• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    A method for making silver nanowires is provided, wherein the recovered silver nanowires have a high aspect ratio; and where the total glycol concentration is <0.001 wt% at any time during the process.
    公开号:FR3027609A1
    申请号:FR1560273
    申请日:2015-10-28
    公开日:2016-04-29
    发明作者:Wei Wang；Patrick T Mcgough；Janet M Goss；George L Athens；Jonathan D Lunn
    申请人:Dow Global Technologies LLC；
    IPC主号:
    专利说明:

    [0001] The present invention relates generally to the field of manufacturing silver nanowires. In particular, the present invention relates to a method of manufacturing silver nanowires having a high aspect ratio for use in a variety of applications. Films which exhibit high conductivity in combination with high transparency are of great value for use as electrodes or coatings in a wide range of electronic applications, including, for example, touchscreen display devices and photovoltaic cells. Current technology for these applications involves the use of films containing tin-doped indium oxide (ITO) that are deposited by physical vapor deposition processes. The high capital cost of physical vapor deposition processes has led to the desire to find other transparent conductive materials and other coating approaches. The use of dispersed silver nanowires in the form of a percolation network has emerged as a promising alternative to films containing ITO. The use of silver nanowires has the potential advantage that they can be implemented using roll-to-roll techniques. Thus, silver nanowires have the advantage of low cost manufacturing with the potential to provide higher transparency and conductivity than conventional ITO containing films. The "polyol process" has been disclosed for the manufacture of silver-based nanostructures. The polyol process utilizes ethylene glycol (or other glycol) both as a solvent and as a reducing agent in the production of silver nanowires. The use of glycols, however, has several inherent disadvantages. Specifically, the use of a glycol as both a reducing agent and a solvent leads to a decrease in the control of the reaction because the main species of reducing agent (glycolaldehyde) is produced in situ and its presence and concentration are dependent on the extent of exposure to oxygen. Also, the use of a glycol introduces the possibility of formation of combustible glycol / air mixtures in the free space of the reactor used to produce the silver nanowires. Finally, the use of large volumes of glycol creates waste problems, which increases the cost of marketing such operations. [0004] An approach constituting an alternative to the polyol process for making silver nanowires has been disclosed by Miyagishima, et al. in U.S. Patent Application Publication No. 20100078197. Miyagishima, et al. disclose a method for producing metal nanowires, comprising: adding a solution of a metal complex to an aqueous solvent containing at least one halide as a reducing agent, and heating the resulting mixture to 150 ° C or less, wherein the metal nanowires comprise metal nanowires having a diameter of 50 nm or less and a major axis length of 5 μm or more in an amount of 50% by mass or more in terms of the amount of metal relative to the total metal particles. [0005] Another approach constituting an alternative to the polyol process for making silver nanowires has been disclosed by Lunn, et al. in U.S. Patent Application Publication No. 20130283974. Lunn, et al. disclose a method for making silver nanowires having a high aspect ratio, wherein the recovered silver nanowires have an average diameter of 25 to 80 nm and an average length of 10 to 100 μm; and where the total glycol concentration is <0.001 wt% at any time during the process. However, there remains a need for other silver nanowires manufacturing processes. In particular, processes for manufacturing silver nanowires without the use of a glycol, wherein the silver nanowires produced have a high aspect ratio (preferably> 500) and where the production of silver nanoparticles undesirable ones having an aspect ratio <3 is minimized. The present invention provides a method for manufacturing silver nanowires having a high aspect ratio, comprising: providing a container; the supply of water; the supply of a reducing sugar; provision of polyvinylpyrrolidone (PVP); providing a source of copper (II) ions; providing a source of halide ions; providing a source of silver ions; providing a pH adjusting agent; addition of water, reducing sugar, polyvinylpyrrolidone (PVP), copper (II) ion source, halide ion source, and pH adjusting agent to the container to form a combination, wherein the combination has a pH of 2.0 to 4.0; heating the combination at 110 to 160 ° C; then adding the silver ion source to the vessel to form a growth mixture; then maintaining the growth mixture at 110 to 160 ° C for a holding period of 2 to 30 hours to give a product mixture; and recovering a plurality of silver nanowires having a high aspect ratio from the product mixture; and where the total glycol concentration in the vessel is <0.001% by weight at any time during the process. In a particular embodiment, the method of the present invention further comprises: dividing the silver ion source into a first portion and a second portion; heating the combination to 140 to 160 ° C; then adding the first part to the container to form a creation mixture; then cooling the creation mixture to 110 to 135 ° C for a delay period; after the delay period, adding the second portion to the vessel to form the growth mixture. According to a particular characteristic, the growth mixture is maintained at 110 to 135 ° C. during the holding period.
    [0002] According to another particular characteristic, the reducing sugar provided is glucose. According to another particular characteristic, the polyvinylpyrrolidone (PVP) supplied has a weight average molecular weight, Mw, of 40,000 to 150,000 Daltons.
    [0003] According to another particular characteristic, the copper (II) ion source supplied is copper (II) chloride. According to another particular characteristic, the source of halide ions provided is sodium chloride. According to another particular characteristic, the source of silver ions supplied is silver nitrate. In another particular embodiment, the method of the present invention further comprises: dividing the silver ion source into a first portion and a second portion; heating the combination to 140 to 160 ° C; then adding the first part to the container to form a creation mixture; then cooling the creation mixture to 110 to 135 ° C for a delay period; after the delay period, adding the second portion to the vessel to form the growth mixture; and maintaining the growth mixture at 110 to 135 ° C during the hold period; where the reducing sugar provided is glucose; wherein the polyvinylpyrrolidone (PVP) provided has a weight average molecular weight, Mw, of 40,000 to 60,000 Daltons; where the copper (II) ion source supplied is copper (II) chloride; where the halide ion source provided is sodium chloride; and where the silver ion source supplied is silver nitrate. In yet another particular embodiment, the method of the present invention further comprises: dividing the silver ion source into a first portion and a second portion, wherein the first portion comprises 10 to 30% by weight of the silver ion source provided; heating the combination to 145 to 155 ° C; then adding the first part to the container to form a creation mixture; then cooling the creation mixture at 125 to 135 ° C for a delay period of 5 to 15 minutes; after the delay period, adding the second portion to the vessel to form the growth mixture; and maintaining the growth mixture at 125 to 135 ° C during the hold period, where the hold period is 16 to 20 hours; where the reducing sugar provided is D-glucose; wherein the polyvinylpyrrolidone (PVP) provided has a weight average molecular weight, Mw, of 40,000 to 60,000 Daltons; where the copper (II) ion source supplied is copper (II) chloride; where the halide ion source provided is sodium chloride; where the silver ion source supplied is silver nitrate; and wherein the weight ratio of polyvinylpyrrolidone (PVP) to silver ions added to the container is 6: 1 to 7: 1; wherein the weight ratio of halide ions to copper (II) ions added to the container is 2.5: 1 to 3.5: 1; wherein the plurality of silver nanowires having a high aspect ratio recovered have an average diameter of 35 to 50 nm and an average length of 20 to 100 μm; and wherein the plurality of recovered high aspect ratio silver nanowires have an average aspect ratio of> 500. [0008] The present invention provides a method for making high aspect ratio silver nanowires. , comprising: providing a container; the supply of water; the supply of a reducing sugar; provision of polyvinylpyrrolidone (PVP); providing a source of copper (II) ions; providing a source of halide ions; providing a source of silver ions; providing a pH adjusting agent; addition of water, reducing sugar, polyvinylpyrrolidone (PVP), copper (II) ion source, halide ion source, and pH adjusting agent to the container to form a combination, wherein the combination has a pH of 2.0 to 4.0; heating the combination at 110 to 160 ° C; then adding the silver ion source to the vessel to form a growth mixture; maintaining the growth mixture at 110 to 160 ° C for a holding period of 2 to 30 hours to provide a product mixture; and recovering a plurality of silver nanowires having a high aspect ratio from the product mixture; wherein the total glycol concentration in the container is <0.001% by weight at any time during the process; and wherein the plurality of silver nanowires having a high aspect ratio recovered have an average diameter of 25 to 80 nm and an average length of 10 to 100 μm. The present invention provides a method for producing silver nanowires having a high aspect ratio, comprising: providing a container; the supply of water; the supply of a reducing sugar; provision of polyvinylpyrrolidone (PVP); providing a source of copper (II) ions; providing a source of halide ions; providing a source of silver ions; providing a pH adjusting agent; addition of water, reducing sugar, polyvinylpyrrolidone (PVP), copper (II) ion source, halide ion source, and pH adjusting agent to the container to form a combination, wherein the combination has a pH of 2.0 to 4.0; dividing the silver ion source into a first portion and a second portion; heating the combination to 140 to 160 ° C; then adding the first part to the container to form a creation mixture; then cooling the creation mixture to 110 to 135 ° C for a delay period; after the delay period, adding the second portion to the vessel to form a growth mixture; maintaining the growth mixture at 110 to 160 ° C for a holding period of 2 to 30 hours to provide a product mixture; and recovering a plurality of silver nanowires having a high aspect ratio from the product mixture; and where the total glycol concentration in the vessel is <0.001% by weight at any time during the process. The present invention provides a method for making silver nanowires having a high aspect ratio, comprising: providing a container; the supply of water; the supply of a reducing sugar; provision of polyvinylpyrrolidone (PVP); providing a source of copper (II) ions; providing a source of halide ions; providing a source of silver ions; providing a pH adjusting agent; addition of water, reducing sugar, polyvinylpyrrolidone (PVP), copper (II) ion source, halide ion source, and pH adjusting agent to the container to form a combination, wherein the combination has a pH of 2.0 to 4.0; dividing the silver ion source into a first portion and a second portion; heating the combination to 140 to 160 ° C and then adding the first portion to the container to form a creation mixture; then cooling the creation mixture to 110 to 135 ° C for a delay period; after the delay period, adding the second portion to the vessel to form a growth mixture; maintaining the growth mixture at 110 to 135 ° C for a hold period of 2 to 30 hours; and recovering a plurality of silver nanowires having a high aspect ratio from the product mixture; wherein the total glycol concentration in the container is <0.001% by weight at any time during the process. The present invention provides a method for manufacturing silver nanowires having a high aspect ratio, comprising: providing a container; the supply of water; supplying a reducing sugar, where the reducing sugar provided is glucose; providing polyvinylpyrrolidone (PVP), wherein the polyvinylpyrrolidone (PVP) provided has a weight average molecular weight, Mw, of from 40000 to 60000 Daltons; providing a source of copper (II) ions, wherein the source of copper (II) ions provided is copper (II) chloride; providing a source of halide ions, wherein the source of halide ions provided is sodium chloride; providing a source of silver ions, where the silver ion source supplied is silver nitrate; providing a pH adjusting agent; addition of water, reducing sugar, polyvinylpyrrolidone (PVP), copper (II) ion source, halide ion source, and pH adjusting agent to the container to form a combination, wherein the combination has a pH of 2.0 to 4.0; dividing the silver ion source into a first portion and a second portion; heating the combination to 140 to 160 ° C and then adding the first portion to the container to form a creation mixture; then cooling the creation mixture to 110 to 135 ° C for a delay period; after the delay period, adding the second portion to the vessel to form a growth mixture; maintaining the growth mixture at 110 to 135 ° C for a hold period of 2 to 30 hours; and recovering a plurality of silver nanowires having a high aspect ratio from the product mixture; wherein the total glycol concentration in the container is <0.001% by weight at any time during the process. The present invention provides a method for making silver nanowires having a high aspect ratio, comprising: providing a container; the supply of water; supplying a reducing sugar, where the reducing sugar provided is D-glucose; providing polyvinylpyrrolidone (PVP), wherein the polyvinylpyrrolidone (PVP) provided has a weight average molecular weight, Mw, of from 40000 to 60000 Daltons; providing a source of copper (II) ions, wherein the source of copper (II) ions provided is copper (II) chloride; providing a source of halide ions, wherein the source of halide ions provided is sodium chloride; providing a source of silver ions, where the silver ion source supplied is silver nitrate; providing a pH adjusting agent; addition of water, reducing sugar, polyvinylpyrrolidone (PVP), copper (II) ion source, halide ion source, and pH adjusting agent to the container to form a combination, wherein the combination has a pH of 2.0 to 4.0; dividing the silver ion source into a first portion and a second portion, wherein the first portion represents 10 to 30% by weight of the silver ion source provided; heating the combination to 145 to 155 ° C and then adding the first portion to the vessel to form a creation mixture; then cooling the creation mixture at 125 to 135 ° C for a delay period of 5 to 15 minutes; after the delay period, adding the second portion to the vessel to form a growth mixture; maintaining the growth mixture at 125 to 135 ° C for a holding period of 16 to 20 hours; and recovering a plurality of silver nanowires having a high aspect ratio from the product mixture; wherein the total glycol concentration in the container is <0.001% by weight at any time during the process; wherein the weight ratio of polyvinylpyrrolidone (PVP) to silver ions added to the container is 6: 1 to 7: 1; wherein the weight ratio of halide ions to copper (II) ions added to the container is 2.5: 1 to 3.5: 1; wherein the plurality of silver nanowires having a high aspect ratio recovered have an average diameter of 35 to 50 nm and an average length of 40 to 100 μm; and wherein the plurality of silver nanowires having a high aspect ratio recovered have an average aspect ratio of> 500.
    [0004] DETAILED DESCRIPTION [0012] A method for making silver nanowires having a high aspect ratio has been found that provides silver nanowires having an average diameter of 25 to 60 nm and an average length of 35 to 100 μm. while avoiding the inherent disadvantages that are associated with the use of glycols and while also reducing the fraction of silver nanoparticles produced having an aspect ratio <3. It is difficult to separate silver nanowires having a ratio high aspect ratio with silver nanoparticles having an aspect ratio of <3. Thus, it is considered that it is significantly advantageous to have a process where the formation of silver nanoparticles produced having a ratio of aspect <3 is minimized so that the fraction of silver nanoparticles, NPF, for silver nanowires produced is <0.2 (as determined by the method described here in the examples). The term "total glycol concentration" as used herein with respect to the contents of the container means the combined total of the concentration of all glycols (eg, ethylene glycol, propylene glycol, butylene glycol, poly (ethylene glycol), poly (propylene glycol)) present in the container. The term "high aspect ratio" as used herein with respect to recovered silver nanowires means that the average aspect ratio of recovered silver nanowires is> 500. [0015] The term "fraction of silver nanoparticles" or "NPF" used herein is the fraction of silver nanoparticles of a sample of silver nanowires determined according to the following equation: NPF = NPA / TA where TA is the area of total surface of a substrate that is occluded by a given deposited sample of silver nanowires; and, NPA is the portion of the total occluded surface area attributable to silver nanoparticles having an aspect ratio <3 included in the deposited sample of silver nanowires. [0016] Preferably, the method for manufacturing silver nanowires having a high aspect ratio of the present invention comprises: providing a container; the supply of water; the supply of a reducing sugar; provision of polyvinylpyrrolidone (PVP); providing a source of copper (II) ions; providing a source of halide ions; providing a source of silver ions; providing a pH adjusting agent; addition of water, reducing sugar, polyvinylpyrrolidone (PVP), copper (II) ion source, halide ion source, and pH adjusting agent to the container to form a combination, wherein the combination has a pH of 2.0 to 4.0 (preferably, 2.2 to 3.3); heating the combination at 110 to 160 ° C; then adding the silver ion source to the vessel (preferably with stirring) to form a growth mixture; maintaining the growth mixture at 110 to 160 ° C for a holding period of 2 to 30 hours to provide a product mixture; and recovering a plurality of silver nanowires having a high aspect ratio from the product mixture; wherein the total glycol concentration in the container is <0.001% by weight at any time during the process. Preferably, wherein the weight ratio of polyvinylpyrrolidone (PVP) to silver ions added to the container is 4: 1 to 10: 1; and wherein the weight ratio of halide ions to copper (II) ions added to the container is 1: 1 to 5: 1. Preferably, wherein the plurality of silver nanowires having a high aspect ratio recovered have an average diameter of 25 to 80 nm and an average length of 10 to 100 μm. Preferably, wherein the plurality of silver nanowires having a high aspect ratio recovered have an average aspect ratio of> 500 (more preferably, 800, particularly preferably 1000). Preferably, the water supplied in the process for producing silver nanowires having a high aspect ratio of the present invention is at least one of deionized water and distilled water to limit impurities. accidental. More preferably, the water provided in the process for making silver nanowires having a high aspect ratio of the present invention is deionized and distilled. Most preferably, the water provided in the process for making silver nanowires having a high aspect ratio of the present invention is ultrapure water which meets or exceeds the requirements for Type 1 water according to ASTM D1193-99e1 (Standard Specification for "Standard Specification for Reagent Water"). Preferably, the reducing sugar provided in the process for making silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of at least one of the aldoses (e.g., glucose). glyceraldehyde, galactose, mannose); disaccharides with a free hemiacetal unit (eg, lactose and maltose); and sugars carrying a ketone (eg, fructose). More preferably, the reducing sugar provided in the process for making silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of at least one of an aldose, lactose, maltose and fructose. More preferably, the reducing sugar provided in the process for making silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of at least one of glucose, glyceraldehyde, galactose , mannose, lactose, fructose and maltose. Most preferably, the reducing sugar provided in the process for making silver nanowires having a high aspect ratio of the present invention is D-glucose. [0019] Preferably, the polyvinylpyrrolidone (PVP) provided in the process for making silver nanowires having a high aspect ratio of the present invention has a weight average molecular weight, Mw, of 20000 to 300000 Daltons. More preferably, the polyvinylpyrrolidone (PVP) provided in the process for making silver nanowires having a high aspect ratio of the present invention has a weight average molecular weight, Mw, of 30,000 to 200,000 Daltons. Particularly preferably, the polyvinylpyrrolidone (PVP) provided in the process for producing silver nanowires having a high aspect ratio of the present invention has a weight average molecular weight, Mw, of from 40000 to 150,000 Daltons, preferably still from 40000 to 60000 Daltons. Preferably, the copper (II) ion source provided in the process for producing silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of at least one of CuCl2 and Cu (NO3) 2. More preferably, the copper (II) ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of CuCl 2 and Cu (NO 3) 2. Particularly preferably, the copper (II) ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is CuCl 2, where CuCl 2 is a copper (II) chloride dihydrate. [0021] Preferably, the halide ion source provided in the process for producing silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of at least one of a source of chloride ions, a source of fluoride ions, a source of bromide ions and a source of iodide ions. More preferably, the halide ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is selected from the group consisting of at least one of an ion source chloride and a source of fluoride ions. More preferably, the halide ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is a source of chloride ions. Particularly preferably, the halide ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is a source of chloride ions, where the source of chloride ions is a alkali metal chloride. Preferably, the alkali metal chloride is selected from the group consisting of at least one of sodium chloride, potassium chloride and lithium chloride. More preferably, the alkali metal chloride is selected from the group consisting of at least one of sodium chloride and potassium chloride. Particularly preferably, the alkali metal chloride is sodium chloride. [0022] Preferably, the silver ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is a silver complex. More preferably, the silver ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is a silver complex, wherein the silver complex is selected from the group consisting of at least one of silver nitrate (AgNO3) and silver acetate (AgC2H302). Most preferably, the silver ion source provided in the process for making silver nanowires having a high aspect ratio of the present invention is silver nitrate (AgNO 3). Preferably, the silver ion source provided in the process for producing silver nanowires having a high aspect ratio of the present invention has a silver concentration of 0.005 to 1 molar (M) (more preferably from 0.01 to 1 M, particularly preferably from 0.4 to 1 M). [0023] Preferably, the pH adjusting agent provided in the process for making silver nanowires having a high aspect ratio of the present invention is an acid. More preferably, the pH adjusting agent provided in the process for making silver nanowires having a high aspect ratio of the present invention is an acid, wherein the acid is selected from the group consisting of least one of the inorganic acids (eg, nitric acid, sulfuric acid, hydrochloric acid, fluorosulfuric acid, phosphoric acid, fluoroantimonic acid) and organic acids (e.g. methanesulfonic acid, ethanesulphonic acid, benzenesulphonic acid, acetic acid, fluoroacetic acid, chloroacetic acid, citric acid, gluconic acid, lactic acid). Preferably, the pH adjusting agent provided in the process for making silver nanowires having a high aspect ratio of the present invention has a pH <2.0. More preferably, the pH adjusting agent provided in the process for making silver nanowires having a high aspect ratio of the present invention includes nitric acid. Most preferably, the pH adjusting agent provided in the process for making silver nanowires having a high aspect ratio of the present invention is aqueous nitric acid. [0024] Preferably, in the process for producing high aspect ratio silver nanowires of the present invention, water, reducing sugar, polyvinylpyrrolidone (PVP), copper ion source (II ), the halide ion source and the pH adjusting agent are added to a container (preferably, where the container is a reactor, more preferably, where the container is a reactor equipped with a stirrer) for form a combination; then, the silver ion source is added to the combination in the container (preferably with stirring) to form a growth mixture while maintaining the combination at 110 to 160 ° C (preferably 125 to 155 ° C). more preferably at 130 to 150 ° C) during the addition of the silver ion source and after the addition of the silver ion source for a hold period of 2 to 30 hours (preferably 4 to 30 hours, more preferably 10 to 25 hours, particularly preferably 16 to 20 hours) to give the product mixture. Preferably, the water, the reducing sugar, the polyvinylpyrrolidone (PVP), the source of copper (II) ions, the source of halide ions and the pH adjusting agent are added to the container in any order in an individual succession (ie, one at a time), simultaneously (ie, all at the same time), or semisimultaneously (that is, some individually one at a time, some simultaneously at the same time or in the form of sub-combinations). More preferably, at least two of water, reducing sugar, polyvinylpyrrolidone (PVP), copper (II) ion source, halide ion source and pH adjusting agent are mixed together. to form a sub-combination prior to addition to the container. [0026] Preferably, the water is divided into at least two volumes of water (more preferably at least three volumes of water, particularly preferably at least four volumes of water) to facilitate the formation of water. at least two sub-combinations which include water prior to addition to the container. More preferably, the water is divided into at least four volumes of water, wherein a first volume of water is combined with reducing sugar and polyvinylpyrrolidone (PVP) to form a reducing sugar / PVP sub-combination, where a second volume of water is combined with the copper (II) ion source to form a sub-combination of copper (II) ions, where a third volume of water is combined with the halide ion source to form a sub-combination of halide ions and where a fourth volume of water is combined with the silver ion source to form a sub-combination of silver ions. Preferably, the reducing sugar / PVP sub-combination, the copper (II) ion sub-combination, the halide ion sub-combination and the pH adjusting agent are added to the container in any order within an individual succession (ie, one at a time), simultaneously (ie, all at the same time), or semi-simultaneously (ie, some individually one at a time, some simultaneously at the same time or in the form of additional sub-combinations) to form the combination. More preferably, the reducing sugar / polyvinylpyrrolidone (PVP) sub-combination is added to the vessel, followed by the addition to the vessel of the sub-combination of copper (II) ions, the sub-combination of halide ions and pH adjusting agent in any order in an individual succession (i.e., one at a time), simultaneously (i.e., all at the same time), or simultaneously (c) that is, some individually one at a time, some simultaneously at the same time or in the form of additional sub-combinations) to form the combination. Particularly preferably, the reducing sugar / polyvinylpyrrolidone (PVP) sub-combination is added to the vessel, followed by the addition of the copper (II) ion sub-combination to the vessel, followed by the addition of the sub-combination of combination of halide ions to the vessel, followed by addition of the pH adjusting agent to the vessel to form the combination. The silver ion sub-combination is then added to the combination in the container. Preferably, in the process for making silver nanowires having a high aspect ratio of the present invention, the total glycol concentration in the container is <0.001 wt% at any time during the process. Preferably, in the process for producing silver nanowires having a high aspect ratio of the present invention, the weight ratio of the polyvinylpyrrolidone (PVP) to the silver ions added to the container is 4: 1 to 10 : 1 (more preferably, 5: 1 to 8: 1, particularly preferably 6: 1 to 7: 1). Preferably, in the process for producing silver nanowires having a high aspect ratio of the present invention, the weight ratio of halide ions to copper (II) ions added to the container is 1: 1 to 5 : 1 (more preferably, 2: 1 to 4: 1, particularly preferably 2.5: 1 to 3.5: 1). Preferably, in the method for producing silver nanowires having a high aspect ratio of the present invention, the plurality of silver nanowires having a high aspect ratio recovered from the product mixture have an average diameter of 25 to 80 nm (more preferably 25 to 60 nm, particularly preferably 35 to 50 nm) and an average length of 10 to 100 μm (preferably 20 to 100 μm); more preferably,> 20 to 100 μm). Preferably, the plurality of silver nanowires having a high aspect ratio recovered from the product mixture have an average aspect ratio of> 500. Preferably, in the process for making silver nanowires having a high aspect ratio of the present invention, the plurality of silver nanowires having a high aspect ratio recovered from the product mixture have a fraction of silver nanoparticles, NPF, <0.2 ( preferably <0.17, more preferably <0.15, most preferably <0.13) (as determined by the method described herein in the examples). Preferably, the method for producing silver nanowires having a high aspect ratio of the present invention further comprises: dividing the silver ion source supplied into at least two individual parts, where the Individual portions are added to the container with a delay period (preferably 1 to 60 minutes, more preferably 1 to 20 minutes, particularly preferably 5 to 15 minutes) between additions of individual portions.
    [0005] More preferably, the method of the present invention further comprises: dividing the source of silver ions supplied into a first portion and a second portion (preferably, wherein the first portion represents 10 to 30% by weight of the source of silver ions provided, more preferably, wherein the first portion is 15 to 25% by weight of the silver ion source provided, particularly preferably, wherein the first portion is 20% by weight of the ion source money provided); heating the combination at 140 to 160 ° C (preferably at 145 to 155 ° C) and prior to adding the first portion to the vessel to form a creation mixture; and then cooling the creation mixture to 110 to 150 ° C (preferably 110 to 135 ° C, more preferably 125 to 135 ° C) for a delay period (preferably 1 to 60 minutes; more preferably, from 1 to 20 minutes, particularly preferably from 5 to 15 minutes); after the delay period, adding the second portion to the vessel to form a growth mixture. [0033] Preferably, the method for producing silver nanowires having a high aspect ratio of the present invention further comprises: dividing the silver ion source provided into a first portion and a second portion (of Preferably, wherein the first portion is 10 to 30% by weight of the silver ion source provided, more preferably, wherein the first portion is 15 to 25% by weight of the silver ion source provided, particularly preferably where the first part represents 20% by weight of the silver ion source supplied); heating the combination at 140 to 160 ° C (preferably at 145 to 155 ° C) prior to adding the first portion to the vessel to form a creation mixture; and then cooling the creation mixture to 110 to 150 ° C (preferably 110 to 135 ° C, more preferably 125 to 135 ° C) for a delay period (preferably 1 to 60 minutes; more preferably, from 1 to 20 minutes, particularly preferably from 5 to 15 minutes); after the delay period, adding the second portion to the vessel to form a growth mixture; and maintaining the growth mixture at 110 to 150 ° C (preferably at 110 to 135 ° C, more preferably at 125 to 135 ° C) for a holding period of 2 to 30 hours (preferably 4 to 30 hours, more preferably 10 to 25 hours, particularly preferably 16 to 20 hours) to give a product mixture. Some embodiments of the present invention will now be described in detail in the following examples. The water used in the following examples was obtained by means of a Barnstead NANOPure ThermoScientific purification system with a 0.2 μm pore size hollow fiber filter positioned downstream of the purification unit. the water.
    [0006] Example 1: Preparation of a reducing sugar / PVP-containing sub-combination Polyvinylpyrrolidone (PVP) having a weight average molecular weight, Mw, of 55,000 Daltons (52.2 g,> 98% from Sigma -Aldrich) was dissolved in 1958 mL of deionized water in a flask. Then D-glucose (13.5 g,> 99% from Sigma-Aldrich) was added to the contents of the stirred flask until dissolved to form a reducing sugar / PVP sub-combination. Example 2: Preparation of a sub-combination containing copper (II) ions [0038] Copper (II) chloride (0.6137 g,> 99% from Mallinckrodt Chemicals) was dissolved in 900 mL of water deionized to form a sub-combination of copper (II) ions in a beaker.
    [0007] Example 3: Preparation of a sub-combination containing halide ions [0039] Sodium chloride (0.2104 g) was dissolved in 900 mL of deionized water to form a sub-combination of halide ions in a beaker .
    [0008] Example 4: Preparation of a silver ion-containing sub-combination [0040] Silver nitrate (12.70 g,> 99% from Sigma-Aldrich) was dissolved in 612 mL of deionized water to form a sub-combination of silver ions in a balloon. Comparative Example C1: Preparation of Silver Nanowires [0041] An 8 L stainless steel pressure reactor equipped with a suspended mixer and a temperature control device was used. A portion (21.3 mL) of a halide ion sub-combination prepared according to Example 3 was added to a reducing sugar / PVP sub-combination prepared according to Example 1 in a flask. A portion (21.3 mL) of a copper (II) ion sub-combination prepared according to Example 2 was then added to the flask. The glassware used in the measurement of the halide ion sub-combination and the copper (II) ion sub-combination was then rinsed with deionized water (407 mL) into the flask. The contents of the flask were then transferred to the reactor. The flask was then rinsed with deionized water (191 mL) into the reactor. The pH of the reactor contents was observed to be 3.86. The mixer was started at a stirring speed of 200 rpm. The reactor was then closed and purged with nitrogen four times to a pressure of> 414 x 103 Pa (60 psig) with holding under pressure for three minutes for each purge. The reactor was left with a nitrogen blanket at 116 x 103 Pa (16.8 psig) after the final purge. The temperature control device was then set at 150 ° C. After the reactor contents reached 150 ° C, 20% by weight of the silver ion sub-combination prepared according to Example 4 was added to the reactor in 1 minute. The reactor contents were then stirred for ten minutes while the set point of the temperature control device was maintained at 150 ° C. For the next ten minutes, the temperature of the reactor contents was lowered to 130 ° C. The remaining 80% by weight of the silver ion sub-combination prepared according to Example 4 was then added to the reactor contents for the next ten minutes as well as an additional 102 mL of deionized water. The reactor contents were then stirred for eighteen hours while the setting point of the temperature control device was maintained at 130 ° C. The reactor contents were then cooled to room temperature for the next thirty minutes. The reactor was then vented to relieve the accumulated pressure in the vessel. The mixer was stopped. The contents of the reactor were then collected. Example 5: Prenaration of silver nanowires [0042] An 8 liter stainless steel pressure reactor equipped with a three-blade propeller-type stirrer, a temperature control unit with an external resistive heating jacket, and an internal cooling tube to facilitate temperature control was used. A portion (21.3 mL) of a halide ion sub-combination prepared according to Example 3 was added to a reducing sugar / PVP sub-combination prepared according to Example 1 in a flask. A portion (21.3 mL) of a copper (II) ion sub-combination prepared according to Example 2 was then added to the flask. The glassware used in the measurement of the halide ion sub-combination and the copper (II) ion sub-combination was then rinsed with deionized water (407 mL) into the flask. The pH of the flask contents was then adjusted from an initial pH of 3.86 to a pH of 2.29 with nitric acid (reagent grade ACS, 70%). The contents of the flask were then transferred to the reactor. The flask was then rinsed with deionized water (191 mL) into the reactor. The mixer was started at a stirring speed of 200 rpm. The reactor was then closed and purged with nitrogen four times to a pressure of> 414 x 103 Pa (60 psig) with holding under pressure for three minutes for each purge. The reactor was left with a nitrogen blanket at 116 x 103 Pa (16.8 psig) after the final purge. The temperature control device was then set at 150 ° C. After the reactor contents reached 150 ° C, 20% by weight of the silver ion sub-combination prepared according to Example 4 was added to the reactor in 1 minute to form a creation mixture. The creation mixture was then stirred for ten minutes while the set point of the temperature control device was maintained at 150 ° C. During the next ten minutes, the set point of the temperature control device was decreased linearly to 130 ° C. The remaining 80% by weight of the silver ion sub-combination prepared according to Example 4 was then added to the reactor for the next ten minutes as well as an additional 102 mL of deionized water to form a growth mixture. The growth mixture was then stirred for eighteen hours while the setting point of the temperature control device was maintained at 130 ° C to form a product mixture. The product mixture was then cooled to room temperature for the next thirty minutes. The reactor was then vented to release any accumulated pressure in the vessel. The mixer was stopped. The product mixture was then collected.
    [0009] Analysis of the silver nanowires collected The silver nanowires produced in the comparative example C1 and in Example 5 were then analyzed with a FEI Nova Nano field emitting gun (SEM) scanning electron microscope (SEM). SEM using FEI's Automated Image Acquisition (AIA) program. A drop of purified dispersion was taken from the UV / Vis cuvette and applied to a sample holder of SEM coated with a silica wafer before being dried under vacuum. The backscattering electronic images were collected with a FEI Nova Nano SEM Field Emission Scanning Electron Microscope. FEI's Automated Image Acquisition (AIA) program was used to move the deck, focus and collect the images. Eighteen images of each sample were acquired at a horizontal field width of 6 μm.
    [0010] Semi-automatic image analysis using the Image] software classified the objects as threads or particles based on an aspect ratio of 3. The yarn widths were measured automatically as well as the total area of wires in the pictures. Particles were classified with respect to the individual size and the total area of particles in the images. The Image] software was also used to determine the diameter of the silver nanowires in Table 1. It was observed that the average silver nanowire length exceeded 20 μm, based on the SEM images obtained for the analysis. diameters. The Image software was used to analyze the SEM images of the silver nanowires produced in Comparative Example C1 and Example 5 to give a relative measure of the silver nanoparticles having an aspect ratio. 3 in the product samples. The metric used for this measurement is the nanoparticle fraction, MFN, determined according to the following expression: NPF = N PA / TA; Where TA is the total surface area of the substrate that is occluded by a given deposited sample of silver nanowires; and NPA is the portion of the total occluded surface area attributable to silver nanoparticles having an aspect ratio <3. UV / Vis spectral analysis of silver nanowires produced in the example Comparative Cl and Example 5 was carried out using a Shimadzu UV 2401 spectrophotometer. The raw UV / Vis absorption spectra were normalized so that the local minimum near 320 nm and the local maximum near 375 nm cover the range from 0 to 1. The maximum absorption wavelength, λmax, and the normalized absorption at 500 nm, Abs500, are shown in Table 1. TABLE 1 Analysis Width (nm) spectral λmax Deviation (nm Abs50 Exem Median Mean type MFN 1 0 Cl 44.6 53.7 33.4 0.23 380 0.39 5 38.2 47.8 35.2 0.12 378 0.2720
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. A process for producing silver nanowires having a high aspect ratio, characterized by comprising: providing a container; the supply of water; the supply of a reducing sugar; provision of polyvinylpyrrolidone (PVP); providing a source of copper (II) ions; providing a source of halide ions; providing a source of silver ions; providing a pH adjusting agent; addition of water, reducing sugar, polyvinylpyrrolidone (PVP), copper (II) ion source, halide ion source, and pH adjusting agent to the container to form a combination, wherein the combination has a pH of 2.0 to 4.0; heating the combination at 110 to 160 ° C; then adding the silver ion source to the vessel to form a growth mixture; then maintaining the growth mixture at 110 to 160 ° C for a holding period of 2 to 30 hours to give a product mixture; and recovering a plurality of silver nanowires having a high aspect ratio from the product mixture; and where the total glycol concentration in the vessel is <0.001% wt at any time during the process.
    [0002]
    The method of claim 1, further comprising: dividing the silver ion source into a first portion and a second portion, heating the combination to 140 to 160 ° C; then adding the first part to the container to form a creation mixture; then cooling the creation mixture to 110 to 135 ° C for a delay period; after the delay period, adding the second portion to the vessel to form the growth mixture.
    [0003]
    3. Process according to claim 2, characterized in that the growth mixture is maintained at 110 to 135 ° C during the holding period.
    [0004]
    4. Method according to any one of the preceding claims, characterized in that the reducing sugar provided is glucose.
    [0005]
    5. A process according to any one of the preceding claims, characterized in that the polyvinylpyrrolidone (PVP) supplied has a weight average molecular weight, Mw, of 40,000 to 150,000 Daltons.
    [0006]
    6. Process according to any one of the preceding claims, characterized in that the copper (II) ion source supplied is copper (II) chloride.
    [0007]
    7. Method according to any one of the preceding claims, characterized in that the source of halide ions supplied is sodium chloride.
    [0008]
    8. Process according to any of the preceding claims, characterized in that the silver ion source supplied is silver nitrate.
    [0009]
    9. A method according to any one of claims 2 to 8, characterized in that it further comprises: dividing the silver ion source into a first portion and a second portion; heating the combination to 140 at 160 ° C; then adding the first part to the container to form a creation mixture; then cooling the creation mixture to 110 to 135 ° C for a delay period; after the delay period, adding the second portion to the vessel to form the growth mixture; and maintaining the growth mixture at 110 to 135 ° C during the hold period; where the reducing sugar provided is glucose; wherein the polyvinylpyrrolidone (PVP) provided has a weight average molecular weight, Mw, of 40,000 to 60,000 Daltons; where the copper (II) ion source supplied is copper (II) chloride; where the halide ion source provided is sodium chloride; and where the silver ion source supplied is silver nitrate.
    [0010]
    10. Process according to any one of claims 2 to 8, characterized in that it further comprises: the division of the source of silver ions into a first part and a second part, where the first part represents 10 to 30 ° h by weight of the silver ion source supplied; heating the combination to 145 to 155 ° C; then adding the first part to the container to form a creation mixture; then cooling the creation mixture at 125 to 135 ° C for a delay period of 5 to 15 minutes; after the delay period, adding the second portion to the vessel to form the growth mixture; and maintaining the growth mixture at 125 to 135 ° C during the hold period, where the hold period is 16 to 20 hours; Wherein the reducing sugar provided is D-glucose, wherein the polyvinylpyrrolidone (PVP) supplied has a weight average molecular weight, Mw, of from 40000 to 60000 Daltons; where the copper (II) ion source supplied is copper (II) chloride; where the halide ion source provided is sodium chloride; where the silver ion source supplied is silver nitrate; and wherein the weight ratio of polyvinylpyrrolidone (PVP) to silver ions added to the container is 6: 1 to 7: 1; wherein the weight ratio of halide ions to copper (II) ions added to the container is 2.5: 1 to 3.5: 1; wherein the plurality of recovered high aspect ratio silver nanowires have an average diameter of 35 to 50 nm and an average length of 20 to 100 μm; and wherein the plurality of silver nanowires having a high aspect ratio recovered have an average aspect ratio of> 500.
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    同族专利:
    公开号 | 公开日
    CN105537607A|2016-05-04|
    KR20160049981A|2016-05-10|
    JP2016166402A|2016-09-15|
    TW201615850A|2016-05-01|
    DE102015013219A1|2016-04-28|
    US20160114396A1|2016-04-28|
    US9776249B2|2017-10-03|
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    优先权:
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    US201462069430P| true| 2014-10-28|2014-10-28|
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