WO2021232648A1 - Device for macro-purifying metal-based nanowire - Google Patents

Device for macro-purifying metal-based nanowire Download PDF

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WO2021232648A1
WO2021232648A1 PCT/CN2020/117146 CN2020117146W WO2021232648A1 WO 2021232648 A1 WO2021232648 A1 WO 2021232648A1 CN 2020117146 W CN2020117146 W CN 2020117146W WO 2021232648 A1 WO2021232648 A1 WO 2021232648A1
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filter
stirring
filtering
metal
macro
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唐宏浩
叶怀宇
张国旗
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深圳第三代半导体研究院
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B04CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
    • B04BCENTRIFUGES
    • B04B5/00Other centrifuges
    • B04B5/12Centrifuges in which rotors other than bowls generate centrifugal effects in stationary containers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B04CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
    • B04BCENTRIFUGES
    • B04B7/00Elements of centrifuges
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes

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  • the utility model relates to the field of nano-material preparation, in particular to a device for macro-purifying metal-based nanowires.
  • the polyol method is most commonly used at present (using PVP as a capping agent and high-boiling ethylene glycol as a solvent and reducing agent) to obtain metal nanowires with suitable size and aspect ratio.
  • PVP a capping agent
  • high-boiling ethylene glycol as a solvent and reducing agent
  • metal nanowires with suitable size and aspect ratio have better mechanical and optoelectronic properties. Therefore, based on this theory, a lot of research work is devoted to improving the synthesis method to prepare metal nanowires with ultra-long-diameter ratio.
  • the currently reported methods for preparing metal nanowires with ultra-length-to-diameter ratios have inherent shortcomings, such as complex processes and cumbersome steps, which are not conducive to large-scale and reproducible preparation in actual production.
  • improving the photoelectric performance of the transparent electrode by increasing the aspect ratio also has side effects.
  • the diameter of the metal nanowire reduces the actual conductive coverage area in the transparent electrode, which is detrimental to charge collection in optoelectronic devices.
  • Another method is to improve the photoelectric performance of metal nanowires from the source without changing the aspect ratio of the metal nanowires. Impurities such as non-conductive polymer PVP, metal nanoparticles, nano short rods and so on that wrap the metal nanowires are removed by purification. Conventional centrifugal washing is the most commonly used method. However, this method is inefficient and takes a long time. Excessive centrifugation can also cause metal nanowires to agglomerate.
  • the dynamic stirring centrifugal filtration device includes:
  • the dynamic stirring centrifugal filter device includes: a filter base, a solution injection system, a filter cylinder, and a filtrate outflow system;
  • the filter cylinder includes a filter frame, a stirring device, and a filter membrane; the filter membrane includes a first filter area, a second filter area, and a third filter area in the vertical direction.
  • the first filter area, the second filter area The inward included angle between any two of the filter area and the third filter area is less than 180 degrees, and a plurality of filter holes are distributed on the first filter area, the second filter area and the third filter area.
  • the first filter area, the second filter area, and the third filter area are at an angle to each other, which will increase the filter area of the filter membrane and improve the filter efficiency.
  • the direction toward the stirring paddle is an inward direction.
  • the pore sizes of the filter holes on the first filter zone, the second filter zone and the third filter zone are different.
  • the pore size of the first filtration region is 100 nm-1 ⁇ m, and/or the pore size of the second filtration region is 1 ⁇ m-5 ⁇ m, and/or the pore size of the third filtration region is 5 ⁇ m-20 ⁇ m.
  • the stirring device includes an electric motor and a stirring paddle connected to the electric motor.
  • the filtering device includes a stirring paddle selected from one of a single-screw stirring paddle, a double-screw stirring paddle, a single-hole stirring paddle, and a porous stirring paddle.
  • the stirring device includes an electric motor and a stirring paddle connected with the electric motor.
  • the solution injection system injects the replacement solvent during the stirring and filtration to ensure that the concentration of the metal-based nanowires in the stirring centrifugal filter cylinder is relatively stable during the filtration process, and the filtrate flows out of the collection system to collect the filtered by-products.
  • a method for purifying metal-based nanowires using the above-mentioned macro-purifying metal-based nanowire device includes the following steps:
  • the metal-based nanowires are: gold, silver, copper, iron, aluminum, nickel, tin, and the foregoing metal oxides.
  • the diluent is selected from one or more of ethanol, isopropanol, alcohol, distilled water, acetone, n-hexane, and ethyl acetate.
  • the dilution concentration of the metal-based nanowire mother liquor in S1 is 0.2 mg/mL-1.2 mg/mL.
  • the stirring speed is 300-1200 revolutions/min.
  • the filtration pressure comes from the centrifugal force generated when the liquid is stirred, which can be controlled by the stirring speed;
  • the three filter membranes are fixed on the filter tank through the framework of the filter tank, which has a larger filter area compared with the traditional filter and improves the filtration efficiency;
  • the shear force generated by the stirring can clean the surface of the filter membrane, prevent nanowires from gathering and blocking the filter pores of the filter membrane, reducing subsequent filtration efficiency and continuous filtration capacity.
  • the setting of filter membranes with different pore diameters is beneficial to extend the filter membrane The service life of the filter membrane is also realized repeatedly, and the cost is reduced;
  • the solvent can be replaced by a variety of target solvents after the metal nanowires are concentrated through the solution injection system;
  • the purification, concentration and solvent exchange of the nanowires can be realized in one step during stirring, which simplifies the post-treatment process.
  • the device basically solves the core problems of cumbersome steps, complicated processes, and high costs faced by the current industrialized preparation and purification of metal nanowires.
  • Figure 1 is a schematic diagram of an apparatus for macro-purification of metal-based nanowires.
  • This embodiment provides a method for macro-purifying metal-based nanowires, and the experimental device is shown in FIG. 1.
  • the first filter area has a filter pore size of 0.1 ⁇ m
  • the second filter area has a filter pore size of 1 ⁇ m
  • the third filter area filters
  • the hole size is 10 ⁇ m
  • the stirring speed is set at 500 revolutions per minute
  • the double screw stirring paddle is used
  • the rinsing solvent is set to ethanol.
  • This embodiment provides a method for macro-purifying metal-based nanowires, and the experimental device is shown in FIG. 1.
  • the first filter area has a filter pore size of 0.2 ⁇ m
  • the second filter area has a filter pore size of 2 ⁇ m
  • the third filter The size of the regional filter hole is 15 ⁇ m
  • the stirring speed is set at 800 rpm
  • a porous screw stirring paddle is used
  • the rinsing solvent is set to isopropanol.
  • This embodiment provides a method for macro-purifying metal-based nanowires, and the experimental device is shown in FIG. 1.
  • the pore size is 20 ⁇ m
  • the stirring speed is set at 500 rpm
  • a single-hole stirring paddle is used
  • the rinsing solvent is set to distilled water.
  • the process conditions and raw materials used in this comparative example are the same as those in Example 1, except that the filter membrane is installed on the stirring filter rod in a vertical direction.

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Abstract

A device for macro-purifying a metal-based nanowire, comprising a dynamic stirring and centrifugal filtering device, wherein the dynamic stirring and centrifugal filtering device comprises: a solution injection system, a filtering cylinder and a filtrate outflow system. The filtering cylinder comprises a filtering framework, a stirring device and a filtering membrane, wherein the filtering membrane sequentially comprises, in a perpendicular direction, a first filtering region, a second filtering region and a third filtering region; an inward included angle between any two of the first filtering region, the second filtering region and the third filtering region is less than 180 degrees; and a plurality of filtering holes are provided on the first filtering region, the second filtering region and the third filtering region. The device basically solves the core problems of tedious steps, a complex process, high costs, etc. suffered during industrial preparation and a purification post-treatment of a metal-based nanowire at present.

Description

一种宏量提纯金属基纳米线的装置Device for macro-purifying metal-based nanowires 技术领域Technical field
本实用新型涉及纳米材料制备领域,尤其涉及一种宏量提纯金属基纳米线的装置。The utility model relates to the field of nano-material preparation, in particular to a device for macro-purifying metal-based nanowires.
背景技术Background technique
近年来,柔性透明电极在可穿戴、柔性、半透明电子产品和器件中的应用越来越受关注,其应用范围涵盖传感器、触摸屏、人造皮肤、晶体管和光学显示器等器件。这种受重视的原因部分归因于新技术新材料的发展,因而促使其在多领域的应用。具体到柔性透明电极上,目前市售的氧化铟锡(ITO)导电透明膜在应用于柔性透明电极时存在其内在的局限性,如制备成本高、导电面粗糙度高、材料脆性差、柔韧性差等缺点。基于这些问题,为制备低成本、机械性能好和柔韧性好的柔性透明电极,几种可替代的导电材料如碳纳米管、石墨烯、导电聚合物、金属网格和金属纳米线受到研究者的重视。其中碳基和聚合物基材料由于固有电导率低因而其光电性能受到限制;金属网格导电性好,但存在莫瑞干涉效应,尽管莫瑞效应可以通过降低金属网格线宽来消除,如采用黄光制程工艺实现,相应的制备成本也极大的增加。和前面的材料相比,金属纳米线导电网络在光电性能和清晰度方面具有优势,其纳米尺度的导电网络宽度,完全消除了莫瑞干涉效应,因而有着最好的应用前景。In recent years, the application of flexible transparent electrodes in wearable, flexible, and translucent electronic products and devices has attracted more and more attention, and its application range covers sensors, touch screens, artificial skin, transistors, and optical displays. The reason for this attention is partly attributed to the development of new technologies and new materials, which promotes its application in many fields. Specifically for flexible transparent electrodes, currently commercially available conductive transparent indium tin oxide (ITO) films have inherent limitations when applied to flexible transparent electrodes, such as high production costs, high conductive surface roughness, poor material brittleness, and flexibility Shortcomings such as poor sex. Based on these problems, several alternative conductive materials such as carbon nanotubes, graphene, conductive polymers, metal grids, and metal nanowires have been studied by researchers in order to prepare flexible transparent electrodes with low cost, good mechanical properties and good flexibility. Attention. Among them, carbon-based and polymer-based materials have limited photoelectric performance due to their inherent low conductivity; metal grids have good electrical conductivity, but there is a Murray interference effect, although the Murray effect can be eliminated by reducing the line width of the metal grid, such as It is realized by adopting the yellow light process technology, and the corresponding preparation cost is also greatly increased. Compared with the previous materials, the conductive network of metal nanowires has advantages in terms of photoelectric performance and clarity. Its nano-scale conductive network width completely eliminates the Murray interference effect, so it has the best application prospects.
然而,在金属纳米线的制备环节,目前还存在一些工艺上的问题需要解决。比如,为了获得高质量的、完整的并且具有优异光电性能的金属纳米线,往往需要花费大量的人力以及金钱对制备的金属纳米线进行后处理纯化,这不利于控制生产成本。基于金属纳米线的透明电极的性能取决于三个过程:(1)合成的金属纳米线的长径比及其尺寸大小的单分散性;(2)纳米线纯化的纯度,后 处理除去纳米短棒、颗粒以及作为表面活性剂的聚合物;(3)纳米线涂布成膜时导电网络的均匀性。关于第一个过程,目前最常采用多元醇法制备(利用PVP作为封端剂以及高沸点乙二醇作为溶剂和还原剂),以得到尺寸和长径比合适的金属纳米线。根据渗流理论,长径比更高的金属纳米线具有更优异的机械和光电性能。因而基于这一理论,很多研究工作致力于改进合成方法以制备超长径比的金属纳米线。但是,目前报道的制备超长径比的金属纳米线方法存在固有的缺点,如工艺复杂、步骤繁琐等,不利于在实际生产中大规模和可重复性的制备。此外,通过提高长径比改善透明电极的光电性能也存在副作用,比如金属纳米线的直径降低透明电极中实际的导电覆盖面积,这在光电子器件中对电荷收集是不利的。另外一个方法就是从源头上在不改变金属纳米线长径比的情况下提升金属纳米线光电性能。通过纯化除去包裹金属纳米线的不导电聚合物PVP、金属纳米颗粒、纳米短棒等杂质。常规的离心洗涤是最常用的方法,然而这个方法效率低下、耗费时间长,过多的离心还会造成金属纳米线团聚。新的方法包括用滤布过滤、正压过滤、以及倾析等得到报道。尽管这些新方法提高了净化效率,但后处理步骤仍然被分解为小规模、多步骤、耗时的过程。此外,交叉流动过滤可以实现同尺寸金属纳米线与金属纳米粒子分离,但该方法产量较低。因此,为进一步提高金属纳米线质量,降低生产成本以实现用于商业应用,有必要进行开发一种工业上可扩展的,高性能的,成本可控的方法,用于大规模提纯金属纳米线。However, in the process of preparing metal nanowires, there are still some process problems that need to be resolved. For example, in order to obtain high-quality, complete metal nanowires with excellent photoelectric properties, it often takes a lot of manpower and money to post-process and purify the prepared metal nanowires, which is not conducive to controlling production costs. The performance of transparent electrodes based on metal nanowires depends on three processes: (1) the aspect ratio of the synthesized metal nanowires and the monodispersity of the size; (2) the purity of the nanowire purification, and the post-processing to remove the nano-shorts Rods, particles and polymers as surfactants; (3) The uniformity of the conductive network when the nanowires are coated and formed into a film. Regarding the first process, the polyol method is most commonly used at present (using PVP as a capping agent and high-boiling ethylene glycol as a solvent and reducing agent) to obtain metal nanowires with suitable size and aspect ratio. According to the percolation theory, metal nanowires with a higher aspect ratio have better mechanical and optoelectronic properties. Therefore, based on this theory, a lot of research work is devoted to improving the synthesis method to prepare metal nanowires with ultra-long-diameter ratio. However, the currently reported methods for preparing metal nanowires with ultra-length-to-diameter ratios have inherent shortcomings, such as complex processes and cumbersome steps, which are not conducive to large-scale and reproducible preparation in actual production. In addition, improving the photoelectric performance of the transparent electrode by increasing the aspect ratio also has side effects. For example, the diameter of the metal nanowire reduces the actual conductive coverage area in the transparent electrode, which is detrimental to charge collection in optoelectronic devices. Another method is to improve the photoelectric performance of metal nanowires from the source without changing the aspect ratio of the metal nanowires. Impurities such as non-conductive polymer PVP, metal nanoparticles, nano short rods and so on that wrap the metal nanowires are removed by purification. Conventional centrifugal washing is the most commonly used method. However, this method is inefficient and takes a long time. Excessive centrifugation can also cause metal nanowires to agglomerate. New methods including filter cloth filtration, positive pressure filtration, and decantation have been reported. Although these new methods have improved purification efficiency, the post-processing steps are still broken down into small-scale, multi-step, and time-consuming processes. In addition, cross-flow filtration can realize the separation of metal nanowires and metal nanoparticles of the same size, but the yield of this method is low. Therefore, in order to further improve the quality of metal nanowires and reduce production costs for commercial applications, it is necessary to develop an industrially scalable, high-performance, and cost-controllable method for large-scale purification of metal nanowires. .
发明内容Summary of the invention
针对上述现有技术中所存在的技术问题,本实用新型提供了一种宏量提纯金属基纳米线的装置,所述动态搅拌离心过滤装置包括:In view of the above-mentioned technical problems in the prior art, the present invention provides a device for macro-purifying metal-based nanowires. The dynamic stirring centrifugal filtration device includes:
所述动态搅拌离心过滤装置包括:过滤底座、溶液注入系统、过滤缸、滤液流出系统;The dynamic stirring centrifugal filter device includes: a filter base, a solution injection system, a filter cylinder, and a filtrate outflow system;
所述过滤缸包括过滤骨架、搅拌装置和过滤膜;所述过滤膜在垂直方向上 依次包括第一过滤区、第二过滤区和第三过滤区,所述第一过滤区、所述第二过滤区和所述第三过滤区任意两个之间向内夹角小于180度,所述第一过滤区、所述第二过滤区和所述第三过滤区上分布有多个过滤孔。The filter cylinder includes a filter frame, a stirring device, and a filter membrane; the filter membrane includes a first filter area, a second filter area, and a third filter area in the vertical direction. The first filter area, the second filter area The inward included angle between any two of the filter area and the third filter area is less than 180 degrees, and a plurality of filter holes are distributed on the first filter area, the second filter area and the third filter area.
第一过滤区域、第二过滤区域、第三过滤区域互成角度,会增加滤膜的过滤面积,提高过滤效率。所述朝向搅拌桨方向为向内方向。The first filter area, the second filter area, and the third filter area are at an angle to each other, which will increase the filter area of the filter membrane and improve the filter efficiency. The direction toward the stirring paddle is an inward direction.
优选地,所述第一过滤区、所述第二过滤区和所述第三过滤区上过滤孔的孔径大小不同。Preferably, the pore sizes of the filter holes on the first filter zone, the second filter zone and the third filter zone are different.
优选地,所述第一过滤区域的孔径为100nm-1μm,和/或,所述第二过滤区域的孔径为1μm-5μm,和/或,所述第三过滤区域的孔径为5μm-20μm。Preferably, the pore size of the first filtration region is 100 nm-1 μm, and/or the pore size of the second filtration region is 1 μm-5 μm, and/or the pore size of the third filtration region is 5 μm-20 μm.
不同孔径滤膜的使用会提高过滤效率,而且也会延长使用寿命。The use of filter membranes with different pore sizes will increase the filtration efficiency and also extend the service life.
优选地,所述搅拌装置包括电动马达和与所述电动马达相连的搅拌桨。Preferably, the stirring device includes an electric motor and a stirring paddle connected to the electric motor.
优选地,所述过滤装置包括搅拌桨,所述搅拌桨选自单螺旋搅拌桨、双螺旋搅拌桨、单孔搅拌桨、多孔搅拌桨中的一种。Preferably, the filtering device includes a stirring paddle selected from one of a single-screw stirring paddle, a double-screw stirring paddle, a single-hole stirring paddle, and a porous stirring paddle.
所述搅拌装置包括电动马达和与所述电动马达相连的搅拌桨。The stirring device includes an electric motor and a stirring paddle connected with the electric motor.
所述溶液注入系统在搅拌过滤时注入置换溶剂,以保证过滤过程中搅拌离心过滤缸内金属基纳米线浓度相对稳定,所述滤液流出收集系统收集滤出的副产物。The solution injection system injects the replacement solvent during the stirring and filtration to ensure that the concentration of the metal-based nanowires in the stirring centrifugal filter cylinder is relatively stable during the filtration process, and the filtrate flows out of the collection system to collect the filtered by-products.
一种使用上述宏量提纯金属基纳米线装置的提纯金属基纳米线的方法,包括以下步骤:A method for purifying metal-based nanowires using the above-mentioned macro-purifying metal-based nanowire device includes the following steps:
S1:使用稀释剂稀释金属基纳米线母液,并通过溶液注入系统注入过滤缸中;S1: Use diluent to dilute the mother liquid of metal-based nanowires and inject it into the filter tank through the solution injection system;
S2:以固定搅拌速度开启搅拌;搅拌时淋洗溶剂经溶液注入系统持续流入以补偿流走的滤液损失;使得处于搅拌状态的金属纳米线的浓度维持相对稳定,并起到置换溶剂的作用;S2: Start the stirring at a fixed stirring speed; while stirring, the elution solvent continuously flows in through the solution injection system to compensate for the loss of the filtrate flowing away; the concentration of the metal nanowires in the stirring state is maintained relatively stable, and the solvent is replaced;
S3:搅拌20-50min停止加入淋洗溶剂,继续搅拌浓缩溶液;S3: Stir for 20-50min, stop adding the rinse solvent, and continue to stir the concentrated solution;
S4:当浓缩溶液浓度达到1mg mL -1-15mg mL -1后,在过滤缸的底部收集纯化 的浓缩液。 S4: When the concentration of the solution was concentrated to reach 1mg mL -1 -15mg mL -1, to collect the purified concentrate at the bottom of the filter cylinder.
优选地,所述金属基纳米线为:金、银、铜、铁、铝、镍、锡以及上述金属氧化物。Preferably, the metal-based nanowires are: gold, silver, copper, iron, aluminum, nickel, tin, and the foregoing metal oxides.
优选地,所述稀释液选自乙醇、异丙醇、酒精、蒸馏水、丙酮、正己烷、乙酸乙酯中的一种或几种。Preferably, the diluent is selected from one or more of ethanol, isopropanol, alcohol, distilled water, acetone, n-hexane, and ethyl acetate.
优选地,S1中金属基纳米线母液稀释浓度为0.2mg/mL-1.2mg/mL。Preferably, the dilution concentration of the metal-based nanowire mother liquor in S1 is 0.2 mg/mL-1.2 mg/mL.
优选地,所述搅拌速度为300-1200转/min。Preferably, the stirring speed is 300-1200 revolutions/min.
本实用新型的有益效果至少包括:The beneficial effects of the utility model include at least:
一、基于搅拌精确调控过滤的压力,过滤的压力来源于液体搅拌时产生的离心力,这可通过搅拌转速控制;1. Accurately control the filtration pressure based on stirring. The filtration pressure comes from the centrifugal force generated when the liquid is stirred, which can be controlled by the stirring speed;
二、具有更大的过滤面积,允许更多的液体同时过滤,三种滤膜通过过滤缸上的骨架固定在过滤缸上,与传统的过滤相比有更大的过滤面积,提高过滤效率;2. It has a larger filter area, allowing more liquid to be filtered at the same time. The three filter membranes are fixed on the filter tank through the framework of the filter tank, which has a larger filter area compared with the traditional filter and improves the filtration efficiency;
三、搅拌产生的剪切力可对滤膜表面清洗,防止纳米线聚集和堵塞滤膜滤孔,降低后续过滤效率和持续过滤能力,此外,通过不同孔径的滤膜设置,有利于延长滤膜的使用寿命,同时也实现了滤膜的反复利用,降低了成本;3. The shear force generated by the stirring can clean the surface of the filter membrane, prevent nanowires from gathering and blocking the filter pores of the filter membrane, reducing subsequent filtration efficiency and continuous filtration capacity. In addition, the setting of filter membranes with different pore diameters is beneficial to extend the filter membrane The service life of the filter membrane is also realized repeatedly, and the cost is reduced;
四、可通过溶液注入系统将金属纳米线浓缩后溶剂置换为多种目标溶剂;4. The solvent can be replaced by a variety of target solvents after the metal nanowires are concentrated through the solution injection system;
五、纳米线的提纯、浓缩和溶剂换相可在搅拌中一步实现,简化了后处理工艺。该装置基本解决了目前金属纳米线工业化制备和纯化后处理所面临的步骤繁琐、工艺复杂、成本高昂等核心难题。5. The purification, concentration and solvent exchange of the nanowires can be realized in one step during stirring, which simplifies the post-treatment process. The device basically solves the core problems of cumbersome steps, complicated processes, and high costs faced by the current industrialized preparation and purification of metal nanowires.
附图说明Description of the drawings
图一为宏量提纯金属基纳米线的装置示意图。Figure 1 is a schematic diagram of an apparatus for macro-purification of metal-based nanowires.
具体实施方式Detailed ways
下面结合本实用新型实施例中的附图,对本实用新型实施例中的技术方案 进行清楚、完整地描述,显然,所描述的实施例仅是本实用新型一部分实施例,而不是全部的实施例。基于本实用新型中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本实用新型保护范围。The following describes the technical solutions in the embodiments of the present utility model clearly and completely with reference to the drawings in the embodiments of the present utility model. Obviously, the described embodiments are only a part of the embodiments of the present utility model, rather than all the embodiments. . Based on the embodiments of the present utility model, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present utility model.
实施例1Example 1
本实施例提供一种宏量提纯金属基纳米线的方法,实验装置如图1所示。This embodiment provides a method for macro-purifying metal-based nanowires, and the experimental device is shown in FIG. 1.
1.母液稀释处理以及搅拌过滤离心装置的预设置。1. Pre-setting of mother liquor dilution treatment and stirring, filtering and centrifugal device.
将铜纳米线母液用乙醇稀释至浓度0.5mg/mL,在搅拌过滤杠上装上滤膜,第一过滤区域滤孔尺寸为0.1μm,第二过滤区域滤孔尺寸为1μm,第三过滤区域滤孔尺寸为10μm,搅拌速度设置在500转/分钟,采用双螺旋搅拌桨,淋洗溶剂设置为乙醇。Dilute the copper nanowire mother liquor with ethanol to a concentration of 0.5 mg/mL, install a filter membrane on the stirring filter bar, the first filter area has a filter pore size of 0.1 μm, the second filter area has a filter pore size of 1 μm, and the third filter area filters The hole size is 10 μm, the stirring speed is set at 500 revolutions per minute, the double screw stirring paddle is used, and the rinsing solvent is set to ethanol.
2.搅拌过滤浓缩。2. Stirring, filtering and concentrating.
将300毫升稀释液倒入装有过滤膜的搅拌离心过滤缸中,开启搅拌,淋洗溶剂从过滤装置的上方经溶液注入系统持续流入以补偿流走的滤液损失,使得处于搅拌状态的铜纳米线的浓度维持相对稳定,并起到置换溶剂的作用。经过30min时间的搅拌过滤后,停止加入淋洗溶剂,同时继续搅拌使溶液浓缩成所需的浓度(5mg mL -1),所需浓缩时间为40min。最后在搅拌离心过滤缸的底部收集纯化的纳米线浓缩液。 Pour 300 ml of diluent into a stirred centrifugal filter tank equipped with a filter membrane, turn on the stirring, and the rinsing solvent will continue to flow in from the top of the filter device through the solution injection system to compensate for the loss of filtrate flowing away, so that the copper nanometer is in a stirred state. The concentration of the thread remains relatively stable and acts as a replacement for the solvent. After 30 minutes of stirring and filtering, stop adding the rinse solvent while continuing to stir to concentrate the solution to the required concentration (5 mg mL -1 ). The required concentration time is 40 minutes. Finally, the purified nanowire concentrate is collected at the bottom of the stirred centrifugal filter tank.
实施例2Example 2
本实施例提供一种宏量提纯金属基纳米线的方法,实验装置如图1所示。This embodiment provides a method for macro-purifying metal-based nanowires, and the experimental device is shown in FIG. 1.
1.母液稀释处理以及搅拌过滤离心装置的预设置。1. Pre-setting of mother liquor dilution treatment and stirring, filtering and centrifugal device.
将银纳米线母液用异丙醇稀释至浓度0.5mg/mL,在搅拌过滤杠上装上滤膜,第一过滤区域滤孔尺寸为0.2μm,第二过滤区域滤孔尺寸为2μm,第三过滤区域滤孔尺寸为15μm,搅拌速度设置在800转/分钟,采用多孔螺旋搅拌桨,淋洗溶剂设置为异丙醇。Dilute the silver nanowire mother liquor with isopropanol to a concentration of 0.5 mg/mL, install a filter membrane on the stirring filter bar, the first filter area has a filter pore size of 0.2 μm, the second filter area has a filter pore size of 2 μm, and the third filter The size of the regional filter hole is 15 μm, the stirring speed is set at 800 rpm, a porous screw stirring paddle is used, and the rinsing solvent is set to isopropanol.
2.搅拌过滤浓缩。2. Stirring, filtering and concentrating.
将300毫升稀释液倒入装有过滤膜的搅拌离心过滤缸中,开启搅拌,淋洗溶剂从过滤装置的上方经溶液注入系统持续流入以补偿流走的滤液损失,使得处于搅拌状态的银纳米线的浓度维持相对稳定,并起到置换溶剂的作用。经过30min时间的搅拌过滤后,停止加入淋洗溶剂,同时继续搅拌使溶液浓缩成所需的浓度(8mg mL -1)所需浓缩时间为30min。最后在搅拌离心过滤缸的底部收集纯化的纳米线浓缩液。 Pour 300 ml of diluent into a stirred centrifugal filter tank equipped with a filter membrane, turn on the stirring, and the rinsing solvent will continue to flow in from the top of the filter device through the solution injection system to compensate for the loss of the filtrate flowing away, so that the silver nanometers are in a stirred state. The concentration of the thread remains relatively stable and acts as a replacement for the solvent. After 30 minutes of stirring and filtering, stop adding the rinse solvent while continuing to stir to concentrate the solution to the required concentration (8 mg mL -1 ). The required concentration time is 30 minutes. Finally, the purified nanowire concentrate is collected at the bottom of the stirred centrifugal filter tank.
实施例3Example 3
本实施例提供一种宏量提纯金属基纳米线的方法,实验装置如图1所示。This embodiment provides a method for macro-purifying metal-based nanowires, and the experimental device is shown in FIG. 1.
1.母液稀释处理以及搅拌过滤离心装置的预设置。1. Pre-setting of mother liquor dilution treatment and stirring, filtering and centrifugal device.
将金纳米线母液用蒸馏水稀释至浓度0.2mg/mL,在搅拌过滤杠上装上滤膜,第一过滤区域滤孔尺寸为0.5μm,第一过滤区域滤孔尺寸为5μm,第一过滤区域滤孔尺寸为20μm,搅拌速度设置在500转/分钟,采用单孔搅拌桨,淋洗溶剂设置为蒸馏水。Dilute the gold nanowire mother liquor with distilled water to a concentration of 0.2mg/mL, and install a filter membrane on the stirring filter rod. The pore size is 20 μm, the stirring speed is set at 500 rpm, a single-hole stirring paddle is used, and the rinsing solvent is set to distilled water.
2.搅拌过滤浓缩。2. Stirring, filtering and concentrating.
将300毫升稀释液倒入装有过滤膜的搅拌离心过滤缸中,开启搅拌,淋洗溶剂从过滤装置的上方经溶液注入系统持续流入以补偿流走的滤液损失,使得处于搅拌状态的金纳米线的浓度维持相对稳定,并起到置换溶剂的作用。经过10min时间的搅拌过滤后,停止加入淋洗溶剂,同时继续搅拌使溶液浓缩成所需的浓度(5mg mL -1)所需浓缩时间为25min。最后在搅拌离心过滤缸的底部收集纯化的纳米线浓缩液。 Pour 300 ml of diluent into a stirred centrifugal filter tank equipped with a filter membrane, turn on the stirring, and the rinsing solvent will continuously flow in from the top of the filter device through the solution injection system to compensate for the loss of filtrate flowing away, so that the gold nanometers are in a stirred state. The concentration of the thread remains relatively stable and acts as a replacement for the solvent. After 10 minutes of stirring and filtering, stop adding the rinse solvent while continuing to stir to concentrate the solution to the required concentration (5 mg mL -1 ). The concentration time required is 25 minutes. Finally, the purified nanowire concentrate is collected at the bottom of the stirred centrifugal filter tank.
对比例1Comparative example 1
该对比例所使用的工艺条件及原料与实施例1相同,不同之处为搅拌过滤杠上装上滤膜为垂直方向的滤膜。The process conditions and raw materials used in this comparative example are the same as those in Example 1, except that the filter membrane is installed on the stirring filter rod in a vertical direction.
序号Serial number 浓缩浓度Concentrated concentration 所需时间Time required
实施例1Example 1 5mg mL -1 5mg mL -1 40min40min
对比例1Comparative example 1 5mg mL -1 5mg mL -1 150min150min
最后说明的是,以上优选实施例仅用以说明本实用新型的技术方案而非限制,尽管通过上述优选实施例已经对本实用新型进行了详细的描述,但本领域技术人员应当理解,可以在形式上和细节上对其作出各种各样的改变,而不偏离本实用新型权利要求书所限定的范围。Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present utility model and not to limit it. Although the present utility model has been described in detail through the above preferred embodiments, those skilled in the art should understand that it can be in the form Various changes have been made to the above and details without departing from the scope defined by the claims of the present invention.

Claims (5)

  1. 一种宏量提纯金属基纳米线的装置,包括动态搅拌离心过滤装置,其特征在于,所述动态搅拌离心过滤装置包括:溶液注入系统、过滤缸、滤液流出系统;A device for macro-purifying metal-based nanowires, including a dynamic stirring centrifugal filter device, characterized in that the dynamic stirring centrifugal filter device includes: a solution injection system, a filter cylinder, and a filtrate outflow system;
    所述过滤缸包括过滤骨架、搅拌装置和过滤膜;所述过滤膜在垂直方向上依次包括第一过滤区、第二过滤区和第三过滤区,所述第一过滤区、所述第二过滤区和所述第三过滤区任意两个之间向内夹角小于180度,所述第一过滤区、所述第二过滤区和所述第三过滤区上分布有多个过滤孔;所述搅拌装置包括电动马达和与所述电动马达相连的搅拌桨。The filter cylinder includes a filter frame, a stirring device, and a filter membrane; the filter membrane includes a first filter area, a second filter area, and a third filter area in the vertical direction. The first filter area, the second filter area The inward included angle between any two of the filter area and the third filter area is less than 180 degrees, and a plurality of filter holes are distributed on the first filter area, the second filter area, and the third filter area; The stirring device includes an electric motor and a stirring paddle connected with the electric motor.
  2. 如权利要求1所述的一种宏量提纯金属基纳米线的装置,其特征在于,所述第一过滤区、所述第二过滤区和所述第三过滤区上过滤孔的孔径大小不同。The device for macro-purifying metal-based nanowires according to claim 1, wherein the pore sizes of the filter holes on the first filter zone, the second filter zone and the third filter zone are different .
  3. 如权利要求1所述的一种宏量提纯金属基纳米线的装置,其特征在于,所述第一过滤区域的孔径为100nm-1μm,和/或,所述第二过滤区域的孔径为1μm-5μm,和/或,所述第三过滤区域的孔径为5μm-20μm。The apparatus for macro-purification of metal-based nanowires according to claim 1, wherein the pore size of the first filter region is 100 nm-1 μm, and/or the pore size of the second filter region is 1 μm -5 μm, and/or, the pore size of the third filter region is 5 μm-20 μm.
  4. 如权利要求1所述的一种宏量提纯金属基纳米线的装置,其特征在于,所述过滤装置包括搅拌桨,所述搅拌桨选自单螺旋搅拌桨、双螺旋搅拌桨、单孔搅拌桨、多孔搅拌桨中的一种。The device for macro-purification of metal-based nanowires according to claim 1, wherein the filtering device comprises a stirring paddle, and the stirring paddle is selected from the group consisting of single-screw stirring paddles, double-screw stirring paddles, and single-hole stirring paddles. One of paddles and porous stirring paddles.
  5. 如权利要求1所述的一种宏量提纯金属基纳米线的装置,其特征在于,所述溶液注入系统在搅拌过滤时注入置换溶剂,以保证过滤过程中搅拌离心过滤缸内金属基纳米线浓度相对稳定,所述滤液流出收集系统收集滤出的副产物。The device for macro-purification of metal-based nanowires according to claim 1, wherein the solution injection system injects a replacement solvent during the stirring and filtration to ensure that the metal-based nanowires in the centrifugal filter tank are stirred during the filtration process. The concentration is relatively stable, and the filtrate flows out of the collection system to collect the filtered by-products.
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