WO2024037029A1 - Method utilizing dropwise addition to improve synthesis yield and quality of silver nanowires - Google Patents

Method utilizing dropwise addition to improve synthesis yield and quality of silver nanowires Download PDF

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WO2024037029A1
WO2024037029A1 PCT/CN2023/090459 CN2023090459W WO2024037029A1 WO 2024037029 A1 WO2024037029 A1 WO 2024037029A1 CN 2023090459 W CN2023090459 W CN 2023090459W WO 2024037029 A1 WO2024037029 A1 WO 2024037029A1
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reaction
reaction solution
reaction liquid
silver nanowires
silver
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PCT/CN2023/090459
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French (fr)
Chinese (zh)
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汪颖
曾西平
叶晃青
李艳玲
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深圳市华科创智技术有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0547—Nanofibres or nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the invention belongs to the technical field of nanomaterials, and specifically relates to a method for improving the synthesis yield and quality of silver nanowires through secondary dripping.
  • silver nanowires have attracted widespread attention due to their excellent electrical and thermal conductivity and mechanical properties. Their related materials are used in many fields such as energy, catalysis, biology, and electronics. Improving the yield and quality problems in the actual production of silver nanowires, and synthesizing silver nanowires with high purity and high aspect ratio will greatly improve production efficiency and save production costs.
  • the current method of improving the synthesis size and length of silver nanowires requires adding a large amount of silver nitrate replenishing solution, which is costly; the actual operation is difficult and the repeatability is poor.
  • the object of the present invention is to provide a method for preparing silver nanowires, which is simple to operate and can synthesize silver nanowires with higher purity and larger aspect ratio.
  • the present invention adopts the following technical solutions.
  • a method for preparing silver nanowires comprising the following steps: (1) dissolving a silver salt in a polyol to obtain a first reaction solution; (2) dissolving polyvinylpyrrolidone and a soluble halide salt in a polyol to obtain a third reaction solution. two reaction liquids; (3) heat the second reaction liquid and keep it constant after reaching the target temperature; (4) add the first reaction liquid dropwise to the second reaction liquid to react; (5) when the After the first reaction liquid is added dropwise, the third reaction liquid is added dropwise into the reaction system within 20 minutes; the composition of the third reaction liquid is the same as that of the second reaction liquid, but the mass concentration of the silver salt is less than the second reaction liquid.
  • the third reaction liquid is added to the reaction system within 0.5 to 20 minutes.
  • the third reaction liquid is added to the reaction system within 1.5 to 20 minutes.
  • the third reaction liquid is added to the reaction system within 5 to 15 minutes.
  • the mass concentration of silver salt in the third reaction liquid is 0.05 to 0.5 times that of the first reaction liquid.
  • the mass concentration of silver salt in the third reaction liquid is that of the first reaction liquid. 0.05 to 0.4 times; more preferably, the mass concentration of the silver salt in the third reaction liquid is 0.1 to 0.4 times that of the first reaction liquid.
  • the volume ratio of the third reaction liquid to the first reaction liquid is (0.3 ⁇ 1):1; preferably, the volume ratio of the third reaction liquid to the first reaction liquid is (0.5 ⁇ 1) 1):1.
  • the mass concentration of silver salt in the first reaction liquid is 0.1-0.35g/mL; and/or the mass concentration of polyvinylpyrrolidone in the second reaction liquid is 10-20g/L, and the soluble The mass concentration of brine salt is 0.05 ⁇ 0.2g/L.
  • the mass concentration of the silver salt in the first reaction solution is 0.15-0.25g/mL.
  • the mass concentration of polyvinylpyrrolidone in the second reaction liquid is 10-15g/L, and the mass concentration of the soluble halide salt is 0.05-0.15g/L.
  • the target temperature is 120 ⁇ 150°C; and/or the dripping acceleration rate of the first reaction liquid is 0.5 ⁇ 0.9mL/min; and/or the dripping rate of the third reaction liquid is The acceleration rate is 0.5 ⁇ 0.9mL/min.
  • the dripping rates of the first reaction liquid and the third reaction liquid are the same.
  • the silver salt is selected from silver nitrate; and/or the polyol is selected from at least one of ethylene glycol, glycerin, 1,5-pentanediol and 1,3-propanediol. ; And/or, the soluble halide salt is selected from at least one of sodium chloride, potassium chloride, sodium bromide and potassium bromide.
  • the invention provides a method for preparing silver nanowires, which method can effectively improve the yield and quality of silver nanowire synthesis.
  • the present invention found that by adding silver salt solution dropwise to the reaction system twice at a suitable time, silver nanowires with higher purity and larger aspect ratio can be synthesized. Further, by controlling the mass concentration and volume of the silver salt dropped twice, a better preparation effect can be obtained.
  • the preparation method of the present invention can be well applied to the actual production of silver nanowires. Under the condition of ensuring the cost, it can efficiently synthesize silver nanowires with higher yield and quality, and has the advantages of simple operation, strong repeatability and good effect on silver. The advantages of significantly improving the yield and quality of nanowire synthesis will greatly improve production efficiency and save production costs.
  • Figure 1 is a monitoring chart of the conductivity of the reaction systems of Example 1 and Comparative Example 1.
  • Figure 2 is a comparative diagram of the diameters of silver nanowires prepared in Example 1 and Comparative Examples 1 to 3.
  • Figure 3 is a comparison chart of the lengths of silver nanowires prepared in Example 1 and Comparative Example 1.
  • Figure 4 is a comparison chart of the yield and purity of silver nanowires prepared in Example 1 and Comparative Example 1.
  • the "plurality” mentioned in the present invention means two or more.
  • “And/or” describes the relationship between related objects, indicating that there can be three relationships.
  • a and/or B can mean: A exists alone, A and B exist simultaneously, and B exists alone.
  • the character “/” generally indicates that the related objects are in an "or” relationship.
  • This embodiment provides a method for preparing silver nanowires, which method includes the following steps:
  • the preparation method of the third reaction solution is as follows: Dissolve 0.15g silver nitrate in 15mL ethylene glycol to obtain the third reaction solution.
  • This embodiment provides a method for preparing silver nanowires, which method includes the following steps:
  • the third reaction solution is configured as follows: Dissolve 1.5g silver nitrate in 15mL ethylene glycol to obtain the third reaction solution.
  • This embodiment provides a method for preparing silver nanowires, which method includes the following steps:
  • This comparative example provides a method for preparing silver nanowires.
  • the method is the same as Example 1 except that the third reaction solution is not dropped, and specifically includes the following steps:
  • This comparative example provides a method for preparing silver nanowires.
  • the method is the same as Example 1 except that the time for dropping the third reaction solution is different, and specifically includes the following steps:
  • the preparation method of the third reaction solution is as follows: Dissolve 0.15g silver nitrate in 15mL ethylene glycol to obtain the third reaction solution.
  • This comparative example provides a method for preparing silver nanowires.
  • the method is the same as Example 1 except that the mass concentration of the silver salt in the third reaction solution dropped is different.
  • the method includes the following steps:
  • the preparation method of the third reaction solution is as follows: Dissolve 2g of silver nitrate in 15mL of ethylene glycol to obtain the third reaction solution.
  • Example 1 The conductivity change diagram of the reaction system in Example 1 (represented by two drops in the figure) and Comparative Example 1 (represented by one drop in the figure) is shown in Figure 1. It can be seen from Figure 1 that Example 1 passes Controlling the second dropwise addition of the third reaction solution successfully extended the plateau period (the nucleation stage in the growth of silver nanowires).
  • Comparative Example 2 the third reaction solution was added dropwise only 25 minutes after the first reaction solution was added. Compared with Example 1, the length-to-diameter ratio of the silver nanowires prepared was larger, the yield was lower, and the by-products were The quantity increased; the yield and aspect ratio of silver nanowires in Comparative Example 2 were not significantly different from those in Comparative Example 1 ( Figure 2). This is because the third reaction solution is added dropwise at the end of the growth of silver nanowires, and the newly added silver ions can only be reduced to silver atoms in the solution and cannot be used to generate silver nanowires.
  • the concentration of the third reaction solution dropped in Comparative Example 3 is not within the scope of the present invention, resulting in uneven length and diameter of the silver nanowires in the product, containing a large number of silver nanorods and silver nanoparticles, and reducing the purity of the produced silver nanowires. (figure 2).
  • the present invention can significantly improve the yield and purity of silver nanowires, and can synthesize silver nanowires with higher purity and larger aspect ratio.

Abstract

A method for preparing silver nanowires. The method comprises the following steps: (1) dissolving a silver salt in polyol to obtain a first reaction solution; (2) dissolving polyvinylpyrrolidone and soluble halide salt in the polyol to obtain a second reaction solution; (3) heating the second reaction solution, reaching a target temperature and keeping the temperature constant; (4) dropwise adding the first reaction solution into the second reaction solution to react same; (5) after finishing the dropwise adding of the first reaction solution, within 20 minutes, beginning the dropwise adding of a third reaction solution into the reaction system. Using two-step dropwise addition of a silver salt solution into a reaction system at suitable times and controlling the mass concentration and volume of the silver salt during the two-step dropwise addition effectively improves the yield and quality of silver nanowire synthesis, and results in silver nanowires having higher purity and a larger length-to-diameter ratio. The method has the advantages of being easy to operate, highly repeatable, etc., greatly improves production efficiency, and saves production costs.

Description

一种通过二次滴加改善银纳米线合成产量及质量的方法A method to improve the yield and quality of silver nanowire synthesis through secondary dripping 技术领域Technical field
本发明属于纳米材料技术领域，具体涉及一种通过二次滴加改善银纳米线合成产量及质量的方法。The invention belongs to the technical field of nanomaterials, and specifically relates to a method for improving the synthesis yield and quality of silver nanowires through secondary dripping.
背景技术Background technique
近年来，银纳米线因其出色的导电导热和力学性能，引起了人们的广泛关注，其相关的材料应用于能源，催化，生物，电子等诸多领域。改善银纳米线实际生产中的产量和质量问题，合成高纯度和高长径比的银纳米线将很大程度上提高生产效率，节约生产成本。目前改善纳米银线合成尺寸与长度的方法需加入大量硝酸银补充液，成本较高；且实际操作困难，重复性差。In recent years, silver nanowires have attracted widespread attention due to their excellent electrical and thermal conductivity and mechanical properties. Their related materials are used in many fields such as energy, catalysis, biology, and electronics. Improving the yield and quality problems in the actual production of silver nanowires, and synthesizing silver nanowires with high purity and high aspect ratio will greatly improve production efficiency and save production costs. The current method of improving the synthesis size and length of silver nanowires requires adding a large amount of silver nitrate replenishing solution, which is costly; the actual operation is difficult and the repeatability is poor.
发明内容Contents of the invention
基于此，本发明的目的在于提供一种制备银纳米线的方法，所述方法操作简单，可以合成纯度更高、长径比更大的银纳米线。Based on this, the object of the present invention is to provide a method for preparing silver nanowires, which is simple to operate and can synthesize silver nanowires with higher purity and larger aspect ratio.
为达到上述目的，本发明采用如下技术方案。In order to achieve the above object, the present invention adopts the following technical solutions.
一种制备银纳米线的方法，包括以下步骤：(1)将银盐溶于多元醇中，得到第一反应液；(2)将聚乙烯吡咯烷酮和可溶性卤盐溶于多元醇中，得到第二反应液；(3)加热所述第二反应液，达到目标温度后保持恒定；(4)向所述第二反应液中滴加所述第一反应液进行反应；(5)当所述第一反应液滴加完毕后，于20min内开始向所述反应体系中滴加第三反应液；所述第三反应液的组成与所述第二反应液相同，但银盐的质量浓度小于所述第二反应液。A method for preparing silver nanowires, comprising the following steps: (1) dissolving a silver salt in a polyol to obtain a first reaction solution; (2) dissolving polyvinylpyrrolidone and a soluble halide salt in a polyol to obtain a third reaction solution. two reaction liquids; (3) heat the second reaction liquid and keep it constant after reaching the target temperature; (4) add the first reaction liquid dropwise to the second reaction liquid to react; (5) when the After the first reaction liquid is added dropwise, the third reaction liquid is added dropwise into the reaction system within 20 minutes; the composition of the third reaction liquid is the same as that of the second reaction liquid, but the mass concentration of the silver salt is less than the second reaction liquid.
在一些实施例中，步骤(5)中当所述第一反应液滴加完毕后，于0.5～20min内开始向所述反应体系中加入第三反应液。In some embodiments, after the dropwise addition of the first reaction liquid is completed in step (5), the third reaction liquid is added to the reaction system within 0.5 to 20 minutes.
在一些优选的实施例中，步骤(5)中当所述第一反应液滴加完毕后，于1.5～20min内开始向所述反应体系中加入第三反应液。In some preferred embodiments, after the dropwise addition of the first reaction liquid is completed in step (5), the third reaction liquid is added to the reaction system within 1.5 to 20 minutes.
在一些更优选的实施例中，步骤(5)中当所述第一反应液滴加完毕后，于5～15min内开始向所述反应体系中加入第三反应液。In some more preferred embodiments, after the dropwise addition of the first reaction liquid is completed in step (5), the third reaction liquid is added to the reaction system within 5 to 15 minutes.
在一些实施例中，所述第三反应液中银盐的质量浓度为所述第一反应液的0.05～0.5倍。In some embodiments, the mass concentration of silver salt in the third reaction liquid is 0.05 to 0.5 times that of the first reaction liquid.
在一些优选的实施例中，所述第三反应液中银盐的质量浓度为所述第一反应液的 0.05～0.4倍；更优选地，所述第三反应液中银盐的质量浓度为所述第一反应液的0.1～0.4倍。In some preferred embodiments, the mass concentration of silver salt in the third reaction liquid is that of the first reaction liquid. 0.05 to 0.4 times; more preferably, the mass concentration of the silver salt in the third reaction liquid is 0.1 to 0.4 times that of the first reaction liquid.
在一些实施例中，所述第三反应液与第一反应液的体积比为(0.3～1)：1；优选地，所述第三反应液与第一反应液的体积比为(0.5～1)：1。In some embodiments, the volume ratio of the third reaction liquid to the first reaction liquid is (0.3~1):1; preferably, the volume ratio of the third reaction liquid to the first reaction liquid is (0.5~1) 1):1.
在一些实施例中，所述第一反应液中银盐的质量浓度为0.1～0.35g/mL；和/或，所述第二反应液中聚乙烯吡咯烷酮的质量浓度为10～20g/L，可溶性卤盐的质量浓度为0.05～0.2g/L。In some embodiments, the mass concentration of silver salt in the first reaction liquid is 0.1-0.35g/mL; and/or the mass concentration of polyvinylpyrrolidone in the second reaction liquid is 10-20g/L, and the soluble The mass concentration of brine salt is 0.05~0.2g/L.
在一些实施例中，所述第一反应液中银盐的质量浓度为0.15～0.25g/mL。In some embodiments, the mass concentration of the silver salt in the first reaction solution is 0.15-0.25g/mL.
在一些实施例中，所述第二反应液中聚乙烯吡咯烷酮的质量浓度为10～15g/L，可溶性卤盐的质量浓度为0.05～0.15g/L。In some embodiments, the mass concentration of polyvinylpyrrolidone in the second reaction liquid is 10-15g/L, and the mass concentration of the soluble halide salt is 0.05-0.15g/L.
在一些实施例中，所述目标温度为120～150℃；和/或，所述第一反应液的滴加速率为0.5～0.9mL/min；和/或，所述第三反应液的滴加速率为0.5～0.9mL/min。In some embodiments, the target temperature is 120˜150°C; and/or the dripping acceleration rate of the first reaction liquid is 0.5˜0.9mL/min; and/or the dripping rate of the third reaction liquid is The acceleration rate is 0.5~0.9mL/min.
在一些实施例中，所述第一反应液和第三反应液的滴加速率相同。In some embodiments, the dripping rates of the first reaction liquid and the third reaction liquid are the same.
在一些实施例中，所述银盐选自硝酸银；和/或，所述多元醇选自乙二醇、丙三醇、1，5-戊二醇和1，3-丙二醇中的至少一种；和/或，所述可溶性卤盐选自氯化钠、氯化钾、溴化钠和溴化钾中的至少一种。In some embodiments, the silver salt is selected from silver nitrate; and/or the polyol is selected from at least one of ethylene glycol, glycerin, 1,5-pentanediol and 1,3-propanediol. ; And/or, the soluble halide salt is selected from at least one of sodium chloride, potassium chloride, sodium bromide and potassium bromide.
本发明提供了一种制备银纳米线的方法，所述方法能有效改善银纳米线合成的产量及质量。本发明发现，通过在合适的时间向反应体系中二次滴加银盐溶液，可以合成纯度更高、长径比更大的银纳米线。进一步地，通过控制二次滴加的银盐的质量浓度和体积，可以获得更好的制备效果。本发明所述制备方法能很好地运用到银纳米线的实际生产当中，在保证成本的情况下，高效合成产量和质量更高的银纳米线，具有操作简单、可重复性强以及对银纳米线合成产量和质量的改善效果明显等优点，将很大程度上提高生产效率，节约生产成本。The invention provides a method for preparing silver nanowires, which method can effectively improve the yield and quality of silver nanowire synthesis. The present invention found that by adding silver salt solution dropwise to the reaction system twice at a suitable time, silver nanowires with higher purity and larger aspect ratio can be synthesized. Further, by controlling the mass concentration and volume of the silver salt dropped twice, a better preparation effect can be obtained. The preparation method of the present invention can be well applied to the actual production of silver nanowires. Under the condition of ensuring the cost, it can efficiently synthesize silver nanowires with higher yield and quality, and has the advantages of simple operation, strong repeatability and good effect on silver. The advantages of significantly improving the yield and quality of nanowire synthesis will greatly improve production efficiency and save production costs.
附图说明Description of drawings
图1为实施例1和对比例1反应体系的电导率监测图。Figure 1 is a monitoring chart of the conductivity of the reaction systems of Example 1 and Comparative Example 1.
图2为实施例1、对比例1～3制备获得的银纳米线的直径对比图。Figure 2 is a comparative diagram of the diameters of silver nanowires prepared in Example 1 and Comparative Examples 1 to 3.
图3为实施例1和对比例1制备获得的银纳米线的长度对比图。Figure 3 is a comparison chart of the lengths of silver nanowires prepared in Example 1 and Comparative Example 1.
图4为实施例1和对比例1制备获得的银纳米线产量和纯度对比图。Figure 4 is a comparison chart of the yield and purity of silver nanowires prepared in Example 1 and Comparative Example 1.
具体实施方式Detailed ways
本发明下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。实施例中所用到的各种常用化学试剂，均为市售产品。 Experimental methods without specifying specific conditions in the following examples of the present invention usually follow conventional conditions or conditions recommended by the manufacturer. Various commonly used chemical reagents used in the examples are all commercially available products.
除非另有定义，本发明所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不用于限制本发明。Unless otherwise defined, all technical and scientific terms used in the present invention have the same meanings commonly understood by those skilled in the technical field belonging to the present invention. The terms used in the description of the present invention are only for the purpose of describing specific embodiments and are not used to limit the present invention.
本发明的术语“包括”和“具有”以及它们任何变形，意图在于覆盖不排他的包含。例如包含了一系列步骤的过程、方法、装置、产品或设备没有限定于已列出的步骤或模块，而是可选地还包括没有列出的步骤，或可选地还包括对于这些过程、方法、产品或设备固有的其它步骤。The terms "including" and "having" and any variations thereof herein are intended to cover a non-exclusive inclusion. For example, a process, method, device, product or equipment that includes a series of steps is not limited to the listed steps or modules, but optionally also includes unlisted steps, or optionally also includes steps for these processes, Other steps inherent to the method, product, or device.
在本发明中提及的“多个”是指两个或两个以上。“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B这三种情况。字符“/”一般表示前后关联对象是一种“或”的关系。The "plurality" mentioned in the present invention means two or more. "And/or" describes the relationship between related objects, indicating that there can be three relationships. For example, A and/or B can mean: A exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the related objects are in an "or" relationship.
下面结合具体实施例进行说明。Description will be made below with reference to specific embodiments.
实施例1Example 1
本实施例提供一种制备银纳米线的方法，所述方法包括以下步骤：This embodiment provides a method for preparing silver nanowires, which method includes the following steps:
(1)将3g硝酸银溶于15mL乙二醇中，获得第一反应液；(1) Dissolve 3g silver nitrate in 15mL ethylene glycol to obtain the first reaction solution;
(2)将6gPVP和0.03gKCl溶于500mL乙二醇中，获得第二反应液；将第二反应液置于500mL烧瓶中，并***在线电导率测试仪电极；(2) Dissolve 6gPVP and 0.03gKCl in 500mL ethylene glycol to obtain the second reaction liquid; place the second reaction liquid in a 500mL flask and insert the online conductivity tester electrode;
(3)加热所述第二反应液，升温到140℃并保持恒定；(3) Heat the second reaction liquid to a temperature of 140°C and keep it constant;
(4)进行首轮滴加：向所述第二反应液中以0.75mL/min的速率匀速滴加所述第一反应液进行反应，并计时和监测电导率数值；(4) Perform the first round of dropping: add the first reaction solution dropwise to the second reaction solution at a constant rate of 0.75 mL/min to react, and time and monitor the conductivity value;
(5)当所述第一反应液滴加完毕10min后，开始向所述反应体系中以0.75mL/min的速率匀速滴加15mL第三反应液；所述第三反应液配置方法如下：将0.15g硝酸银溶于15mL乙二醇中，获得第三反应液。(5) When the first reaction solution is added dropwise for 10 minutes, start adding 15 mL of the third reaction solution uniformly into the reaction system at a rate of 0.75 mL/min; the preparation method of the third reaction solution is as follows: Dissolve 0.15g silver nitrate in 15mL ethylene glycol to obtain the third reaction solution.
反应过程中持续观察电导率测试仪中电导率的变化，待反应结束后，将最终产物进行制样测SEM。During the reaction process, continue to observe the changes in conductivity in the conductivity tester. After the reaction is completed, prepare a sample of the final product for SEM measurement.
实施例2Example 2
本实施例提供一种制备银纳米线的方法，所述方法包括以下步骤：This embodiment provides a method for preparing silver nanowires, which method includes the following steps:
(1)将3g硝酸银溶于15mL乙二醇中，获得第一反应液；(1) Dissolve 3g silver nitrate in 15mL ethylene glycol to obtain the first reaction solution;
(2)将6gPVP和0.03gKCl溶于500mL乙二醇中，获得第二反应液；将第二反应液置于500mL烧瓶中，并***在线电导率测试仪电极；(2) Dissolve 6gPVP and 0.03gKCl in 500mL ethylene glycol to obtain the second reaction liquid; place the second reaction liquid in a 500mL flask and insert the online conductivity tester electrode;
(3)加热所述第二反应液，升温到130℃并保持恒定； (3) Heat the second reaction liquid to a temperature of 130°C and keep it constant;
(4)进行首轮滴加：向所述第二反应液中以0.65mL/min的速率匀速滴加所述第一反应液进行反应，并计时和监测电导率数值；(4) Perform the first round of dropping: add the first reaction solution dropwise to the second reaction solution at a constant rate of 0.65 mL/min to react, and time and monitor the conductivity value;
(5)当所述第一反应液滴加完毕15min后，开始向所述反应体系中以0.65mL/min的速率匀速滴加15mL第三反应液；所述第三反应液配置方法如下：将1.5g硝酸银溶于15mL乙二醇中，获得第三反应液。(5) After 15 minutes of adding the first reaction solution, start adding 15 mL of the third reaction solution uniformly into the reaction system at a rate of 0.65 mL/min; the third reaction solution is configured as follows: Dissolve 1.5g silver nitrate in 15mL ethylene glycol to obtain the third reaction solution.
反应过程中持续观察电导率测试仪中电导率的变化，待反应结束后，将最终产物进行制样测SEM。During the reaction process, continue to observe the changes in conductivity in the conductivity tester. After the reaction is completed, prepare a sample of the final product for SEM measurement.
实施例3Example 3
本实施例提供一种制备银纳米线的方法，所述方法包括以下步骤：This embodiment provides a method for preparing silver nanowires, which method includes the following steps:
(1)将3g硝酸银溶于15mL乙二醇中，获得第一反应液；(1) Dissolve 3g silver nitrate in 15mL ethylene glycol to obtain the first reaction solution;
(2)将6gPVP和0.03gKCl溶于500mL乙二醇中，获得第二反应液；将第二反应液置于500mL烧瓶中，并***在线电导率测试仪电极；(2) Dissolve 6gPVP and 0.03gKCl in 500mL ethylene glycol to obtain the second reaction liquid; place the second reaction liquid in a 500mL flask and insert the online conductivity tester electrode;
(3)加热所述第二反应液，升温到150℃并保持恒定；(3) Heat the second reaction liquid to a temperature of 150°C and keep it constant;
(4)进行首轮滴加：向所述第二反应液中以0.8mL/min的速率匀速滴加所述第一反应液进行反应，并计时和监测电导率数值；(4) Perform the first round of dropping: add the first reaction solution dropwise to the second reaction solution at a constant rate of 0.8 mL/min to react, and time and monitor the conductivity value;
(5)当所述第一反应液滴加完毕5min后，开始向所述反应体系中以0.8mL/min的速率匀速滴加10mL第三反应液；所述第三反应液配置方法如下：将0.9g硝酸银溶于15mL乙二醇中，获得第三反应液。(5) When the first reaction solution is added dropwise for 5 minutes, start adding 10 mL of the third reaction solution uniformly into the reaction system at a rate of 0.8 mL/min; the preparation method of the third reaction solution is as follows: Dissolve 0.9g silver nitrate in 15mL ethylene glycol to obtain the third reaction solution.
反应过程中持续观察电导率测试仪中电导率的变化，待反应结束后，将最终产物进行制样测SEM。During the reaction process, continue to observe the changes in conductivity in the conductivity tester. After the reaction is completed, prepare a sample of the final product for SEM measurement.
对比例1Comparative example 1
本对比例提供一种制备银纳米线的方法，所述方法除了不滴加第三反应液外，其他与实施例1相同，具体包括以下步骤：This comparative example provides a method for preparing silver nanowires. The method is the same as Example 1 except that the third reaction solution is not dropped, and specifically includes the following steps:
(1)将3g硝酸银溶于15mL乙二醇中，获得第一反应液；(1) Dissolve 3g silver nitrate in 15mL ethylene glycol to obtain the first reaction solution;
(2)将6gPVP和0.03gKCl溶于500mL乙二醇中，获得第二反应液；将第二反应液置于500mL烧瓶中，并***在线电导率测试仪电极；(2) Dissolve 6gPVP and 0.03gKCl in 500mL ethylene glycol to obtain the second reaction liquid; place the second reaction liquid in a 500mL flask and insert the online conductivity tester electrode;
(3)加热所述第二反应液，升温到140℃并保持恒定；(3) Heat the second reaction liquid to a temperature of 140°C and keep it constant;
(4)进行首轮滴加：向所述第二反应液中以0.75mL/min的速率匀速滴加所述第一反应液进行反应，并计时和监测电导率数值。(4) Perform the first round of dropwise addition: add the first reaction solution dropwise to the second reaction solution at a constant rate of 0.75 mL/min to react, and time and monitor the conductivity value.
反应过程中持续观察电导率测试仪中电导率的变化，待反应结束后，将最终产物进行制 样测SEM。During the reaction process, continue to observe the changes in conductivity in the conductivity tester. After the reaction is completed, prepare the final product. Sample test SEM.
对比例2Comparative example 2
本对比例提供一种制备银纳米线的方法，所述方法除了滴加第三反应液的时间不同外，其他与实施例1相同，具体包括以下步骤：This comparative example provides a method for preparing silver nanowires. The method is the same as Example 1 except that the time for dropping the third reaction solution is different, and specifically includes the following steps:
(1)将3g硝酸银溶于15mL乙二醇中，获得第一反应液；(1) Dissolve 3g silver nitrate in 15mL ethylene glycol to obtain the first reaction solution;
(2)将6gPVP和0.03gKCl溶于500mL乙二醇中，获得第二反应液；将第二反应液置于500mL烧瓶中，并***在线电导率测试仪电极；(2) Dissolve 6gPVP and 0.03gKCl in 500mL ethylene glycol to obtain the second reaction liquid; place the second reaction liquid in a 500mL flask and insert the online conductivity tester electrode;
(3)加热所述第二反应液，升温到140℃并保持恒定；(3) Heat the second reaction liquid to a temperature of 140°C and keep it constant;
(4)进行首轮滴加：向所述第二反应液中以0.75mL/min的速率匀速滴加所述第一反应液进行反应，并计时和监测电导率数值；(4) Perform the first round of dropping: add the first reaction solution dropwise to the second reaction solution at a constant rate of 0.75 mL/min to react, and time and monitor the conductivity value;
(5)当所述第一反应液滴加完毕25min后，开始向所述反应体系中以0.75mL/min的速率匀速滴加15mL第三反应液；所述第三反应液配置方法如下：将0.15g硝酸银溶于15mL乙二醇中，获得第三反应液。(5) 25 minutes after the addition of the first reaction solution is completed, 15 mL of the third reaction solution is added dropwise into the reaction system at a constant rate of 0.75 mL/min; the preparation method of the third reaction solution is as follows: Dissolve 0.15g silver nitrate in 15mL ethylene glycol to obtain the third reaction solution.
反应过程中持续观察电导率测试仪中电导率的变化，待反应结束后，将最终产物进行制样测SEM。During the reaction process, continue to observe the changes in conductivity in the conductivity tester. After the reaction is completed, prepare a sample of the final product for SEM measurement.
对比例3Comparative example 3
本对比例提供一种制备银纳米线的方法，所述方法除了滴加的第三反应液的银盐的质量浓度不同外，其他与实施例1相同，所述方法包括以下步骤：This comparative example provides a method for preparing silver nanowires. The method is the same as Example 1 except that the mass concentration of the silver salt in the third reaction solution dropped is different. The method includes the following steps:
(1)将3g硝酸银溶于15mL乙二醇中，获得第一反应液；(1) Dissolve 3g silver nitrate in 15mL ethylene glycol to obtain the first reaction solution;
(2)将6gPVP和0.03gKCl溶于500mL乙二醇中，获得第二反应液；将第二反应液置于500mL烧瓶中，并***在线电导率测试仪电极；(2) Dissolve 6gPVP and 0.03gKCl in 500mL ethylene glycol to obtain the second reaction liquid; place the second reaction liquid in a 500mL flask and insert the online conductivity tester electrode;
(3)加热所述第二反应液，升温到140℃并保持恒定；(3) Heat the second reaction liquid to a temperature of 140°C and keep it constant;
(4)进行首轮滴加：向所述第二反应液中以0.75mL/min的速率匀速滴加所述第一反应液进行反应，并计时和监测电导率数值；(4) Perform the first round of dropping: add the first reaction solution dropwise to the second reaction solution at a constant rate of 0.75 mL/min to react, and time and monitor the conductivity value;
(5)当所述第一反应液滴加完毕10min后，开始向所述反应体系中以0.75mL/min的速率匀速滴加15mL第三反应液；所述第三反应液配置方法如下：将2g硝酸银溶于15mL乙二醇中，获得第三反应液。(5) When the first reaction solution is added dropwise for 10 minutes, start adding 15 mL of the third reaction solution uniformly into the reaction system at a rate of 0.75 mL/min; the preparation method of the third reaction solution is as follows: Dissolve 2g of silver nitrate in 15mL of ethylene glycol to obtain the third reaction solution.
反应过程中持续观察电导率测试仪中电导率的变化，待反应结束后，将最终产物进行制样测SEM。 During the reaction process, continue to observe the changes in conductivity in the conductivity tester. After the reaction is completed, prepare a sample of the final product for SEM measurement.
以上实施例和对比例的检测结果如下：The test results of the above examples and comparative examples are as follows:
实施例1(图中以二次滴加表示)和对比例1(图中以一次滴加表示)中反应体系的的电导率变化图如图1所示，由图1可知，实施例1通过控制二次滴加第三反应液，成功延长了平台期(银纳米线生长中的成核阶段)。The conductivity change diagram of the reaction system in Example 1 (represented by two drops in the figure) and Comparative Example 1 (represented by one drop in the figure) is shown in Figure 1. It can be seen from Figure 1 that Example 1 passes Controlling the second dropwise addition of the third reaction solution successfully extended the plateau period (the nucleation stage in the growth of silver nanowires).
与对比例1相比，实施例1制备获得的银纳米线的直径明显变小(图2)，长度明显变大(图3)，副产物银纳米颗粒含量明显下降，银纳米线产量和纯度明显提升(图4)。Compared with Comparative Example 1, the diameter of the silver nanowires prepared in Example 1 is significantly smaller (Figure 2), the length is significantly larger (Figure 3), the content of by-product silver nanoparticles is significantly reduced, and the yield and purity of silver nanowires are significantly reduced. Significant improvement (Figure 4).
对比例2在第一反应液滴加完毕25min后才开始滴加第三反应液，与实施例1相比，其制备获得的银纳米线的长径比较更大、产量更低，且副产物数量增多；对比例2中银纳米线的产量和长径比与对比例1无明显差别(图2)。这是因为第三反应液的滴加于银纳米线生长快结束的阶段，新加入的银离子只能在溶液中被还原为银原子而不能用于生成银纳米线。In Comparative Example 2, the third reaction solution was added dropwise only 25 minutes after the first reaction solution was added. Compared with Example 1, the length-to-diameter ratio of the silver nanowires prepared was larger, the yield was lower, and the by-products were The quantity increased; the yield and aspect ratio of silver nanowires in Comparative Example 2 were not significantly different from those in Comparative Example 1 (Figure 2). This is because the third reaction solution is added dropwise at the end of the growth of silver nanowires, and the newly added silver ions can only be reduced to silver atoms in the solution and cannot be used to generate silver nanowires.
对比例3滴加的第三反应液浓度不在本发明范围内，导致产物中的银纳米线长度和直径不均匀，含有大量银纳米短棒和银纳米颗粒，产出的银纳米线的纯度降低(图2)。The concentration of the third reaction solution dropped in Comparative Example 3 is not within the scope of the present invention, resulting in uneven length and diameter of the silver nanowires in the product, containing a large number of silver nanorods and silver nanoparticles, and reducing the purity of the produced silver nanowires. (figure 2).
实施例2～3中反应体系的的电导率变化图以及制备获得的银纳米线产量和质量与实施例相似，具体数据省略。The conductivity change diagram of the reaction system and the yield and quality of the prepared silver nanowires in Examples 2 to 3 are similar to those in the Examples, and the specific data are omitted.
综上所述，本发明通过在合适的时间点滴加合适量的银盐溶液，可以明显提高银纳米线产量和纯度，可以合成纯度更高、长径比更大的银纳米线。To sum up, by adding an appropriate amount of silver salt solution at an appropriate time point, the present invention can significantly improve the yield and purity of silver nanowires, and can synthesize silver nanowires with higher purity and larger aspect ratio.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对以上实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above embodiments can be combined in any way. To simplify the description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, All should be considered to be within the scope of this manual.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。 The above-mentioned embodiments only express several implementation modes of the present invention. The descriptions are relatively specific and detailed, but should not be construed as limiting the patent scope of the present invention. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the scope of protection of the patent of the present invention should be determined by the appended claims.

Claims (10)

  1. 一种制备银纳米线的方法，其特征在于，包括以下步骤：(1)将银盐溶于多元醇中，得到第一反应液；(2)将聚乙烯吡咯烷酮和可溶性卤盐溶于多元醇中，得到第二反应液；(3)加热所述第二反应液，达到目标温度后保持恒定；(4)向所述第二反应液中滴加所述第一反应液进行反应；(5)当所述第一反应液滴加完毕后，于20min内开始向所述反应体系中滴加第三反应液；所述第三反应液的组成与所述第二反应液相同，但银盐的质量浓度小于所述第二反应液。A method for preparing silver nanowires, characterized by comprising the following steps: (1) dissolving silver salt in polyol to obtain a first reaction solution; (2) dissolving polyvinylpyrrolidone and soluble halide salt in polyol in, obtain the second reaction liquid; (3) heat the second reaction liquid and keep it constant after reaching the target temperature; (4) drop the first reaction liquid into the second reaction liquid to react; (5) ) After the first reaction liquid has been added dropwise, start adding the third reaction liquid dropwise into the reaction system within 20 minutes; the composition of the third reaction liquid is the same as that of the second reaction liquid, except that the silver salt The mass concentration is less than that of the second reaction liquid.
  2. 如权利要求1所述的制备银纳米线的方法，其特征在于，步骤(5)中当所述第一反应液滴加完毕后，于0.5～20min内开始向所述反应体系中加入第三反应液。The method for preparing silver nanowires according to claim 1, characterized in that, in step (5), after the dropwise addition of the first reaction liquid is completed, the third reaction liquid is added to the reaction system within 0.5 to 20 minutes. The reaction solution.
  3. 如权利要求1所述的制备银纳米线的方法，其特征在于，步骤(5)中当所述第一反应液滴加完毕后，于1.5～20min内开始向所述反应体系中加入第三反应液。The method for preparing silver nanowires according to claim 1, characterized in that, in step (5), after the dropwise addition of the first reaction liquid is completed, the third reaction liquid is added to the reaction system within 1.5 to 20 minutes. The reaction solution.
  4. 如权利要求1所述的制备银纳米线的方法，其特征在于，步骤(5)中当所述第一反应液滴加完毕后，于5～15min内开始向所述反应体系中加入第三反应液。The method for preparing silver nanowires according to claim 1, characterized in that, in step (5), after the dropwise addition of the first reaction liquid is completed, the third reaction liquid is added to the reaction system within 5 to 15 minutes. The reaction solution.
  5. 如权利要求1所述的制备银纳米线的方法，其特征在于，所述第三反应液中银盐的质量浓度为所述第一反应液的0.05～0.5倍。The method of preparing silver nanowires according to claim 1, wherein the mass concentration of silver salt in the third reaction solution is 0.05 to 0.5 times that of the first reaction solution.
  6. 如权利要求1所述的制备银纳米线的方法，其特征在于，所述第三反应液中银盐的质量浓度为所述第一反应液的0.05～0.4倍；优选地，所述第三反应液中银盐的质量浓度为所述第一反应液的0.1～0.4倍。The method for preparing silver nanowires according to claim 1, wherein the mass concentration of silver salt in the third reaction solution is 0.05 to 0.4 times that of the first reaction solution; preferably, the third reaction solution The mass concentration of the silver salt in the liquid is 0.1 to 0.4 times that of the first reaction liquid.
  7. 如权利要求1所述的制备银纳米线的方法，其特征在于，所述第三反应液与第一反应液的体积比为(0.3～1)：1；优选地，所述第三反应液与第一反应液的体积比为(0.5～1)：1。The method for preparing silver nanowires according to claim 1, wherein the volume ratio of the third reaction liquid to the first reaction liquid is (0.3-1):1; preferably, the third reaction liquid The volume ratio to the first reaction liquid is (0.5~1):1.
  8. 如权利要求1～7任一项所述的制备银纳米线的方法，其特征在于，所述第一反应液中银盐的质量浓度为0.1～0.35g/mL；和/或，所述第二反应液中聚乙烯吡咯烷酮的质量浓度为10～20g/L，可溶性卤盐的质量浓度为0.05～0.2g/L。The method for preparing silver nanowires according to any one of claims 1 to 7, wherein the mass concentration of silver salt in the first reaction solution is 0.1 to 0.35g/mL; and/or the second reaction solution The mass concentration of polyvinylpyrrolidone in the reaction solution is 10-20g/L, and the mass concentration of the soluble halide salt is 0.05-0.2g/L.
  9. 如权利要求1～7任一项所述的制备银纳米线的方法，其特征在于，所述目标温度为120～150℃；和/或，所述第一反应液的滴加速率为0.5～0.9mL/min；和/或，所述第三反应液的滴加速率为0.5～0.9mL/min。The method for preparing silver nanowires according to any one of claims 1 to 7, wherein the target temperature is 120-150°C; and/or the dropping acceleration rate of the first reaction liquid is 0.5-150°C. 0.9 mL/min; and/or, the dripping acceleration rate of the third reaction liquid is 0.5-0.9 mL/min.
  10. 如权利要求1～7任一项所述的制备银纳米线的方法，其特征在于，所述银盐选自硝酸银；和/或，所述多元醇选自乙二醇、丙三醇、1，5-戊二醇和1，3-丙二醇中的至少一种；和/或，所述可溶性卤盐选自氯化钠、氯化钾、溴化钠和溴化钾中的至少一种。 The method for preparing silver nanowires according to any one of claims 1 to 7, wherein the silver salt is selected from silver nitrate; and/or the polyol is selected from ethylene glycol, glycerol, At least one of 1,5-pentanediol and 1,3-propanediol; and/or the soluble halide salt is selected from at least one of sodium chloride, potassium chloride, sodium bromide and potassium bromide.
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