• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    A method for making silver nanowires having a high aspect ratio is provided wherein the total glycol concentration is <0.001 wt.% At any time during the process.
    公开号:FR3027540A1
    申请号:FR1560276
    申请日:2015-10-28
    公开日:2016-04-29
    发明作者:Patrick T Mcgough；George L Athens
    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. [0002] 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, touch screen display devices 10 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 by 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 25 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 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, while producing silver nanowires having a desirable high aspect ratio, the manufacturing method described by Lunn, et al. Also leads to the formation of silver nanowire populations having an extended diameter distribution which can lead to a lack of uniformity in the electrical properties of the films produced therewith. [0007] Thus, there remains a need for other methods for manufacturing silver nanowires. In particular, processes for manufacturing silver nanowires which do not involve the use of a glycol, wherein the produced silver nanowires have a high aspect ratio (preferably> 500) in combination with a narrow distribution of diameters of silver nanowires. 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; bubbling into the silver ion source of an inert gas to extract entrained oxygen gas from the silver ion source and to give a low concentration of oxygen gas in a silver ion gas space in contact with the source silver ions; adding water, reducing sugar, polyvinylpyrrolidone (PVP), copper ion source (II) and the halide ion source to the container to form a combination; venting a gas space from the container in contact with the combination into the container to provide a reduced oxygen gas concentration in the gas space of the container; then heating the combination to 110 to 160 ° C; then adding the silver ion source to the vessel to form a growth mixture, while maintaining the reduced oxygen gas concentration in the container gas space and the low oxygen gas concentration in the gas space silver ions; maintaining the growth mixture at 100 to 150 ° C and the reduced oxygen gas concentration in the container gas space 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; where the total glycol concentration in the container is <0.001% by weight. 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, while maintaining the low oxygen gas concentration in the gas space silver ions; where the combination is heated to 140 to 155 ° C; then adding the first part to the container to form a creation mixture, while maintaining the reduced oxygen gas concentration in the container gas space and the low oxygen gas concentration in the ion gas space money; then cooling the creation mixture to 100 to 150 ° C for a period of time; then, after the delay period, adding the second portion to the vessel to form the growth mixture, while maintaining the reduced oxygen gas concentration in the vessel gas space and the low oxygen gas concentration in the vessel. silver ion gas space; where the reduced oxygen gas concentration in the container gas space is 2000 ppm. According to a particular characteristic, the growth mixture is maintained at 100 to 150 ° C. during the holding period. 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. According to another particular characteristic, the copper (II) ion source supplied is copper (II) chloride.
    [0002] 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.
    [0003] In another particular embodiment, the combination is heated to 140 to 155 ° C; the creation mixture is cooled to 110 to 140 ° C during the delay period; the growth mixture is maintained at 110 to 140 ° C during the holding period; the reducing sugar provided is glucose; the polyvinylpyrrolidone (PVP) provided has a weight average molecular weight, Mw, of 40,000 to 60,000 Daltons; the copper (II) ion source supplied is copper (II) chloride; the source of halide ions provided is sodium chloride; and the silver ion source provided is silver nitrate. In yet another particular embodiment, the first portion is 10 to 30% by weight of the silver ion source supplied; the combination is heated to 145 to 155 ° C prior to the addition of the silver ion source to the container; the creation mixture is cooled to 125 to 135 ° C during the delay period, where the delay period is 5 to 15 minutes; the growth mixture is maintained at 125 to 135 ° C during the hold period, where the hold period is 16 to 20 hours; the reduced oxygen gas concentration in the container gas space is 400 ppm; the low concentration of oxygen gas in the silver ion gas space is 5. 1000 ppm; and the plurality of silver nanowires having a high aspect ratio recovered have an average diameter of 40 nm with a standard deviation of diameters of 5.26 nm and an average aspect ratio of> 500. [0009] 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; bubbling into the silver ion source of an inert gas to extract entrained oxygen gas from the silver ion source and to give a low concentration of oxygen gas in a silver ion gas space in contact with the source silver ions; adding water, reducing sugar, polyvinylpyrrolidone (PVP), copper ion source (II) and the halide ion source to the container to form a combination; venting a gas space from the container in contact with the combination into the container to provide a reduced oxygen gas concentration in the gas space of the container; then heating the combination to 140 to 155 ° C; dividing the silver ion source into a first portion and a second portion, while maintaining the low oxygen gas concentration in the silver ion gas space; then adding the first part to the container to form a creation mixture, while maintaining the reduced oxygen gas concentration in the container gas space and the low oxygen gas concentration in the ion gas space money; then cooling the creation mixture to 100 to 150 ° C for a period of time; then, after the delay period, adding the second portion to the vessel to form a growth mixture, while maintaining the reduced oxygen gas concentration in the container gas space and the low oxygen gas concentration in the vessel. silver ion gas space; maintaining the growth mixture at 100 to 150 ° C and the reduced oxygen gas concentration in the container gas space 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 vessel is <0.001% by weight; and where the reduced oxygen gas concentration in the container gas space is 2000 ppm. 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; bubbling into the silver ion source of an inert gas to extract entrained oxygen gas from the silver ion source and to give a low concentration of oxygen gas in a silver ion gas space in contact with the source silver ions; adding water, reducing sugar, polyvinylpyrrolidone (PVP), copper ion source (II) and the halide ion source to the container to form a combination; venting a gas space from the container in contact with the combination into the container to provide a reduced oxygen gas concentration in the gas space of the container; then heating the combination to 140 to 155 ° C; dividing the silver ion source into a first portion and a second portion, while maintaining the low oxygen gas concentration in the silver ion gas space; then adding the first part to the container to form a creation mixture, while maintaining the reduced oxygen gas concentration in the container gas space and the low oxygen gas concentration in the ion gas space money; then cooling the creation mixture to 110 to 140 ° C for a period of time; then, after the delay period, adding the second portion to the vessel to form a growth mixture, while maintaining the reduced oxygen gas concentration in the container gas space and the low oxygen gas concentration in the vessel. silver ion gas space; maintaining the growth mixture at 110 to 140 ° C and the reduced oxygen gas concentration in the container gas space 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 vessel is <0.001% by weight; and where the reduced oxygen gas concentration in the gas space of the vessel is .5_. 2000 ppm. 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 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; bubbling into the silver ion source of an inert gas to extract entrained oxygen gas from the silver ion source and to give a low concentration of oxygen gas in a silver ion gas space in contact with the source silver ions; adding water, reducing sugar, polyvinylpyrrolidone (PVP), copper ion source (II) and the halide ion source to the container to form a combination; venting a gas space from the container in contact with the combination into the container to provide a reduced oxygen gas concentration in the gas space of the container; then heating the combination to 145 to 155 ° C; dividing the silver ion source into a first portion and a second portion, while maintaining the low oxygen gas concentration in the silver ion gas space; then adding the first part to the container to form a creation mixture, while maintaining the reduced oxygen gas concentration in the container gas space and the low oxygen gas concentration in the ion gas space money; then cooling the creation mixture to 125 to 135 ° C for a delay period, where the delay period is 5 to 15 minutes; then, after the delay period, adding the second portion to the vessel to form a growth mixture, while maintaining the reduced oxygen gas concentration in the container gas space and the low oxygen gas concentration in the vessel. silver ion gas space; maintaining the growth mixture at 125 to 135 ° C and the reduced oxygen gas concentration in the container gas space for a holding period of 16 to 20 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 vessel is <0.001% by weight; where the reduced oxygen gas concentration in the container gas space is 400 ppm; where the low oxygen gas concentration in the silver ion gas space is 1000 ppm; and wherein the plurality of silver nanowires having a high aspect ratio recovered have a mean diameter of 40 nm with a standard deviation of 26 nm diameters and an average aspect ratio of> 500.
    [0004] DETAILED DESCRIPTION [0012] A method for making silver nanowires having a high aspect ratio has been found which surprisingly provides silver nanowires having an average diameter of 20 to 60 nm and an average length of 20 to 60 nm. at 100 μm, while avoiding the inherent disadvantages that are associated with the use of glycols and while providing silver nanowires having a high degree of uniformity of diameters. Silver nanowire populations having a narrow diameter distribution as provided by the method of the present invention provide an advantage in the preparation of films having more uniform conductive properties and transparency in the film. 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. [0014] The term "high aspect ratio" as used herein with respect to the recovered silver nanowires means that the average aspect ratio of the recovered silver nanowires is> 500. Preferably, the method for making 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; bubbling into the silver ion source of an inert gas (preferably, during a bubbling time of 5 minutes, more preferably from 5 minutes to 2 hours, particularly preferably from 5 minutes to 1.5 minutes). hour) to extract the entrained oxygen gas from the silver ion source and to give a low concentration of oxygen gas in a silver ion gas space in contact with the silver ion source; adding water, reducing sugar, polyvinylpyrrolidone (PVP), copper ion source (II) and the halide ion source to the container to form a combination; venting a gas space from the container in contact with the combination into the container to provide a reduced oxygen gas concentration in the gas space of the container; then heating the combination to 110 to 160 ° C (preferably 140 to 155 ° C, more preferably 145 to 155 ° C, particularly preferably 150 ° C); then adding the silver ion source to the vessel (preferably with stirring) to form a growth mixture, while maintaining the reduced oxygen gas concentration in the container gas space and the low oxygen gas concentration in the silver ion gas space (preferably, where the silver ion source is added to the combination under a surface of the combination in the container); maintaining the growth mixture at 100 to 150 ° C (preferably at 110 to 140 ° C, more preferably at 120 to 135 ° C, particularly preferably at 125 to 135 ° C) and concentration reduced oxygen gas in the container gas space for a holding period of 2 to 30 hours (preferably 4 to 20 hours, more preferably 6 to 18 hours, particularly preferably 7 to 10 hours) to give a mixture of products; 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, in the process for producing silver nanowires having a high aspect ratio of the present invention: the bubbling step in the silver ion source of an inert gas comprises (preferably, consists of) bubbling into the silver ion source of an inert gas (preferably, wherein the inert gas is selected from the group consisting of argon, helium, methane, and nitrogen (from more preferably, argon, helium and nitrogen, more preferably argon and nitrogen, particularly preferably nitrogen) during a bubbling time of 5 minutes (more preferably 5 minutes to 2 hours, particularly preferably 5 minutes to 1.5 hours) prior to addition to the vessel to extract entrained oxygen gas from the silver ion source and to give a low concentration of oxygen gas in a vessel. silver ion gas gap in contact with the silver ion source. Preferably, the low oxygen gas concentration in the silver ion gas space is 5,000 ppm (preferably 5, 1000 ppm, more preferably 400 ppm, particularly preferably 5 ppm). ). Preferably, in the process for manufacturing silver nanowires having a high aspect ratio of the present invention: the step of purging the gas space of the container in contact with the combination in the container for giving the reduced oxygen gas concentration in the gas space of the vessel, includes: (i) isolating the gas space of the vessel from a surrounding atmosphere outside the vessel; (ii) then pressurizing the vessel gas space with an inert gas (preferably, wherein the inert gas is selected from the group consisting of argon, helium, methane, and nitrogen (more preferably argon, helium and nitrogen, more preferably argon and nitrogen, particularly preferably nitrogen); and (iii) thereafter purging the gas space of the vessel to provide the reduced oxygen gas concentration in the gas space of the vessel. Preferably, the gas space of the vessel is vented to a pressure in the vessel which is> the atmospheric pressure of the surrounding atmosphere) to give the reduced oxygen gas concentration in the gas space of the vessel.
    [0005] Preferably, the reduced oxygen gas concentration is 5. 2000 ppm (more preferably 5.400 ppm, particularly preferably 5. 20 ppm). [0018] More preferably, in the process for manufacturing silver nanowires having a high aspect ratio of the present invention: the step of purging the gas space of the container in contact with the combination in the container to give the reduced oxygen gas concentration in the gas space of the container, includes: (i) isolating the gas space of the container from a surrounding atmosphere outside the container; (ii) then pressurizing the vessel gas space with an inert gas (preferably, wherein the inert gas is selected from the group consisting of argon, helium, methane, and nitrogen (more preferably argon, helium and nitrogen, more preferably argon and nitrogen, particularly preferably nitrogen); and (iii) thereafter purging the gas space of the vessel to provide the reduced oxygen gas concentration in the gas space of the vessel (preferably, where the gas space of the vessel is vented to a pressure in the container which is> the atmospheric pressure of the surrounding atmosphere outside the container); and, (iv) repeating steps (ii) and (iii) at least three times to give the reduced oxygen gas concentration in the container gas space (preferably, where the reduced oxygen gas concentration is 2000). ppm (more preferably, 400 ppm, particularly preferably 5. 20 ppm)). 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 Reagent Grade Water) ("Standard Specification for Reagent Water"). Preferably, the reducing sugar 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 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. [0021] 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 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. [0022] 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. Most preferably, the copper (II) ion source provided in the process for producing high aspect ratio silver nanowires of the present invention is CuCl 2, where CuCl 2 is a copper (II) chloride. dihydrate. [0023] 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 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. [0024] Preferably, the silver ion source provided in the process for producing 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). [0025] 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, while maintaining the low concentration of oxygen gas in the silver ion gas space; and adding the individual portions to the container with a delay period between the additions of the individual parts to form the growth mixture, while maintaining the reduced oxygen gas concentration in the container gas space and the low gas concentration oxygen in the silver ion gas space. Preferably, the delay period between the additions of the individual portions is 1 to 60 minutes (more preferably 1 to 20 minutes, particularly preferably 5 to 15 minutes). Preferably, the method for producing silver nanowires having a high aspect ratio of the present invention further comprises: dividing the supplied silver ion source into a first portion and a second portion, while maintaining the low concentration of oxygen gas in the silver ion gas space (preferably, where the first portion is 10 to 30% by weight of the silver ion source provided, more preferably, where the first part is represents 15 to 25% by weight of the source of silver ions provided, particularly preferably, where the first part represents 20% by weight of the silver ion source supplied); then adding the first part to the container to form a creation mixture, while maintaining the reduced oxygen gas concentration in the container gas space and the low oxygen gas concentration in the ion gas space money; and then cooling the creation mixture to 100 to 150 ° C (preferably 110 to 140 ° C, more preferably 120 to 135 ° C, particularly preferably 125 to 135 ° C) for a period of time. delay (preferably, wherein the delay period is 1 to 60 minutes, more preferably 1 to 20 minutes, particularly preferably 5 to 15 minutes); then, after the delay period, adding the second portion to the vessel to form the growth mixture, while maintaining the reduced oxygen gas concentration in the vessel gas space and the low oxygen gas concentration in the vessel. silver ion gas space; where the reduced oxygen gas concentration in the container gas space is .5. 2000 ppm (preferably 400 ppm, particularly preferably 5 ppm); and, preferably, wherein the low oxygen gas concentration in the silver ion gas space is 5000 ppm (preferably 1000 ppm, more preferably 400 ppm, particularly preferably 5 ppm). Preferably, the method for producing silver nanowires having a high aspect ratio of the present invention further comprises: cooling the creation mixture to 100 to 150 ° C (preferably 110 to 140 ° C); Preferably, at 120 to 135 ° C, particularly preferably at 125 to 135 ° C) during the delay period (preferably, where the delay period is 1 to 60 minutes (more preferably, 1 to 20 minutes, particularly preferably 5 to 15 minutes.) More preferably, the process for making silver nanowires having a high aspect ratio of the present invention further comprises: cooling the creation mixture to 100 to 150 ° C (preferably at 110 to 140 ° C, more preferably at 120 to 135 ° C, particularly preferably at 125 to 135 ° C) for a second half of the delay period (from preference, where the period delay time is 1 to 60 minutes (more preferably 1 to 20 minutes, particularly preferably 5 to 15 minutes). The method for producing silver nanowires having a high aspect ratio of the present invention optionally further comprises: providing a pH adjusting agent; and adding the pH adjusting agent to the container, wherein the combination has a pH of 2.0 to 4.0 (preferably 2.5 to 3.75, more preferably 3, 0 to 3.5, particularly preferably from 3.1 to 3.3) prior to the addition of the silver ion source to the vessel. Preferably, the pH adjusting agent provided is an acid. More preferably, the pH adjusting agent provided is an acid selected from the group consisting of at least one of inorganic acids (eg, nitric acid, sulfuric acid, hydrochloric acid, fluorosulfuric acid, phosphoric acid, fluoroantinnonic acid) and organic acids (for example, methanesulfonic acid, ethanesulphonic acid, benzenesulphonic acid, acetic acid, fluoroacetic acid, chloroacetic acid, citric acid, gluconic acid, lactic acid). Preferably, the pH adjusting agent provided has a pH <2.0. More preferably, the pH adjusting agent provided includes nitric acid. Most preferably, the pH adjusting agent provided is aqueous nitric acid. Preferably, in the process for producing silver nanowires having a high aspect ratio of the present invention, the water, the reducing sugar, the polyvinylpyrrolidone (PVP) supplied, the source of copper ions ( II), the halide ion source and the pH adjusting agent, if any, are added to the container in any order in an individual succession (i.e., 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 sub-combinations). More preferably, at least two of water, reducing sugar, polyvinylpyrrolidone (PVP) provided, copper (II) ion source, halide ion source and pH adjusting agent, are provided. There are some, are mixed together to form a sub-combination before addition to the container. [0030] 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 the reducing sugar and the polyvinylpyrrolidone (PVP) provided to form a reducing sugar / PVP sub-combination, where a second volume of water is combined with the source of copper (II) ions 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 wherein 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, if any, are added to the container in any order in an individual succession (i.e., one at a time), simultaneously (i.e. all at the same time), or semisimultaneously (i.e., some individually a at the same 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 the pH adjusting agent, if any, in any order in an individual succession (i.e., one at a time) simultaneously (i.e. all at the same time) ), or semi-simultaneously (ie, some individually one at a time, some simultaneously simultaneously 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 combination of halide ions to the vessel, followed by the addition of the pH adjusting agent, if any, to the vessel to form the combination. The silver ion sub-combination is then added to the combination in the container. [0031] 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. [0032] Preferably, in the process for making silver nanowires having a high aspect ratio of the present invention, the weight ratio of the polyvinylpyrrolidone (PVP) to silver 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 the halide ions to the 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). [0034] Preferably, in the process for producing silver nanowires having a high aspect ratio of the present invention, the plurality of recovered silver nanowires have a mean diameter of 5.40 nm (preferably 20 nm). at 40 nm, more preferably from 20 to 35 nm, particularly preferably from 20 to 30 nm). More preferably, in the method for making silver nanowires having a high aspect ratio of the present invention, the plurality of recovered silver nanowires have a mean diameter. 40 nm (preferably 20 to 40 nm, more preferably 20 to 35 nm, particularly preferably 20 to 30 nm) and an average length of 10 to 100 μm. Preferably, the plurality of recovered silver nanowires have an average aspect ratio of> 500. [0035] Preferably, in the process for making silver nanowires having a high aspect ratio of the present invention, the The plurality of recovered silver nanowires have a standard deviation of diameters 5 to 26 nm (preferably 1 to 26 nm, more preferably 5 to 20 nm, particularly preferably 10 to 15 nm). More preferably, in the process for making silver nanowires having a high aspect ratio of the present invention, the plurality of recovered silver nanowires have a mean diameter of 40 nm (preferably 20 to 40 nm). more preferably 20 to 35 nm, particularly preferably 20 to 30 nm) with a standard deviation of diameters 26 nm (preferably 1 to 26 nm, more preferably 5 to 20 nm). nm, particularly preferably from 10 to 15 nm). Particularly preferably, in the process for making silver nanowires having a high aspect ratio of the present invention, the plurality of recovered silver nanowires have a mean diameter of 5.40 nm (preferably 20 to 40 nm, more preferably 20 to 35 nm, particularly preferably 20 to 30 nm) with a standard deviation of 26 nm (preferably 1 to 26 nm, more preferably at 20 nm, particularly preferably 10 to 15 nm) and an average length of 10 to 100 μm. 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 Si: halide ion sub-combination [0038] The halide ion sub-combination used herein in some examples was prepared by dissolving sodium chloride (0.1169 g, available from Sigma Aldrich) in the water (500 mL).
    [0007] Example S2: Sub-combination of copper (II) ions [0039] The sub-combination of copper (II) ions used here in certain examples was prepared by dissolving copper (II) chloride dihydrate (0.3410 g available from Sigma Aldrich) in water (500 mL).
    [0008] Example 53: reducing sugar / polyvinyl hydrolidone (PVP) sub-combination [0040] The reducing sugar / polyvinylpyrrolidone (PVP) sub-combination used here in some examples was prepared by combining polyvinylpyrrolidone (PVP) (5.14 g, Sokalan). K30 P available from BASF having a weight average molecular weight of 50000 g / mol) and D-glucose (1.33 g,> 99% from Sigma-Aldrich) in water (254 mL).
    [0009] Example S4: Combination [0041] The combination used herein in some examples was prepared by combining a reducing sugar / polyvinylpyrrolidone (PVP) sub-combination prepared according to Example S3; a sub-combination of halide ions (2.1 mL) prepared according to Example Si; and a copper (II) ion sub-combination (2.1 mL) prepared according to Example S2. Example S5: silver ion sub-combination [0042] The silver ion sub-combination used here in some examples was prepared by adding AgNO3 (1.25 g, ACS reagent grade, 99.0% available from Sigma Aldrich) to water (68 mL). Example S6: silver ion sub-combination The silver ion sub-combination used here in some examples was prepared by addition of AgNO 3 (1.25 g, ACS reagent grade, 99.0% available from Sigma Aldrich) to water (68 mL) and sparging with nitrogen for five minutes before use.
    [0010] Comparative Example C1: Preparation of Silver Nanowires [0044] A 600 ml 316 stainless steel Parr reactor, mixing means and a temperature control system were used. A combination prepared according to Example S4 was added to the reactor. The reactor was then closed and the combination in the reactor was heated to 150 ° C. Then 1 / 5th of a silver ion sub-combination prepared according to Example S5 was charged to the reactor at a rate of 13.7 mL / min to form a creation mixture. The creation mixture was then mixed for ten minutes while the setting point of the temperature control device was maintained at 150 ° C. Then, for the next ten minutes, the set point of the temperature control device was lowered linearly to 130 ° C. Then the remaining 4 / 5ths of the silver ion sub-combination prepared according to Example S5 were charged to the reactor at a rate of 5.5 mL / min to form a growth mixture. The growth mixture was then mixed 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. The reactor was then vented to release any accumulated pressure in the vessel and the product mixture was collected. Example 1: Preparation of silver nanowires A 600 ml 316 stainless steel Parr reactor, mixing means and a temperature control system were used. A combination prepared according to Example S4 was added to the reactor. 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 117 x 103 Pa (16.8 psig) after the final purge. The temperature control device was then set at 150 ° C. After the combination reached 150 ° C, 1 / 5th of the silver ion sub-combination prepared according to Example S6 was added to the reactor at a rate of 13.7 mL / min to form a creation mixture. . The creation mixture was then mixed for ten minutes while the setting point of the temperature control device was maintained at 150 ° C. Then, for the next ten minutes, the set point of the temperature control device was lowered linearly to 130 ° C. Then the remaining 4 / 5ths of the silver ion sub-combination prepared according to Example S6 were charged to the reactor at a rate of 5.5 mL / min to form a growth mixture. The growth mixture was then mixed 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. The reactor was then vented to release any accumulated pressure in the vessel and the product mixture was collected.
    [0011] Analysis of the silver nanowires collected The silver nanowires produced in Comparative Example C1 and Example 1 were then analyzed with a FEI Nova Nano SEM field emitting gun (SEM) using Automated Image Acquisition (AIA) from FEI. For each sample, the AIA was performed at five subheadings using magnifications of 42 μm, 12 μm and 6 μm of the optical field. Image software) was used to determine the diameter and length of silver nanowires. The results are shown in Table 1. The average length of the silver nanowires was found to exceed 20 μm, based on the SEM images obtained for the diameter analysis. The UV / Vis spectral analysis of the silver nanowires produced in Comparative Example C1 and in Example 1 was carried out using a Shimadzu UV 2401 spectrophotometer. The raw UV / Vis absorption spectra have been 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.
    [0012] TABLE 1 Width (nm) Spectral Analysis Media Mov Dev-Axial Axis Ex ne ne type (nm) Abs500 Cl 40.5 48.9 26.1 383 0.48 1 33.7 39.2 21.3 377 0, 22
    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; bubbling into the silver ion source of an inert gas to extract entrained oxygen gas from the silver ion source and to give a low concentration of oxygen gas in a silver ion gas space in contact with the ion source. silver ion source; adding water, reducing sugar, polyvinylpyrrolidone (PVP), copper ion source (II) and the halide ion source to the container to form a combination; venting a gas space from the container in contact with the combination into the vessel to provide a reduced oxygen gas concentration in the gas space of the vessel; then heating the combination to 110 to 160 ° C; and then adding the silver ion source to the vessel to form a growth mixture, while maintaining the reduced oxygen gas concentration in the container gas space and the low oxygen gas concentration in the vessel space. silver ion gas; maintaining the growth mixture at 100 to 150 ° C and the reduced oxygen gas concentration in the container gas space for a holding period of 2 to 30 hours to provide a product mixture; andrecovering a plurality of silver nanowires having a high aspect ratio from the product mixture; where the total glycol concentration in the container is <0.001% by weight.
    [0002]
    2. Method according to claim 1, characterized in that it further comprises: the division of the source of silver ions into a first part and a second part, while maintaining the low concentration of oxygen gas in the space of silver ion gas; where the combination is heated to 140 to 155 ° C; then adding the first part to the container to form a creation mixture, while maintaining the reduced oxygen gas concentration in the container gas space and the low oxygen gas concentration in the ion gas space money; then cooling the creation mixture to 100 to 150 ° C for a period of time; then, after the delay period, adding the second portion to the vessel to form the growth mixture, while maintaining the reduced oxygen gas concentration in the vessel gas space and the low oxygen gas concentration in the vessel. silver ion gas space; where the reduced oxygen gas concentration in the container gas space is 2000 ppm.
    [0003]
    3. Process according to any of the preceding claims, characterized in that the growth mixture is maintained at 100 to 150 ° 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. 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 one of the preceding claims, characterized in that the source of silver ions supplied is silver nitrate.
    [0009]
    9. Process according to claim 2, characterized in that the combination is heated to 140 to 155 ° C; the creation mixture is cooled to 110 to 140 ° C during the delay period; the growth mixture is maintained at 110 to 140 ° C during the holding period; the reducing sugar provided is glucose; the polyvinylpyrrolidone (PVP) provided has a weight average molecular weight, Mw, of 40,000 to 60,000 Daltons; the copper (II) ion source supplied is copper (II) chloride; the source of halide ions provided is sodium chloride; and the silver ion source provided is silver nitrate.
    [0010]
    10. The method of claim 9, characterized in that the first part is 10 to 30% by weight of the silver ion source supplied; the combination is heated to 145 to 155 ° C prior to the addition of the silver ion source to the container; the creation mixture is cooled to 125 to 135 ° C during the delay period, where the delay period is 5 to 15 minutes, the growth mixture is maintained at 125 to 135 ° C during the holding period, where the period Hold is 16 to 20 hours; the reduced oxygen gas concentration in the container gas space is 400 ppm; the low concentration of oxygen gas in the silver ion gas space is 1000 ppm; and the plurality of silver nanowires having a high aspect ratio recovered have an average diameter of 5 nm with a standard deviation of diameters of 5. 26 nm and a mean aspect ratio of> 500.
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    同族专利:
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