepared in example 5 of the present invention, it was found that the silver nanofiber had a wire diameter of-50 nm and a length of 5 μm, and the wire diameter of the silver nanofiber had high uniformity and almost no particles.
Example 6
A method for preparing silver nano-fibers by using organic halides in an auxiliary manner specifically comprises the following steps:
(1) 1.253g of silver acetate and 1.263g of polyvinylpyrrolidone-polyethylene glycol diblock copolymer (molecular weight M) w = 90000) and 0.028g of n-pentyl magnesium bromide are respectively dissolved in triethylene glycol to form solutions a, b and c in sequence for later use;
(2) Uniformly mixing the solutions a-c under the condition of stirring at 20 ℃, wherein the stirring speed is 50r/s, and the stirring time is 70min, so as to obtain a solution d for later use;
(3) Standing the solution d at room temperature of 25 ℃ for reaction for 2h; obtaining a reaction solution e for later use;
(4) Setting the reaction temperature of the solution e to 160 ℃, and preserving the heat for 80min at the temperature to obtain a silver nanofiber solution f;
(5) And (4) carrying out multiple centrifugal washing and purification treatments on the solution f through deionized water and absolute ethyl alcohol, and finally preparing the silver nano fiber. And from the scanning electron micrograph (fig. 7) of the silver nanofiber prepared in example 6 of the present invention, it was found that the silver nanofiber had a wire diameter of-10 nm and a length of 40 μm, and the wire diameter of the silver nanofiber had high uniformity and almost no particles.
Example 7
A method for preparing silver nano-fibers by using organic halides in an auxiliary manner specifically comprises the following steps:
(1) 1.268g of silver carboxylate and 1.263g of polyvinylpyrrolidone-polyethylene glycol diblock copolymer (molecular weight M) w = 100000) and 0.001g tetramethyl ammonium tribromide are respectively dissolved in diethylene glycol to form solutions a, b and c in sequence for later use;
(2) Uniformly mixing the solutions a-c under the stirring condition of 15 ℃, wherein the stirring speed is 25r/s, and the stirring time is 50min, so as to obtain a solution d for later use;
(3) Standing the solution d at room temperature of 25 ℃ for reaction for 1h; obtaining a reaction solution e for later use;
(4) Setting the reaction temperature of the solution e to 165 ℃, and preserving the heat for 90min at the temperature to obtain a silver nanofiber solution f;
(5) And (4) carrying out multiple centrifugal washing and purification treatments on the solution f through deionized water and absolute ethyl alcohol, and finally preparing the silver nano fiber. And from the scanning electron micrograph (fig. 8) of the silver nanofiber prepared in example 7 of the present invention, it was found that the silver nanofiber had a wire diameter of-10 nm and a length of 40 μm, and the wire diameter of the silver nanofiber had high uniformity and almost no particles.
Example 8
A method for preparing silver nano-fibers by using organic halides for assistance specifically comprises the following steps:
(1) 0.024g of silver acetylacetonate, 0.563g of polyvinylpyrrolidone-polyEthylene glycol diblock copolymer (molecular weight M) w = 100000) and 0.269g dicetyl dimethyl ammonium bromide are respectively dissolved in tripropylene glycol to form solutions a, b and c in sequence for later use;
(2) Uniformly mixing the solutions a-c under the condition of stirring at 25 ℃, wherein the stirring speed is 30r/s, and the stirring time is 60min, so as to obtain a solution d for later use;
(3) Standing the solution d at room temperature of 25 ℃ for reaction for 2h; obtaining a reaction solution e for later use;
(4) Setting the reaction temperature of the solution e to 170 ℃, and preserving the heat for 100min at the temperature to obtain a silver nanofiber solution f;
(5) And (4) carrying out multiple times of centrifugal washing and purification treatment on the solution f by using deionized water and absolute ethyl alcohol, and finally preparing the silver nano fiber. And from the scanning electron micrograph (fig. 9) of the silver nanofiber prepared in example 8 of the present invention, it was found that the silver nanofiber had a wire diameter of-10 nm and a length of 40 μm, and the wire diameter of the silver nanofiber had high uniformity and almost no particles.
Example 9
A method for preparing silver nano-fibers by using organic halides in an auxiliary manner specifically comprises the following steps:
(1) 0.008g of silver acetate and 10.263g of polyvinylpyrrolidone-polyethylene glycol diblock copolymer (molecular weight M) w = 60000) and 0.209g dioctadecyldimethylammonium bromide are dissolved in tripropylene glycol to form solutions a, b and c in turn for use;
(2) Uniformly mixing the solutions a-c under the condition of stirring at 25 ℃, wherein the stirring speed is 50r/s, and the stirring time is 60min, so as to obtain a solution d for later use;
(3) Standing the solution d at room temperature of 25 ℃ for reaction for 2h; obtaining a reaction solution e for later use;
(4) Setting the reaction temperature of the solution e to 175 ℃, and preserving the heat for 15min at the temperature to obtain a silver nanofiber solution f;
(5) And (4) carrying out multiple times of centrifugal washing and purification treatment on the solution f by using deionized water and absolute ethyl alcohol, and finally preparing the silver nano fiber. And from the scanning electron micrograph (fig. 10) of the silver nanofiber prepared in example 9 of the present invention, it was found that the silver nanofiber had a wire diameter of-5 nm and a length of 40 μm, and the wire diameter of the silver nanofiber had high uniformity and almost no particles.
Example 10
A method for preparing silver nano-fibers by using organic halides for assistance specifically comprises the following steps:
(1) 0.268g of silver carboxylate and 10.263g of polyvinylpyrrolidone-polyethylene glycol diblock copolymer (molecular weight M) w = 100000) and 0.209g of decaalkyltrimethylammonium bromide are respectively dissolved in diethylene glycol to form solutions a, b and c in sequence for standby;
(2) Uniformly mixing the solutions a-c under the condition of stirring at 25 ℃, wherein the stirring speed is 80r/s, and the stirring time is 20min, so as to obtain a solution d for later use;
(3) Standing the solution d at room temperature of 25 ℃ for reaction for 1h; obtaining a reaction solution e for later use;
(4) Setting the reaction temperature of the solution e to 170 ℃, and preserving the heat for 45min at the temperature to obtain a silver nanofiber solution f;
(5) And (4) carrying out multiple centrifugal washing and purification treatments on the solution f through deionized water and absolute ethyl alcohol, and finally preparing the silver nano fiber. And from the scanning electron micrograph (fig. 11) of the silver nanofiber prepared in example 10 of the present invention, it was found that the silver nanofiber had a wire diameter of-10 nm and a length of 40 μm, and the wire diameter of the silver nanofiber had high uniformity and almost no particles.
Example 11
A method for preparing silver nano-fibers by using organic halides in an auxiliary manner specifically comprises the following steps:
(1) 1.238g of silver acetate and 1.263g of polyvinylpyrrolidone-polyethylene glycol diblock copolymer (molecular weight M) w = 2000000) and 0.216g cetyltrimethylammonium bromide are respectively dissolved in diethylene glycol to form solutions a, b and c in sequence for standby;
(2) Uniformly mixing the solutions a-c under the stirring condition of 25 ℃, wherein the stirring speed is 80r/s, and the stirring time is 15min, so as to obtain a solution d for later use;
(3) Standing the solution d at room temperature of 25 ℃ for reaction for 1h; obtaining a reaction solution e for later use;
(4) Setting the reaction temperature of the solution e to 170 ℃, and preserving the heat for 50min at the temperature to obtain a silver nanofiber solution f;
(5) And (4) carrying out multiple centrifugal washing and purification treatments on the solution f through deionized water and absolute ethyl alcohol, and finally preparing the silver nano fiber. And from the scanning electron micrograph (fig. 12) of the silver nanofiber prepared in example 11 of the present invention, it was found that the silver nanofiber had a wire diameter of-10 nm and a length of 40 μm, and the wire diameter of the silver nanofiber had high uniformity and almost no particles.
In order to further verify the excellent effects of the technical scheme disclosed and protected by the invention, the inventor also carries out the following comparative tests, specifically comprising the following steps:
comparative example 1
Preparing silver nitrate as silver source, polyvinylpyrrolidone (M) w = 75000 molecular weight) as organic protective agent, sodium chloride as auxiliary agent, ethylene glycol as alcohol solvent.
(1) 1.122g of silver nitrate, 1.263g of polyvinylpyrrolidone (M) w 75000) and 0.025g of sodium chloride are respectively dissolved in ethylene glycol to form a solution a, a solution b and a solution c for standby;
(2) Uniformly mixing the solutions a-c under the condition of stirring at 25 ℃, wherein the stirring speed is 20r/s, and the stirring time is 30min, so as to obtain a solution d for later use;
(3) Standing the solution d at room temperature of 25 ℃ for reaction for 1h; obtaining a reaction solution e for later use;
(4) Setting the reaction temperature of the solution e to 180 ℃, and preserving the heat for 20min at the temperature to obtain a silver nanofiber solution f;
(5) And (4) carrying out multiple centrifugal washing and purification treatments on the solution f through deionized water and absolute ethyl alcohol, and finally preparing the silver nano fiber. And it is known from the scanning electron microscope picture (figure 13 in the specification) of the silver nanofiber prepared in comparative example 1 of the present invention that the wire diameter of the silver nanofiber is 40nm and the length is 20 μm, and the wire diameter and the length of the silver nanofiber are poor in uniformity, and there are short silver nanofibers in a crushed state and many particles.
Comparative example 2
In addition to polyvinylpyrrolidone (M) w = molecular weight 90000) as organic protective agent, sodium bromide as adjuvant, propylene glycol as alcohol solvent, the same experiment as in comparative example 1 was performed.
(1) 1.122g of silver nitrate, 1.263g of polyvinylpyrrolidone (M) w 90000) and 0.047g of sodium bromide are respectively dissolved in propylene glycol to form solutions a, b and c in turn for later use;
(2) Uniformly mixing the solutions a-c under the condition of stirring at 25 ℃, wherein the stirring speed is 20r/s, and the stirring time is 30min, so as to obtain a solution d for later use;
(3) Standing the solution d at room temperature of 25 ℃ for reaction for 1h; obtaining a reaction solution e for later use;
(4) Setting the reaction temperature of the solution e to 180 ℃, and preserving the heat for 20min at the temperature to obtain a silver nanofiber solution f;
(5) And (4) carrying out multiple centrifugal washing and purification treatments on the solution f through deionized water and absolute ethyl alcohol, and finally preparing the silver nano fiber. From the scanning electron microscope image (figure 14 in the specification) of the silver nanofiber prepared in comparative example 2 of the present invention, it was found that the silver nanofiber had a wire diameter of 45nm and a length of 10 μm, and the silver nanofiber had a non-uniform wire diameter and many particles.
Comparative example 3
In addition to polyvinylpyrrolidone (M) w = molecular weight 900000) as an organic protective agent and potassium chloride as an auxiliary agent, and the same experiment as in comparative example 1 was performed.
(1) 1.122g of silver nitrate, 1.263g of polyvinylpyrrolidone (M) w 900000 molecular weight) and 0.125g of potassium chloride are dissolved in ethylene glycol to form solutions a, b and c in turn for later use;
(2) Uniformly mixing the solutions a-c under the condition of stirring at 25 ℃, wherein the stirring speed is 20r/s, and the stirring time is 30min, so as to obtain a solution d for later use;
(3) Standing the solution d at room temperature of 25 ℃ for reaction for 1h; obtaining a reaction solution e for later use;
(4) Setting the reaction temperature of the solution e to 180 ℃, and preserving the heat for 20min at the temperature to obtain a silver nanofiber solution f;
(5) And (4) carrying out multiple centrifugal washing and purification treatments on the solution f through deionized water and absolute ethyl alcohol, and finally preparing the silver nano fiber. From the scanning electron microscope image (fig. 15 in the specification) of the silver nanofiber prepared in comparative example 3 of the present invention, it was found that the silver nanofiber had a wire diameter of-30 nm and a length of 25 μm, and the silver nanofiber had a non-uniform wire diameter and many particles.
In addition, the inventor applies the silver nanofibers prepared by the method to the preparation of the flexible transparent conductive film, and tests on photoelectric performance and bending resistance of the prepared conductive film are carried out, and the inventor finds that the prepared film has the characteristics of high light transmittance, low haze and low sheet resistance and has good bending resistance. The specific experimental operations and test results are as follows:
(1) And carrying out sheet resistance test on the conductive film by a four-probe resistance tester. After the instrument is started and stabilized, vertically contacting the four probe probes with the surface of the conductive film, and after the test data displayed on the instrument is stabilized;
(2) The conductive film was subjected to transmittance/haze test by a transmittance/haze tester. And opening the tester, preheating, then performing click calibration, performing instrument calibration, then placing the conductive film in the instrument, and performing click test.
(3) And (3) performing 500 times of bending tests on the manufactured flexible transparent conductive film, wherein the bending radius r is 2mm, and then testing the sheet resistance change of the bent flexible transparent conductive film by using a four-probe resistance tester.
The specific test results are shown in table 1 below:
TABLE 1 light transmittance, haze, and sheet resistance before and after cyclic bending deformation of conductive film
The data comparison in table 1 shows that the transparent conductive film prepared by the present invention has higher light transmittance (90%); lower haze (even as low as 0.6%) and better bending resistance, thus having good application prospect. The silver nanofibers with high length-diameter ratio and good uniformity tend to establish a more sparse and effective permeation network, so that a longer permeation path is provided, the probability of mutual overlapping of the silver nanofibers is reduced, the existence of overlapping resistance is reduced, and the resistance of the whole conductive network is reduced; on the other hand, the more sparse silver nanofiber network can effectively improve the transmittance of visible light, so that the light transmittance of the flexible transparent conductive film is improved, and the haze of the conductive film is reduced.
Claims (8)
1. A method for preparing silver nano-fibers by using organic halide as an assistant comprises the following specific steps:
(1) Respectively dissolving silver salt, organic protective agent and organic halide in mono-condensed or poly-condensed polyol to form solution a, solution b and solution c;
the organic protective agent is a diblock copolymer of polyvinylpyrrolidone and polyethylene glycol, and the molecular weight Mw of the organic protective agent is 30000-3000000;
(2) Uniformly stirring and mixing the solution a, the solution b and the solution c to obtain a solution d;
(3) Standing the solution d at 0-30 ℃ for reaction for 1-1440 min to obtain a reaction solution e;
(4) Keeping the temperature of the solution e at a set temperature for a period of time to obtain a silver nanofiber solution f;
(5) And (4) carrying out multiple separation and purification treatments on the silver nanofiber solution f to finally obtain the silver nanofiber.
2. The method for preparing silver nanofibers with the aid of organic halides as claimed in claim 1, wherein the silver salt is silver acetate, silver carboxylate or silver acetylacetonate; the polyhydric alcohol is diethylene glycol, dipropylene glycol, diglycerol, triethylene glycol, tripropylene glycol or tripropylene glycol.
3. The method for preparing silver nanofibers with the aid of organic halides as claimed in claim 1, wherein the organic halides are tetra n-butyl ammonium dichlorobromide, tetra n-butyl ammonium dibromochloride, tetra n-butyl ammonium dibromoiodide or tetra n-butyl ammonium diiodobromide.
4. The method for preparing silver nanofibers with the assistance of organic halides as claimed in claim 1, wherein the molar ratio of the organic protective agent to the silver salt in the solution d is 0.1 to 1.
5. The method for preparing silver nanofibers with the aid of organic halides as claimed in claim 1, wherein the molar volume concentration of silver salt in solution a is 0.001mol/L to 2.00mol/L, the molar volume concentration of organic protective agent in solution b is 0.001mol/L to 20mol/L, and the molar volume concentration of organic halide in solution c is 0.0001mol/L to 0.020mol/L.
6. The method for preparing silver nanofibers with the aid of organic halides as claimed in claim 1, wherein the solution a, the solution b and the solution c are mixed at a stirring temperature of 0 ℃ to 30 ℃, a stirring speed of 25r/s to 100r/s and a stirring time of 1min to 120min.
7. The method for preparing silver nanofibers by the aid of organic halides, according to claim 1, wherein the reaction temperature of the solution e is 80-250 ℃, and the holding time is 10-1440 min.
8. Use of silver nanofibers prepared according to the method of claim 1 for the preparation of flexible transparent conductive films.
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