WO2024045654A1 - Purification system and purification method for metal nanowires - Google Patents

Purification system and purification method for metal nanowires Download PDF

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Publication number
WO2024045654A1
WO2024045654A1 PCT/CN2023/090270 CN2023090270W WO2024045654A1 WO 2024045654 A1 WO2024045654 A1 WO 2024045654A1 CN 2023090270 W CN2023090270 W CN 2023090270W WO 2024045654 A1 WO2024045654 A1 WO 2024045654A1
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purification
metal nanowires
stage
storage tank
microfluidic
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PCT/CN2023/090270
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French (fr)
Chinese (zh)
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詹世治
曾西平
靳世东
彭礼明
林仪珊
王海波
巫春荣
庄桂生
吴俊青
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深圳市华科创智技术有限公司
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Publication of WO2024045654A1 publication Critical patent/WO2024045654A1/en

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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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • 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
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • 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 relates to the technical field of nanomaterial preparation, and in particular to a purification system and purification method of metal nanowires.
  • Transparent conductive electrodes are one of the most important components in optoelectronic devices such as solar cells, light-emitting diodes, touch screens, and displays.
  • the material for transparent conductive electrodes currently widely used on the market is indium tin oxide.
  • indium tin oxide is relatively expensive and easily brittle under bending conditions, so it is not suitable for flexible electronic devices.
  • academic and industrial circles have successively developed flexible nanoconductive materials such as conductive polymers, carbon nanotubes, graphene, and metal nanowires. Among them, metal nanowires have attracted widespread attention due to their low cost, high performance, and ultra-flexibility.
  • metal nanoelectrodes is usually divided into the following steps: synthesis of metal nanowires, purification of metal nanowires, and preparation and coating of metal nanowire ink.
  • the performance of transparent electrodes based on metal nanowires mainly depends on Three processes: (1) the aspect ratio of the synthesized metal nanowires and the monodispersity of their size; (2) the purity of the nanowires, post-processing to remove nanorods, particles and polymers as surfactants ; (3) The uniformity of the conductive network when nanowire coating is used to form a film.
  • the purification of metal nanowires is a key step that determines the production cost and quality of metal nanowire ink.
  • the purity of metal nanowire purification mainly depends on the effectiveness of post-treatment to remove metal nanorods, metal nanoparticles and polymers as surfactants; traditional metal nanowire purification technologies include centrifugation, membrane filtration, and tangential flow. Methods, extraction methods, electrophoretic separation methods, etc. These methods have problems such as cumbersome operations, numerous steps, low purification efficiency, and require a lot of time and solvents.
  • excessive centrifugation can also cause the agglomeration of metal nanowires, which greatly affects The quality of metallic nanowire inks and the optoelectronic properties of transparent electrodes. Therefore, in order to further improve the quality of metal nanowires and reduce production costs for commercial applications, it is necessary to develop an efficient and fast method for large-scale automated purification of metal nanowires.
  • the present invention provides a purification system and purification method for metal nanowires, which use microfluidic technology through multi-stage purification to separate and obtain metal nanowires with a higher degree of purification.
  • a first aspect of the present invention provides a purification system for metal nanowires, including: a storage system, a multi-stage purification system and a control system;
  • the storage system is composed of multiple independent storage tanks, and different materials are stored in the multiple storage tanks;
  • the multi-stage purification system consists of a primary purification device, a secondary purification device and a tertiary purification device connected in sequence; the primary purification device is provided with a filter membrane, and the secondary purification device is provided with a sprinkler head.
  • the three-stage purification device is composed of a microfluidic purification tower. A plurality of glass microbead purification columns and a plurality of microfluidic chip purification columns are arranged in series in the microfluidic purification tower; different materials are stored in the storage system.
  • the tank is connected to various levels of purification devices through pipelines;
  • the control system includes multiple groups of control modules. Multiple groups of the control modules are electrically connected to the storage system and the multi-stage purification system. The control system controls the storage system to the multi-stage purification system through multiple groups of the control modules. , and material transfer between various levels of purification devices in a multi-stage purification system.
  • the microfluidic chip purification column includes multiple microfluidic chips connected in series.
  • the width of the microchannel in the microfluidic chip is 10-500 ⁇ m and the depth is 5-300 ⁇ m.
  • the glass microbead purification column The size of the glass microbeads in the column is 1-30 ⁇ m; preferably, the width of the microchannel in the microfluidic chip is 50 ⁇ m and the depth is 30 ⁇ m, and the size of the glass microbeads in the glass bead purification column is 25 ⁇ m.
  • Microfluidic chips are mainly composed of micron-level channels and chambers. Taking advantage of the laminar flow characteristics of fluids in microchannels, the diffusion speeds of metal nanowires, particles and other impurities are not consistent. Through the series connection of chips, the fluid path can be extended. thereby manipulating the separation of metal nanowires and impurities.
  • the storage tanks of the storage system include metal nanowire slurry storage tanks, desorbent storage tanks, ultrapure water storage tanks and pure water storage tanks.
  • the metal nanowire original slurry storage tank, the desorbent storage tank and the primary purification device are connected through pipelines, and the ultrapure water storage tank and the sprinkler head of the secondary purification device are connected through Pipe connections.
  • a plurality of metering pumps are arranged between the storage tank and the purification devices at each level, and the control system controls the material transfer process and the material transfer amount through the metering pumps.
  • the purification system also includes an enrichment device. After the metal nanowires are purified by the multi-stage purification system, they enter the enrichment device from the three-stage purification device, thereby obtaining the purified metal nanowire suspension; specifically, the Enrichment device microcentrifuge.
  • a mixing device is connected between the secondary purification device and the tertiary purification device, and the mixing device is connected to the pure water storage tank through a metering pump.
  • the mixing device is mainly used to dilute the secondary purification products entering the three-stage purification device so that they can flow out of the purification column.
  • a second aspect of the present invention provides a method for purifying metal nanowires using the above-mentioned purification system for metal nanowires, including the following steps:
  • Three-stage purification add pure water to the secondary purification product to obtain a dilution, place the dilution in a microfluidic tower for separation, collect the separated products, and centrifuge for enrichment to obtain a metal nanowire purification solution.
  • the desorbent described in step (1) is selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone, methyl isobutyl ketone, chlorobenzene, dichlorobenzene, and methylene chloride. , pentane, hexane, octane, benzene, toluene, xylene, chloroform, carbon tetrachloride, trichlorethylene, tetrachlorethylene, trichloropropane, dichloroethane, kerosene, petroleum ether or Several kinds.
  • metal nanowires are nanowires of gold, silver, copper, iron, aluminum, nickel, tin and their oxides.
  • step (1) the dosage ratio of metal nanowire slurry to desorbent is 1: (2-3), the stirring speed is 50-100r/min, and the stirring time is 10-15min.
  • step (2) the ultrapure water spray speed is 50-1000 mL/min, and the spray time is 3-5 min.
  • the microfluidic tower in step (3) is the microfluidic tower in the aforementioned metal nanowire purification system of the present invention, and the outflow rate of the diluent in the microfluidic tower is 50 to 100 ml/min. , at this flow rate, it is possible to ensure purification quality and achieve mass production at the same time.
  • Metal nanowires prepared based on chemical template methods or other methods because metal nanowires are made of gold It is obtained by the continuous deposition of nanoparticles on the surface of the template (usually an organic carrier), so the surface of the prepared metal nanowires is usually attached with an organic carrier, and due to the incomplete deposition of the metal nanoparticles, the prepared metal nanowire slurry It also contains impurities such as nanorods and nanoparticles.
  • the purification system and purification method of the present invention adopt multi-stage step-by-step purification.
  • the primary purification is desorption purification.
  • the desorbent is used to stir and mix the metal nanowire original slurry to separate the metal nanowires from the organic carriers attached to their surfaces.
  • Secondary purification is elution purification, which uses ultrapure water for spraying and uses ultrapure water to entrain and take away water-soluble impurities such as additives in the preparation process of metal nanowires.
  • the third-level purification is microfluidic purification. First, in the glass bead purification column, the solute moves vertically downward and diffuses in an undirected manner. The metal nanowires are difficult to enter the micropores of the glass beads due to their large diameter.
  • the moving speed is relatively fast. Impurities such as metal nanoparticles are small in size and will continue to diffuse into the micropores of the glass beads, resulting in a slower moving speed.
  • the metal nanowires flow out of the glass bead purification column first. ; The metal nanowires that flow out are still mixed with other impurities, and are then placed in a microfluidic chip purification column.
  • the microfluidic chip has micro-sized channels inside. In the microchannels, the fluid will form a well-defined multi-layered structure. Phase parallel flow (laminar flow). At this time, diffusion becomes the main way of mass transfer at the microscale.
  • the diffusion rates are also different, thereby achieving the separation of metal nanowires from other impurities, and by extending their For the diffusion path, multiple groups of microfluidic chips are used in series to further amplify the separation effect and ultimately achieve the purification of metal nanowires.
  • the purification system of metal nanowires of the present invention has simple parts and equipment structures, and low system construction cost; purification is carried out step by step through a multi-stage purification system, and the primary purification uses a desorbent to separate the metal nanowires from the organic carrier.
  • the secondary purification spray removes water-soluble impurities.
  • the third-stage purification uses glass bead purification columns to amplify the separation effect, and uses microfluidic chips to provide microchannels. Laminar flow and differential diffusion are used in the microchannels to separate metal nanowires from other impurities. the final separation.
  • the use of multi-stage automatic purification can improve the purification speed and quality, and achieve mass production of high-purity metal nanowires.
  • the metal nanowire purification system of the present invention also includes a metering pump, a mixing device and an enrichment device on the basis of a storage tank, various levels of purification devices and a control system. It can be built into a fully automated purification system and saves money. Reduce labor costs, improve system stability, and ensure the success rate of the purification process.
  • the purification method of metal nanowires of the present invention adopts desorption-elution-microfluidic purification
  • conventional solvents are used as the desorbent, and only one desorption and washing process is required, which does not waste a large amount of solvent, thereby reducing raw material costs and saving time; and only ultrapure water is used in the elution stage and microfluidic purification stage. and pure water, no new organic solvents will be introduced; microfluidic technology is used for further separation. Due to the differential flow of fluids in the microchannel, the separation effect can be significantly improved and higher purity metal nanowires can be obtained.
  • Figure 1 is a schematic diagram of the purification system of the present invention
  • Figure 2 is a schematic diagram of the microfluidic purification tower of the present invention.
  • Figure 3 is a schematic diagram of the microfluidic chip of the present invention.
  • Figure 4 is a TEM image of the purified silver nanowires obtained in Example 1 of the present invention.
  • Figure 5 is a TEM image of the purified silver nanowires obtained in Comparative Example 1 of the present invention.
  • the purification system of metal nanowires of the present invention includes: a storage system 100, a multi-stage purification system and a control system 800; the storage system 100 is composed of multiple independent storage tanks. Different materials are stored in the material tank; the multi-stage purification system consists of a primary purification device 300, a secondary purification device 400 and a tertiary purification device 600 connected in sequence; the primary purification device 300 is equipped with a filter membrane, and the secondary purification device 400 is equipped with a filter membrane.
  • a shower head is provided, and the three-stage purification device 600 is composed of a microfluidic purification tower.
  • a plurality of glass microbead purification columns 610 and a plurality of microfluidic chip purification columns 620 are arranged in series in the microfluidic purification tower; a storage system Different storage tanks within 100 are connected to various levels of purification devices through pipelines; the control system 800 includes multiple sets of control modules, and the multiple sets of control modules are electrically connected to the storage system 100 and the multi-level purification system.
  • the control system 800 controls the The module controls the material transfer from the storage system 100 to the multi-stage purification system and between various purification devices in the multi-stage purification system.
  • the purification system of metal nanowires of the present invention includes multi-stage purification devices, corresponding to different purification operations, and is provided with a storage system to store materials required for each level of purification operations, and is also provided with a control system to regulate the internal contents of each device. Material transportation and control of the purification conditions of each purification process, thereby realizing the automation of the entire purification process.
  • each group of control modules is used to control the purification process in the primary purification device, the secondary purification device and the tertiary purification device respectively, and optionally includes a signal collection module, a signal analysis module and an execution module according to different objects;
  • the signal collection module is used to collect status information in each purification device, such as material volume, etc.
  • the signal analysis module is connected to the output end of the signal collection module, and compares the status information collected by the signal collection module with the preset threshold. If If the signals match, the corresponding response strategy is activated and instructions are output.
  • the execution module is connected to the output end of the signal analysis module and is used to execute the instructions output by the signal analysis module.
  • Specific coping strategies include, when the required transportation volume of a material reaches a set threshold, shut down the transportation of this material and start the transportation of the next material at the same time, start the corresponding material stirring and heating operations after all set materials are transported, etc.
  • the microfluidic purification tower contains a plurality of glass microbead purification columns 610 and microfluidic chip purification columns 620 arranged in series.
  • the diluted solution is separated in the microfluidic purification tower after passing through multiple glass bead purification columns 610 and multiple microfluidic chip purification columns 620.
  • the microfluidic chip purification column 620 includes multiple microfluidic chips connected in series. 621, in which each microfluidic chip 621 is set horizontally to avoid the effect of gravity on the inner layer of the microfluidic chip. The influence of flow characteristics ensures the separation effect.
  • the width of the microchannel in the microfluidic chip 621 is 50 ⁇ m and the depth is 30 ⁇ m, and the size of the glass beads in the glass bead purification column 610 is 25 ⁇ m.
  • the storage tank 110 of the storage system 100 includes a metal nanowire slurry storage tank 111 , a desorbent storage tank 112 , an ultrapure water storage tank 113 and a pure water storage tank 114 .
  • the metal nanowire slurry storage tank 111 and the desorbent storage tank 112 are connected to the primary purification device 300 through pipelines, and the ultrapure water storage tank 113 is connected to the sprinkler head of the secondary purification device 400 through pipelines. .
  • multiple metering pumps 200 are provided between the storage tank 110 and the purification devices at each level.
  • the control system 800 controls the material transfer process and the material transfer amount through the metering pumps 200;
  • Purification System It also includes an enrichment device 700. After the metal nanowires are purified by the multi-stage purification system, they enter the enrichment device 700 from the three-stage purification device 600, thereby obtaining the purified metal nanowire suspension; the secondary purification device 400 and the three-stage purification device 400.
  • a mixing device 500 is also connected between the first-stage purification devices 600 , and the mixing device 500 and the pure water storage tank 114 are connected through a metering pump 200 .
  • the primary purification device 300 is connected to the metal nanowire slurry storage tank 111 and the desorbent storage tank 112 to obtain the materials required for primary purification (desorption purification), and transfers the primary purification product to the secondary purification device 400.
  • the secondary purification device 400 is connected to the ultrapure water storage tank 113 to obtain the materials required for secondary purification (elution purification), and transfers the secondary purification product to the mixing device 500, which is connected to the pure water storage tank 113.
  • 114 is connected to obtain the materials required for the third-stage purification (microfluidic purification), and the diluted liquid is sent to the third-level purification device 600. After the third-level purification device 600 completes the purification, the purified product is sent to the enrichment device 700 to obtain the metal. Nanowire purification solution.
  • the purification method of metal nanowires using the above purification system includes the following steps:
  • the purification system used in this embodiment is basically the same as that in Embodiment 1, except that the width of the microchannel in the microfluidic chip 621 in the three-stage purification device 600 is 20 ⁇ m and the depth is 10 ⁇ m. The size of the glass beads is 10 ⁇ m.
  • the purification method of metal nanowires using this purification system includes the following steps:
  • the purification system used in this embodiment is basically the same as that in Embodiment 1, except that the width of the microchannel in the microfluidic chip 621 in the three-stage purification device 600 is 200 ⁇ m and the depth is 100 ⁇ m. The size of the glass beads is 30 ⁇ m.
  • the purification method of metal nanowires using this purification system includes the following steps:
  • the specific operation mode of the metal nanowire purification system of the present invention is as follows:
  • Raw material preparation Add metal nanowire slurry, desorbent, ultrapure water and pure water to the corresponding storage tanks 110 of the storage system 100 respectively.
  • the desorbent is pre-prepared and added into the desorbent storage tank 112. The preparation of the desorbent can be as needed. Make component adjustments;
  • the control system 800 is used to transfer the metal nanowire slurry and desorbent from the storage system 100 to the primary purification device 300 through the metering pump 200 according to the pre-designed feeding sequence and raw material addition amount, and start stirring. After the stirring is completed, filtration is performed to obtain the primary purified product; the control system 800 transmits the primary purified product to the secondary purification device 400 and turns on the metering pump 200 connected to the ultrapure water storage tank 113. The ultrapure water flows from the sprinkler head according to the preset setting. The primary purified product is sprayed and cleaned at a certain speed, and the spray liquid overflows downward in real time.
  • the control system 800 transmits the secondary purified product to the mixing device 500 and turns on the The metering pump 200 connected to pure water adds a specified amount of pure water to dilute the secondary purified product and mix it evenly; the control system transmits the diluted secondary purified product to the third-level purification device 600, and in the third-level purification device 600, the diluted The liquid passes through the glass microbead purification column 610 and the microfluidic chip purification column 620 successively to collect the first outflow component. The control system 800 transfers the first outflow component to the enrichment device 700 for centrifugation. After completion, the metal nanowires are obtained. Purified solution. All the above steps are programmed in advance, and then the control system automatically completes the purification process under the preset program.
  • This comparative example uses purified silver nanowires obtained by conventional multiple elution methods. The specific steps are as follows:
  • the silver nanowire original slurry was washed three times with acetone to obtain purified silver nanowires, whose TEM image is shown in Figure 5.
  • the metal nanowires purified by the method of the present invention have higher purity and fewer small particle impurities; while the silver nanowires purified by three times of elution in Comparative Example 1 have obvious problems.
  • the content of silver nanoparticles and silver nanorods is high, and the purification effect is poor.
  • the purification system and purification method of metal nanowires provided in this application can automatically complete the purification process. chemical process, high purification efficiency, greatly shortened purification cycle, and can effectively remove impurities such as metal nanoparticles, metal nanorods and organic additives.
  • the purification effect is good, can be carried out on a large scale, and has good application value.

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Abstract

A purification system and purification method for metal nanowires. The purification system comprises a storage system (100), a multi-stage purification system, and a control system (800); the storage system (100) consists of a plurality of mutually independent storage tanks (110), and the multi-stage purification system consists of a primary purification device (300), a secondary purification device (400) and a tertiary purification device (600) which are connected in sequence; a filter membrane is provided in the primary purification device (300), a spray head is provided in the secondary purification device (400), the tertiary purification device (600) is formed by a microfluidic purification tower, and a plurality of glass bead purification columns (610) and a plurality of microfluidic chip purification columns (620) are arranged in series in the microfluidic purification tower; and the control system (800) controls the storage system (100) to convey materials to the multi-stage purification system and among the purification devices at all stages in the multi-stage purification system. The purification system uses multi-stage purification, such that the purification speed can be increased to the maximum extent, the purification quality is ensured, and purified metal nanowires having relatively low impurity content are obtained.

Description

一种金属纳米线的纯化系统及纯化方法A purification system and purification method for metal nanowires 技术领域Technical field
本发明涉及纳米材料制备技术领域，具体涉及一种金属纳米线的纯化系统及纯化方法。The invention relates to the technical field of nanomaterial preparation, and in particular to a purification system and purification method of metal nanowires.
背景技术Background technique
透明导电电极是太阳能电池、发光二极管、触控屏、显示器等光电器件中最重要的组成部件之一。目前市场上广泛使用的透明导电电极的材料是氧化铟锡，但是氧化铟锡成本较高，且在弯曲条件下易脆裂，因此并不适用于柔性电子设备。为此，近年来学界和产业界相继研发出导电聚合物、碳纳米管、石墨烯、金属纳米线等柔性纳米导电材料，其中金属纳米线由于低成本、高性能、超柔性而受到广泛关注。Transparent conductive electrodes are one of the most important components in optoelectronic devices such as solar cells, light-emitting diodes, touch screens, and displays. The material for transparent conductive electrodes currently widely used on the market is indium tin oxide. However, indium tin oxide is relatively expensive and easily brittle under bending conditions, so it is not suitable for flexible electronic devices. To this end, in recent years, academic and industrial circles have successively developed flexible nanoconductive materials such as conductive polymers, carbon nanotubes, graphene, and metal nanowires. Among them, metal nanowires have attracted widespread attention due to their low cost, high performance, and ultra-flexibility.
目前，金属纳米电极的生产通常分为以下几步：金属纳米线的合成、金属纳米线的纯化、以及金属纳米线油墨的制备及涂布，其中基于金属纳米线的透明电极的性能主要取决于三个过程：(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。At present, the production of metal nanoelectrodes is usually divided into the following steps: synthesis of metal nanowires, purification of metal nanowires, and preparation and coating of metal nanowire ink. The performance of transparent electrodes based on metal nanowires mainly depends on Three processes: (1) the aspect ratio of the synthesized metal nanowires and the monodispersity of their size; (2) the purity of the nanowires, post-processing to remove nanorods, particles and polymers as surfactants ; (3) The uniformity of the conductive network when nanowire coating is used to form a film.
其中金属纳米线的纯化是决定金属纳米线油墨的生产成本和质量的关键步骤。金属纳米线纯化的纯度主要取决于后处理除去金属纳米短棒、金属纳米颗粒以及作为表面活性剂的聚合物的有效程度；传统的金属纳米线提纯技术有离心法、膜过滤法、切向流法、萃取法、电泳分离法等，这些方法都具有操作繁琐、步骤繁多、纯化效率低、需要耗费大量的时间及溶剂等问题，并且过多的离心还会造成金属纳米线团聚，极大地影响金属纳米线油墨的品质以及透明电极的光电性能。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高效快捷的方法，用于大规模自动化提纯金属纳米线。 Among them, the purification of metal nanowires is a key step that determines the production cost and quality of metal nanowire ink. The purity of metal nanowire purification mainly depends on the effectiveness of post-treatment to remove metal nanorods, metal nanoparticles and polymers as surfactants; traditional metal nanowire purification technologies include centrifugation, membrane filtration, and tangential flow. Methods, extraction methods, electrophoretic separation methods, etc. These methods have problems such as cumbersome operations, numerous steps, low purification efficiency, and require a lot of time and solvents. In addition, excessive centrifugation can also cause the agglomeration of metal nanowires, which greatly affects The quality of metallic nanowire inks and the optoelectronic properties of transparent electrodes. Therefore, in order to further improve the quality of metal nanowires and reduce production costs for commercial applications, it is necessary to develop an efficient and fast method for large-scale automated purification of metal nanowires.
发明内容Contents of the invention
为了解决上述问题，本发明提供了一种金属纳米线的纯化系统及纯化方法，通过多级纯化利用微流控技术，分离得到纯化程度较高的金属纳米线。In order to solve the above problems, the present invention provides a purification system and purification method for metal nanowires, which use microfluidic technology through multi-stage purification to separate and obtain metal nanowires with a higher degree of purification.
本发明第一方面提供一种金属纳米线的纯化系统，包括：储料系统、多级纯化系统和控制系统；A first aspect of the present invention provides a purification system for metal nanowires, including: a storage system, a multi-stage purification system and a control system;
所述储料系统由多个相互独立的储料罐构成，多个储料罐内存储有不同物料；The storage system is composed of multiple independent storage tanks, and different materials are stored in the multiple storage tanks;
所述多级纯化系统由依次连接的初级纯化装置、次级纯化装置和三级纯化装置构成；所述初级纯化装置内设有过滤膜，所述次级纯化装置内设置有喷淋头，所述三级纯化装置由微流控纯化塔构成，所述微流控纯化塔内串联设置有多个玻璃微珠纯化柱和多个微流控芯片纯化柱；所述储料系统内不同储料罐与各级纯化装置通过管道连通；The multi-stage purification system consists of a primary purification device, a secondary purification device and a tertiary purification device connected in sequence; the primary purification device is provided with a filter membrane, and the secondary purification device is provided with a sprinkler head. The three-stage purification device is composed of a microfluidic purification tower. A plurality of glass microbead purification columns and a plurality of microfluidic chip purification columns are arranged in series in the microfluidic purification tower; different materials are stored in the storage system. The tank is connected to various levels of purification devices through pipelines;
所述控制系统包括多组控制模块，多组所述控制模块与所述储料系统、多级纯化系统电联接，所述控制系统通过多组所述控制模块控制储料系统向多级纯化系统、以及多级纯化系统内各级纯化装置间的物料传送。The control system includes multiple groups of control modules. Multiple groups of the control modules are electrically connected to the storage system and the multi-stage purification system. The control system controls the storage system to the multi-stage purification system through multiple groups of the control modules. , and material transfer between various levels of purification devices in a multi-stage purification system.
进一步地，所述微流控芯片纯化柱内包括多个串联的微流控芯片，所述微流控芯片内微通道的宽度为10-500μm，深度为5-300μm，所述玻璃微珠纯化柱内玻璃微珠的尺寸为1-30μm；优选地，所述微流控芯片内微通道的宽度为50μm，深度为30μm，所述玻璃微珠纯化柱内玻璃微珠的尺寸为25μm。Further, the microfluidic chip purification column includes multiple microfluidic chips connected in series. The width of the microchannel in the microfluidic chip is 10-500 μm and the depth is 5-300 μm. The glass microbead purification column The size of the glass microbeads in the column is 1-30 μm; preferably, the width of the microchannel in the microfluidic chip is 50 μm and the depth is 30 μm, and the size of the glass microbeads in the glass bead purification column is 25 μm.
微流控芯片主要是由微米级通道和腔室组成，利用流体在微通道内的层流特性，金属纳米线和粒子以及其它杂质的扩散速度并不一致，通过芯片的串联，可以延长流体路径，从而操纵金属纳米线和杂质的分离。Microfluidic chips are mainly composed of micron-level channels and chambers. Taking advantage of the laminar flow characteristics of fluids in microchannels, the diffusion speeds of metal nanowires, particles and other impurities are not consistent. Through the series connection of chips, the fluid path can be extended. thereby manipulating the separation of metal nanowires and impurities.
进一步地，所述储料系统的储料罐包括金属纳米线原浆储料罐、脱附剂储料罐、超纯水储料罐以及纯水储料罐。Further, the storage tanks of the storage system include metal nanowire slurry storage tanks, desorbent storage tanks, ultrapure water storage tanks and pure water storage tanks.
进一步地，所述金属纳米线原浆储料罐、脱附剂储料罐与所述初级纯化装置通过管道连接，所述超纯水储料罐与所述次级纯化装置的喷淋头通过管道连接。 Further, the metal nanowire original slurry storage tank, the desorbent storage tank and the primary purification device are connected through pipelines, and the ultrapure water storage tank and the sprinkler head of the secondary purification device are connected through Pipe connections.
进一步地，所述储料罐与各级纯化装置之间还设置有多个计量泵，所述控制系统通过所述计量泵控制物料传送过程以及物料传送量。Furthermore, a plurality of metering pumps are arranged between the storage tank and the purification devices at each level, and the control system controls the material transfer process and the material transfer amount through the metering pumps.
进一步地，所述纯化系统还包括富集装置，金属纳米线经多级纯化系统纯化后由三级纯化装置进入富集装置，从而得到纯化后的金属纳米线悬浊液；具体地，所述富集装置微离心机。Further, the purification system also includes an enrichment device. After the metal nanowires are purified by the multi-stage purification system, they enter the enrichment device from the three-stage purification device, thereby obtaining the purified metal nanowire suspension; specifically, the Enrichment device microcentrifuge.
进一步地，所述次级纯化装置和所述三级纯化装置之间还连接有混料装置，所述混料装置与所述纯水储料罐通过计量泵连接。混料装置主要用于对进入三级纯化装置的次级纯化产物进行稀释，便于其在纯化柱中流出。Furthermore, a mixing device is connected between the secondary purification device and the tertiary purification device, and the mixing device is connected to the pure water storage tank through a metering pump. The mixing device is mainly used to dilute the secondary purification products entering the three-stage purification device so that they can flow out of the purification column.
本发明第二方面提供一种使用上述金属纳米线的纯化系统的金属纳米线的纯化方法，包括以下步骤：A second aspect of the present invention provides a method for purifying metal nanowires using the above-mentioned purification system for metal nanowires, including the following steps:
(1)一级纯化：向将金属纳米线原浆中加入脱附剂，搅拌后过滤，得到初级纯化产物；(1) Primary purification: Add desorption agent to the original slurry of metal nanowires, stir and filter to obtain the primary purification product;
(2)次级纯化：用超纯水喷淋清洗初级纯化产物，得到次级纯化产物；(2) Secondary purification: spray and clean the primary purification product with ultrapure water to obtain the secondary purification product;
(3)三级纯化：向次级纯化产物中加入纯水得到稀释液，将稀释液置于微流控塔进行分离，收集分离产物，离心富集，即得到金属纳米线纯化液。(3) Three-stage purification: add pure water to the secondary purification product to obtain a dilution, place the dilution in a microfluidic tower for separation, collect the separated products, and centrifuge for enrichment to obtain a metal nanowire purification solution.
进一步地，步骤(1)所述的脱附剂选自醋酸甲酯、醋酸乙酯、醋酸丙酯、丙酮、甲基丁酮、甲基异丁酮、氯苯、二氯苯、二氯甲烷、戊烷、己烷、辛烷、苯、甲苯、二甲苯、氯仿、四氯化碳、三氯乙烯、四氯乙烯、三氯丙烷、二氯乙烷、煤油、石油醚中的一种或几种。Further, the desorbent described in step (1) is selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone, methyl isobutyl ketone, chlorobenzene, dichlorobenzene, and methylene chloride. , pentane, hexane, octane, benzene, toluene, xylene, chloroform, carbon tetrachloride, trichlorethylene, tetrachlorethylene, trichloropropane, dichloroethane, kerosene, petroleum ether or Several kinds.
进一步地，所述金属纳米线为金、银、铜、铁、铝、镍、锡及其氧化物的纳米线。Further, the metal nanowires are nanowires of gold, silver, copper, iron, aluminum, nickel, tin and their oxides.
具体地，步骤(1)中金属纳米线原浆与脱附剂的用量比为1：(2-3)，搅拌速度为50-100r/min，搅拌时间为10-15min。Specifically, in step (1), the dosage ratio of metal nanowire slurry to desorbent is 1: (2-3), the stirring speed is 50-100r/min, and the stirring time is 10-15min.
具体地，步骤(2)中超纯水喷淋速度为50-1000mL/min，喷淋时间为3-5min。Specifically, in step (2), the ultrapure water spray speed is 50-1000 mL/min, and the spray time is 3-5 min.
进一步具体地，步骤(3)中的微流控塔为本发明前述一种金属纳米线的纯化系统中的微流控塔，稀释液在微流控塔中的流出速度为50～100ml/min，在该流速下，能够同时保证纯化质量并实现量产。More specifically, the microfluidic tower in step (3) is the microfluidic tower in the aforementioned metal nanowire purification system of the present invention, and the outflow rate of the diluent in the microfluidic tower is 50 to 100 ml/min. , at this flow rate, it is possible to ensure purification quality and achieve mass production at the same time.
基于化学模板法或者其他方法制备的金属纳米线，由于金属纳米线是由金 属纳米颗粒在模板(通常为有机载体)表面不断沉积得到的，因此制得的金属纳米线其表面通常附着有有机物载体，并且由于金属纳米颗粒沉积的不完全，制得的金属纳米线原浆中还含有纳米短棒、纳米颗粒等杂质。Metal nanowires prepared based on chemical template methods or other methods, because metal nanowires are made of gold It is obtained by the continuous deposition of nanoparticles on the surface of the template (usually an organic carrier), so the surface of the prepared metal nanowires is usually attached with an organic carrier, and due to the incomplete deposition of the metal nanoparticles, the prepared metal nanowire slurry It also contains impurities such as nanorods and nanoparticles.
本发明的纯化系统及纯化方法采用多级分步纯化，初级纯化为脱附纯化，利用脱附剂与金属纳米线原浆进行搅拌混合，将金属纳米线与附着在其表面的有机物载体分离。次级纯化为淋洗纯化，采用超纯水进行喷淋，利用超纯水裹挟带走水溶性杂质如金属纳米线制备过程中的助剂等。三级纯化为微流控纯化，首先在玻璃微珠纯化柱内，溶质进行垂直向下的运动以及无定向的扩散运动，其中金属纳米线由于直径较大，不易进入玻璃微珠的微孔而分布于颗粒之间，移动速度相对较快，杂质如金属纳米颗粒尺寸较小，会不断扩散进入玻璃微珠的微孔内，导致移动速度较慢，金属纳米线较先流出玻璃微珠纯化柱；流出的金属纳米线中仍然混杂有其他杂质，再将其置于微流控芯片纯化柱内，其中的微流控芯片内部具有微尺寸通道，在微通道内，流体会形成层次分明的多相平行流动(层流)，此时，扩散成为微尺度下传质的主要途径，由于不同物质自身性质不同因而扩散速率也存在差异，从而实现金属纳米线与其他杂质的分离，并且通过延长其扩散路径，采用多个多组微流控芯片串联，即可进一步放大分离效果，最终实现金属纳米线的纯化。The purification system and purification method of the present invention adopt multi-stage step-by-step purification. The primary purification is desorption purification. The desorbent is used to stir and mix the metal nanowire original slurry to separate the metal nanowires from the organic carriers attached to their surfaces. Secondary purification is elution purification, which uses ultrapure water for spraying and uses ultrapure water to entrain and take away water-soluble impurities such as additives in the preparation process of metal nanowires. The third-level purification is microfluidic purification. First, in the glass bead purification column, the solute moves vertically downward and diffuses in an undirected manner. The metal nanowires are difficult to enter the micropores of the glass beads due to their large diameter. Distributed between particles, the moving speed is relatively fast. Impurities such as metal nanoparticles are small in size and will continue to diffuse into the micropores of the glass beads, resulting in a slower moving speed. The metal nanowires flow out of the glass bead purification column first. ; The metal nanowires that flow out are still mixed with other impurities, and are then placed in a microfluidic chip purification column. The microfluidic chip has micro-sized channels inside. In the microchannels, the fluid will form a well-defined multi-layered structure. Phase parallel flow (laminar flow). At this time, diffusion becomes the main way of mass transfer at the microscale. Due to the different properties of different substances, the diffusion rates are also different, thereby achieving the separation of metal nanowires from other impurities, and by extending their For the diffusion path, multiple groups of microfluidic chips are used in series to further amplify the separation effect and ultimately achieve the purification of metal nanowires.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
(1)本发明的金属纳米线的纯化系统，各个零件及设备结构简单，系统搭建成本低；通过多级纯化系统分步进行纯化，初级纯化利用脱附剂将金属纳米线与有机载体分离，次级纯化喷淋去除水溶性杂质，三级纯化利用玻璃微珠纯化柱放大分离效果，并利用微流控芯片提供微通道，在微通道内利用层流及差别扩散实现金属纳米线与其他杂质的最终分离。采用多级自动纯化，能够提高纯化速度和纯化质量，并且实现高纯度金属纳米线的量产。(1) The purification system of metal nanowires of the present invention has simple parts and equipment structures, and low system construction cost; purification is carried out step by step through a multi-stage purification system, and the primary purification uses a desorbent to separate the metal nanowires from the organic carrier. The secondary purification spray removes water-soluble impurities. The third-stage purification uses glass bead purification columns to amplify the separation effect, and uses microfluidic chips to provide microchannels. Laminar flow and differential diffusion are used in the microchannels to separate metal nanowires from other impurities. the final separation. The use of multi-stage automatic purification can improve the purification speed and quality, and achieve mass production of high-purity metal nanowires.
(2)本发明的金属纳米线的纯化系统，在储料罐、各级纯化装置以及控制系统的基础上还包括计量泵、混料装置和富集装置，能够搭建成全自动化的纯化系统，节省人力成本，提高系统的稳定性，保证纯化过程的成功率。(2) The metal nanowire purification system of the present invention also includes a metering pump, a mixing device and an enrichment device on the basis of a storage tank, various levels of purification devices and a control system. It can be built into a fully automated purification system and saves money. Reduce labor costs, improve system stability, and ensure the success rate of the purification process.
(3)本发明的金属纳米线的纯化方法，采用脱附——淋洗——微流控纯化 三级纯化步骤，脱附剂采用常规的溶剂，只需进行一次脱附洗涤，不会造成大量溶剂浪费从而降低原料成本，节省时间；并且淋洗阶段以及微流控纯化阶段仅采用超纯水和纯水，不会引入新的有机溶剂；利用微流控技术进行进一步分离，由于微通道内流体的差速流动，能够明显改善分离效果，得到纯度更高的金属纳米线。(3) The purification method of metal nanowires of the present invention adopts desorption-elution-microfluidic purification In the third-level purification step, conventional solvents are used as the desorbent, and only one desorption and washing process is required, which does not waste a large amount of solvent, thereby reducing raw material costs and saving time; and only ultrapure water is used in the elution stage and microfluidic purification stage. and pure water, no new organic solvents will be introduced; microfluidic technology is used for further separation. Due to the differential flow of fluids in the microchannel, the separation effect can be significantly improved and higher purity metal nanowires can be obtained.
附图说明Description of drawings
为了更清楚的说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单的介绍，显而易见的，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它附图。In order to more clearly explain the embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only These are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without exerting creative efforts.
图1为本发明纯化系统的示意图；Figure 1 is a schematic diagram of the purification system of the present invention;
图2为本发明微流控纯化塔的示意图；Figure 2 is a schematic diagram of the microfluidic purification tower of the present invention;
图3为本发明微流控芯片的示意图；Figure 3 is a schematic diagram of the microfluidic chip of the present invention;
图4为本发明实施例1得到的纯化的银纳米线的TEM图；Figure 4 is a TEM image of the purified silver nanowires obtained in Example 1 of the present invention;
图5为本发明对比例1得到的纯化的银纳米线的TEM图。Figure 5 is a TEM image of the purified silver nanowires obtained in Comparative Example 1 of the present invention.
附图标记：
100、储料系统；110、储料罐；111、金属纳米线原浆储料罐；112、脱附剂
储料罐；113、超纯水储料罐；114、纯水储料罐；200、计量泵；300、初级纯化装置；400、次级纯化装置；500、混料装置；600、三级纯化装置；610、玻璃微珠纯化柱；620、微流控芯片纯化柱；621、微流控芯片；700、富集装置；800、控制系统。Reference signs:
100. Storage system; 110. Storage tank; 111. Metal nanowire slurry storage tank; 112. Desorbent storage tank; 113. Ultrapure water storage tank; 114. Pure water storage tank; 200 , Metering pump; 300, primary purification device; 400, secondary purification device; 500, mixing device; 600, third-level purification device; 610, glass microbead purification column; 620, microfluidic chip purification column; 621, micro Fluid control chip; 700, enrichment device; 800, control system.
具体实施方式Detailed ways
下面将结合具体实施例，对本发明的技术方案进行清楚、完整的描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通的技术人员在没有做出创造性劳动的前提下所获得的所有其它实施例，都属于本发明的保护范围。 The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without any creative work fall within the protection scope of the present invention.
实施例1Example 1
如图1-3所示，本发明金属纳米线的纯化系统包括：储料系统100、多级纯化系统和控制系统800；储料系统100由多个相互独立的储料罐构成，多个储料罐内存储有不同物料；多级纯化系统由依次连接的初级纯化装置300、次级纯化装置400和三级纯化装置600构成；初级纯化装置300内设有过滤膜，次级纯化装置400内设置有喷淋头，三级纯化装置600由微流控纯化塔构成，微流控纯化塔内串联设置有多个玻璃微珠纯化柱610和多个微流控芯片纯化柱620；储料系统100内不同储料罐与各级纯化装置通过管道连通；控制系统800包括多组控制模块，多组所述控制模块与储料系统100、多级纯化系统电联接，控制系统800通过多组控制模块控制储料系统100向多级纯化系统、以及多级纯化系统内各级纯化装置间的物料传送。本发明的金属纳米线的纯化系统包括多级纯化装置，对应不同的纯化操作，并且设置储料系统用于储存各级纯化操作所需的物料，同时还设置有控制系统用以调控各装置内的物料输送以及控制各纯化过程的纯化条件，从而实现整个纯化过程的自动化。As shown in Figures 1-3, the purification system of metal nanowires of the present invention includes: a storage system 100, a multi-stage purification system and a control system 800; the storage system 100 is composed of multiple independent storage tanks. Different materials are stored in the material tank; the multi-stage purification system consists of a primary purification device 300, a secondary purification device 400 and a tertiary purification device 600 connected in sequence; the primary purification device 300 is equipped with a filter membrane, and the secondary purification device 400 is equipped with a filter membrane. A shower head is provided, and the three-stage purification device 600 is composed of a microfluidic purification tower. A plurality of glass microbead purification columns 610 and a plurality of microfluidic chip purification columns 620 are arranged in series in the microfluidic purification tower; a storage system Different storage tanks within 100 are connected to various levels of purification devices through pipelines; the control system 800 includes multiple sets of control modules, and the multiple sets of control modules are electrically connected to the storage system 100 and the multi-level purification system. The control system 800 controls the The module controls the material transfer from the storage system 100 to the multi-stage purification system and between various purification devices in the multi-stage purification system. The purification system of metal nanowires of the present invention includes multi-stage purification devices, corresponding to different purification operations, and is provided with a storage system to store materials required for each level of purification operations, and is also provided with a control system to regulate the internal contents of each device. Material transportation and control of the purification conditions of each purification process, thereby realizing the automation of the entire purification process.
具体地，每组控制模块分别用于控制初级纯化装置、次级纯化装置以及三级纯化装置内的纯化过程，并且根据作用对象的不同可选地包括信号收集模块、信号分析模块以及执行模块；信号收集模块用于收集各纯化装置内的状态信息，如物料量等，信号分析模块与信号收集模块的输出端连接，将信号收集模块收集的状态信息与预先设定的阈值进行比对，若信号相符则启动相应的应对策略并输出指令，执行模块与信号分析模块的输出端连接，用于执行信号分析模块输出的指令。具体的应对策略例如当所需的一种物料输送量达到设定阈值后关闭该物料的输送并同时开启下一物料的输送、所有设定物料输送完毕后启动对应的物料搅拌、升温操作等。Specifically, each group of control modules is used to control the purification process in the primary purification device, the secondary purification device and the tertiary purification device respectively, and optionally includes a signal collection module, a signal analysis module and an execution module according to different objects; The signal collection module is used to collect status information in each purification device, such as material volume, etc. The signal analysis module is connected to the output end of the signal collection module, and compares the status information collected by the signal collection module with the preset threshold. If If the signals match, the corresponding response strategy is activated and instructions are output. The execution module is connected to the output end of the signal analysis module and is used to execute the instructions output by the signal analysis module. Specific coping strategies include, when the required transportation volume of a material reaches a set threshold, shut down the transportation of this material and start the transportation of the next material at the same time, start the corresponding material stirring and heating operations after all set materials are transported, etc.
作为本发明纯化系统的一种优选实施例，如图2所示，微流控纯化塔内包含多个串联设置的玻璃微珠纯化柱610和微流控芯片纯化柱620，混料装置500中的稀释液在微流控纯化塔依次经过多个玻璃微珠纯化柱610和多个微流控芯片纯化柱620后完成分离，微流控芯片纯化柱620内包括多个串联的微流控芯片621，其中每个微流控芯片621均横向设置，避免重力作用对微流控芯片内层 流特性的影响，从而保证分离效果。如图3所示，微流控芯片621内微通道的宽度为50μm，深度为30μm，玻璃微珠纯化柱610内玻璃微珠的尺寸为25μm。As a preferred embodiment of the purification system of the present invention, as shown in Figure 2, the microfluidic purification tower contains a plurality of glass microbead purification columns 610 and microfluidic chip purification columns 620 arranged in series. In the mixing device 500 The diluted solution is separated in the microfluidic purification tower after passing through multiple glass bead purification columns 610 and multiple microfluidic chip purification columns 620. The microfluidic chip purification column 620 includes multiple microfluidic chips connected in series. 621, in which each microfluidic chip 621 is set horizontally to avoid the effect of gravity on the inner layer of the microfluidic chip. The influence of flow characteristics ensures the separation effect. As shown in Figure 3, the width of the microchannel in the microfluidic chip 621 is 50 μm and the depth is 30 μm, and the size of the glass beads in the glass bead purification column 610 is 25 μm.
进一步地，储料系统100的储料罐110包括金属纳米线原浆储料罐111、脱附剂储料罐112、超纯水储料罐113以及纯水储料罐114。金属纳米线原浆储料罐111、脱附剂储料罐112与所述初级纯化装置300通过管道连接，超纯水储料罐113与所述次级纯化装置400的喷淋头通过管道连接。Further, the storage tank 110 of the storage system 100 includes a metal nanowire slurry storage tank 111 , a desorbent storage tank 112 , an ultrapure water storage tank 113 and a pure water storage tank 114 . The metal nanowire slurry storage tank 111 and the desorbent storage tank 112 are connected to the primary purification device 300 through pipelines, and the ultrapure water storage tank 113 is connected to the sprinkler head of the secondary purification device 400 through pipelines. .
作为本发明纯化系统的一种优选实施例，储料罐110与各级纯化装置之间还设置有多个计量泵200，控制系统800通过计量泵200控制物料传送过程以及物料传送量；纯化系统还包括富集装置700，金属纳米线经多级纯化系统纯化后由三级纯化装置600进入富集装置700，从而得到纯化后的金属纳米线悬浊液；次级纯化装置400和所述三级纯化装置600之间还连接有混料装置500，所述混料装置500与所述纯水储料罐114通过计量泵200连接。As a preferred embodiment of the purification system of the present invention, multiple metering pumps 200 are provided between the storage tank 110 and the purification devices at each level. The control system 800 controls the material transfer process and the material transfer amount through the metering pumps 200; Purification System It also includes an enrichment device 700. After the metal nanowires are purified by the multi-stage purification system, they enter the enrichment device 700 from the three-stage purification device 600, thereby obtaining the purified metal nanowire suspension; the secondary purification device 400 and the three-stage purification device 400. A mixing device 500 is also connected between the first-stage purification devices 600 , and the mixing device 500 and the pure water storage tank 114 are connected through a metering pump 200 .
初级纯化装置300与金属纳米线原浆储料罐111、脱附剂储料罐112连接获取初级纯化(脱附纯化)所需的物料，并将初级纯化产物传送给次级纯化装置400，次级纯化装置400与超纯水储料罐113连接获得次级纯化(淋洗纯化)所需的物料，并将次级纯化产物传送给混料装置500，混料装置500与纯水储料罐114连接获得三级纯化(微流控纯化)所需的物料进行稀释，并将稀释液传送给三级纯化装置600，三级纯化装置600纯化完成后将纯化产物传送到富集装置700得到金属纳米线纯化液。The primary purification device 300 is connected to the metal nanowire slurry storage tank 111 and the desorbent storage tank 112 to obtain the materials required for primary purification (desorption purification), and transfers the primary purification product to the secondary purification device 400. The secondary purification device 400 is connected to the ultrapure water storage tank 113 to obtain the materials required for secondary purification (elution purification), and transfers the secondary purification product to the mixing device 500, which is connected to the pure water storage tank 113. 114 is connected to obtain the materials required for the third-stage purification (microfluidic purification), and the diluted liquid is sent to the third-level purification device 600. After the third-level purification device 600 completes the purification, the purified product is sent to the enrichment device 700 to obtain the metal. Nanowire purification solution.
使用上述纯化系统的金属纳米线的纯化方法，包括以下步骤：The purification method of metal nanowires using the above purification system includes the following steps:
(1)将20L银纳米线原浆和40L醋酸甲酯和甲基异丁酮按照1:1配比组成的混合脱附剂混合，以80r/min转速搅拌12min，过滤收集滤渣，得到初级纯化产物；(1) Mix 20L silver nanowire slurry and 40L mixed desorbent composed of methyl acetate and methyl isobutyl ketone in a ratio of 1:1, stir for 12 minutes at 80r/min, filter and collect the filter residue to obtain primary purification product;
(2)用超纯水以200mL/min速度喷淋清洗初级纯化产物3min，得到次级纯化产物；(2) Spray and clean the primary purified product with ultrapure water at a speed of 200 mL/min for 3 minutes to obtain the secondary purified product;
(3)向次级纯化产物中加入1L纯水得到稀释液，将稀释液置于微流控塔进行分离，收集分离产物，离心富集，即得到金属纳米线纯化液，其TEM图如图4所示。 (3) Add 1L pure water to the secondary purified product to obtain a diluent, place the diluted liquid in a microfluidic tower for separation, collect the separated products, and centrifuge for enrichment to obtain a metal nanowire purified liquid. The TEM image is as shown in the figure 4 shown.
上述步骤均在金属纳米线的纯化系统中完成，组分的传送均通过纯化系统的控制系统进行调控。The above steps are all completed in the metal nanowire purification system, and the transmission of components is controlled by the control system of the purification system.
实施例2Example 2
本实施例采用的纯化系统与实施例1基本相同，不同之处在于三级纯化装置600中微流控芯片621内微通道的宽度为20μm，深度为10μm，所述玻璃微珠纯化柱610内玻璃微珠的尺寸为10μm。The purification system used in this embodiment is basically the same as that in Embodiment 1, except that the width of the microchannel in the microfluidic chip 621 in the three-stage purification device 600 is 20 μm and the depth is 10 μm. The size of the glass beads is 10 μm.
使用该纯化系统的金属纳米线的纯化方法，包括以下步骤：The purification method of metal nanowires using this purification system includes the following steps:
(1)将20L铜纳米线原浆和50L甲基丁酮脱附剂混合，以50r/min转速搅拌15min，过滤收集滤渣，得到初级纯化产物；(1) Mix 20L copper nanowire slurry and 50L methyl butanone desorbent, stir for 15 minutes at 50r/min, filter and collect the filter residue to obtain the primary purified product;
(2)用超纯水以50mL/min速度喷淋清洗初级纯化产物4min，得到次级纯化产物；(2) Spray and clean the primary purified product with ultrapure water at a speed of 50 mL/min for 4 minutes to obtain the secondary purified product;
(3)向次级纯化产物中加入1L纯水得到稀释液，将稀释液置于微流控塔进行分离，收集分离产物，离心富集，即得到金属纳米线纯化液。(3) Add 1 L of pure water to the secondary purified product to obtain a diluent, place the diluted liquid in a microfluidic tower for separation, collect the separated product, and centrifuge for enrichment to obtain a metal nanowire purified liquid.
上述步骤均在金属纳米线的纯化系统中完成，组分的传送均通过纯化系统的控制系统进行调控。The above steps are all completed in the metal nanowire purification system, and the transmission of components is controlled by the control system of the purification system.
实施例3Example 3
本实施例采用的纯化系统与实施例1基本相同，不同之处在于三级纯化装置600中微流控芯片621内微通道的宽度为200μm，深度为100μm，所述玻璃微珠纯化柱610内玻璃微珠的尺寸为30μm。The purification system used in this embodiment is basically the same as that in Embodiment 1, except that the width of the microchannel in the microfluidic chip 621 in the three-stage purification device 600 is 200 μm and the depth is 100 μm. The size of the glass beads is 30 μm.
使用该纯化系统的金属纳米线的纯化方法，包括以下步骤：The purification method of metal nanowires using this purification system includes the following steps:
(1)将20L金纳米线原浆和60L丙酮、甲苯和四氯化碳按照1:1:1配比组成的混合脱附剂混合，以50r/min转速搅拌10min,过滤收集滤渣，得到初级纯化产物；(1) Mix 20L gold nanowire slurry with 60L mixed desorbent composed of acetone, toluene and carbon tetrachloride in a ratio of 1:1:1, stir for 10 minutes at 50r/min, filter and collect the filter residue to obtain primary purified product;
(2)用超纯水以50mL/min速度喷淋清洗初级纯化产物5min，得到次级纯化产物；(2) Spray and clean the primary purified product with ultrapure water at a speed of 50 mL/min for 5 minutes to obtain the secondary purified product;
(3)向次级纯化产物中加入1L纯水得到稀释液，将稀释液置于微流控塔进行分离，收集分离产物，离心富集，即得到金属纳米线纯化液。(3) Add 1 L of pure water to the secondary purified product to obtain a diluent, place the diluted liquid in a microfluidic tower for separation, collect the separated product, and centrifuge for enrichment to obtain a metal nanowire purified liquid.
上述步骤均在金属纳米线的纯化系统中完成，组分的传送均通过纯化系统 的控制系统进行调控。The above steps are all completed in the purification system of metal nanowires, and the components are transferred through the purification system control system for regulation.
实施例4Example 4
本发明金属纳米线纯化系统具体运行方式如下：The specific operation mode of the metal nanowire purification system of the present invention is as follows:
(1)原料准备：向储料系统100的对应储料罐110内分别添加金属纳米线原浆、脱附剂、超纯水以及纯水，其中在纯化不同金属纳米线如银纳米线、铜纳米线、金纳米线时，添加对应的原浆即可，并且对于不同的金属纳米线原浆，预先配制好脱附剂添加进入脱附剂储料罐112，脱附剂的配制可根据需要进行组分调整；(1) Raw material preparation: Add metal nanowire slurry, desorbent, ultrapure water and pure water to the corresponding storage tanks 110 of the storage system 100 respectively. When purifying different metal nanowires such as silver nanowires, copper For nanowires and gold nanowires, just add the corresponding original slurry, and for different metal nanowire original slurries, the desorbent is pre-prepared and added into the desorbent storage tank 112. The preparation of the desorbent can be as needed. Make component adjustments;
(2)自动纯化：利用控制系统800按照预先设计的加料顺序及原料添加量将金属纳米线原浆以及脱附剂从储料系统100经计量泵200传送到初级纯化装置300中，开启搅拌，待搅拌结束后进行过滤得到初级纯化产物；控制系统800将初级纯化产物传送到次级纯化装置400并开启连接超纯水储料罐113的计量泵200，超纯水从喷淋头按照预先设定的速度喷出，对初级纯化产物进行喷淋清洗，喷淋液实时向下溢出，喷淋结束后得到次级纯化产物；控制系统800将次级纯化产物传送到混料装置500，并开启连接纯水的计量泵200添加指定量纯水将次级纯化产物进行稀释并混合均匀；控制系统将稀释后的次级纯化产物传送到三级纯化装置600，在三级纯化装置600中，稀释液先后经过玻璃微珠纯化柱610和微流控芯片纯化柱620，收集第一流出组分，控制系统800将第一流出组分传送到富集装置700进行离心，结束后即得到金属纳米线纯化液。上述所有步骤均预先设置程序，然后控制系统在预设程序下自动完成纯化过程。(2) Automatic purification: The control system 800 is used to transfer the metal nanowire slurry and desorbent from the storage system 100 to the primary purification device 300 through the metering pump 200 according to the pre-designed feeding sequence and raw material addition amount, and start stirring. After the stirring is completed, filtration is performed to obtain the primary purified product; the control system 800 transmits the primary purified product to the secondary purification device 400 and turns on the metering pump 200 connected to the ultrapure water storage tank 113. The ultrapure water flows from the sprinkler head according to the preset setting. The primary purified product is sprayed and cleaned at a certain speed, and the spray liquid overflows downward in real time. After the spraying is completed, the secondary purified product is obtained; the control system 800 transmits the secondary purified product to the mixing device 500 and turns on the The metering pump 200 connected to pure water adds a specified amount of pure water to dilute the secondary purified product and mix it evenly; the control system transmits the diluted secondary purified product to the third-level purification device 600, and in the third-level purification device 600, the diluted The liquid passes through the glass microbead purification column 610 and the microfluidic chip purification column 620 successively to collect the first outflow component. The control system 800 transfers the first outflow component to the enrichment device 700 for centrifugation. After completion, the metal nanowires are obtained. Purified solution. All the above steps are programmed in advance, and then the control system automatically completes the purification process under the preset program.
对比例1Comparative example 1
本对比例采用常规多次洗脱方法得到的纯化银纳米线，具体步骤如下：This comparative example uses purified silver nanowires obtained by conventional multiple elution methods. The specific steps are as follows:
将银纳米线原浆用丙酮洗涤3次，得到纯化后的银纳米线，其TEM图如图5所示。The silver nanowire original slurry was washed three times with acetone to obtain purified silver nanowires, whose TEM image is shown in Figure 5.
对比图4和图5，本发明的金属纳米线的纯化方法，得到的金属纳米线纯度更高，小颗粒杂质较少；而对比例1经3次洗脱纯化的银纳米线存在明显的点状杂质，银纳米颗粒以及银纳米棒含量较多，纯化效果较差。Comparing Figure 4 and Figure 5, the metal nanowires purified by the method of the present invention have higher purity and fewer small particle impurities; while the silver nanowires purified by three times of elution in Comparative Example 1 have obvious problems. The content of silver nanoparticles and silver nanorods is high, and the purification effect is poor.
综上，本申请所提供的金属纳米线的纯化系统及纯化方法能够自动完成纯 化过程，纯化效率高纯化周期大大缩短，并且能够有效去除金属纳米颗粒、金属纳米短棒以及有机添加剂等杂质，纯化效果好，可大规模进行，具有良好的应用价值。In summary, the purification system and purification method of metal nanowires provided in this application can automatically complete the purification process. chemical process, high purification efficiency, greatly shortened purification cycle, and can effectively remove impurities such as metal nanoparticles, metal nanorods and organic additives. The purification effect is good, can be carried out on a large scale, and has good application value.
以上借助具体实施例对本发明做了进一步描述，但是应该理解的是，这里具体的描述，不应理解为对本发明的实质和范围的限定，本领域内的普通技术人员在阅读本说明书后对上述实施例做出的各种修改，都属于本发明所保护的范围。 The present invention has been further described above with the help of specific embodiments. However, it should be understood that the specific description here should not be understood as limiting the essence and scope of the present invention. Those of ordinary skill in the art will not be aware of the above after reading this specification. Various modifications made to the embodiments all belong to the scope of protection of the present invention.

Claims (10)

  1. 一种金属纳米线的纯化系统，其特征在于，包括：储料系统、多级纯化系统和控制系统；A metal nanowire purification system, characterized by including: a storage system, a multi-stage purification system and a control system;
    所述储料系统由多个相互独立的储料罐构成，多个储料罐内存储有不同物料；The storage system is composed of multiple independent storage tanks, and different materials are stored in the multiple storage tanks;
    所述多级纯化系统由依次连接的初级纯化装置、次级纯化装置和三级纯化装置构成；所述初级纯化装置内设有过滤膜，所述次级纯化装置内设置有喷淋头，所述三级纯化装置由微流控纯化塔构成，所述微流控纯化塔内串联设置有多个玻璃微珠纯化柱和多个微流控芯片纯化柱；所述储料系统内不同储料罐与各级纯化装置通过管道连通；The multi-stage purification system consists of a primary purification device, a secondary purification device and a tertiary purification device connected in sequence; the primary purification device is provided with a filter membrane, and the secondary purification device is provided with a sprinkler head. The three-stage purification device is composed of a microfluidic purification tower. A plurality of glass microbead purification columns and a plurality of microfluidic chip purification columns are arranged in series in the microfluidic purification tower; different materials are stored in the storage system. The tank is connected to various levels of purification devices through pipelines;
    所述控制系统控制储料系统向多级纯化系统、以及多级纯化系统内各级纯化装置间的物料传送。The control system controls the material transfer from the storage system to the multi-stage purification system and between various purification devices in the multi-stage purification system.
  2. 根据权利要求1所述的金属纳米线的纯化系统，其特征在于，所述微流控芯片纯化柱内包括多个串联的微流控芯片，所述微流控芯片内微通道的宽度为10-500μm，深度为5-300μm，所述玻璃微珠纯化柱内玻璃微珠的尺寸为1-30μm。The purification system of metal nanowires according to claim 1, characterized in that the microfluidic chip purification column includes a plurality of microfluidic chips connected in series, and the width of the microchannel in the microfluidic chip is 10 -500 μm, the depth is 5-300 μm, and the size of the glass beads in the glass bead purification column is 1-30 μm.
  3. 根据权利要求1所述的金属纳米线的纯化系统，其特征在于，所述储料系统的储料罐包括金属纳米线原浆储料罐、脱附剂储料罐、超纯水储料罐以及纯水储料罐。The purification system of metal nanowires according to claim 1, characterized in that the storage tank of the storage system includes a metal nanowire original slurry storage tank, a desorbent storage tank, and an ultrapure water storage tank. And pure water storage tank.
  4. 根据权利要求3所述的金属纳米线的纯化系统，其特征在于，所述金属纳米线原浆储料罐、脱附剂储料罐与所述初级纯化装置通过管道连接，所述超纯水储料罐与所述次级纯化装置的喷淋头通过管道连接。The purification system of metal nanowires according to claim 3, characterized in that the metal nanowire puree storage tank, the desorbent storage tank and the primary purification device are connected through pipelines, and the ultrapure water The storage tank is connected to the sprinkler head of the secondary purification device through pipelines.
  5. 根据权利要求1所述的金属纳米线的纯化系统，其特征在于，所述储料罐与各级纯化装置之间还设置有多个计量泵，所述控制系统通过所述计量泵控制物料传送过程以及物料传送量。The purification system of metal nanowires according to claim 1, characterized in that, a plurality of metering pumps are provided between the storage tank and the purification devices at each level, and the control system controls material transfer through the metering pumps. process and material transfer volume.
  6. 根据权利要求1所述的金属纳米线的纯化系统，其特征在于，所述纯化系统还包括富集装置，金属纳米线经多级纯化系统纯化后由三级纯化装置进入富集装置，从而得到纯化后的金属纳米线悬浊液。The purification system of metal nanowires according to claim 1, characterized in that the purification system further includes an enrichment device. After the metal nanowires are purified by the multi-stage purification system, they enter the enrichment device from the three-stage purification device, thereby obtaining Purified metal nanowire suspension.
  7. 根据权利要求1所述的金属纳米线的纯化系统，其特征在于，所述次级纯化装置和所述三级纯化装置之间还连接有混料装置，所述混料装置与所述纯水 储料罐通过计量泵连接。The purification system of metal nanowires according to claim 1, characterized in that a mixing device is further connected between the secondary purification device and the tertiary purification device, and the mixing device and the pure water The storage tank is connected through a metering pump.
  8. 一种使用权利要求1-7任一项所述金属纳米线的纯化系统的金属纳米线的纯化方法，其特征在于，包括以下步骤：A method for purifying metal nanowires using the metal nanowire purification system according to any one of claims 1 to 7, characterized in that it includes the following steps:
    (1)一级纯化：向金属纳米线原浆中加入脱附剂，搅拌后过滤，得到初级纯化产物；(1) Primary purification: Add desorbent to the metal nanowire slurry, stir and filter to obtain the primary purification product;
    (2)次级纯化：用超纯水喷淋清洗初级纯化产物，得到次级纯化产物；(2) Secondary purification: spray and clean the primary purification product with ultrapure water to obtain the secondary purification product;
    (3)三级纯化：向次级纯化产物中加入纯水得到稀释液，将稀释液置于微流控塔进行分离，收集分离产物，离心富集，即得到金属纳米线纯化液。(3) Three-stage purification: add pure water to the secondary purification product to obtain a dilution, place the dilution in a microfluidic tower for separation, collect the separated products, and centrifuge for enrichment to obtain a metal nanowire purification solution.
  9. 根据权利要求8所述的金属纳米线的纯化方法，其特征在于，步骤(1)所述的脱附剂选自醋酸甲酯、醋酸乙酯、醋酸丙酯、丙酮、甲基丁酮、甲基异丁酮、氯苯、二氯苯、二氯甲烷、戊烷、己烷、辛烷、苯、甲苯、二甲苯、氯仿、四氯化碳、三氯乙烯、四氯乙烯、三氯丙烷、二氯乙烷、煤油、石油醚中的一种或几种。The purification method of metal nanowires according to claim 8, characterized in that the desorbent in step (1) is selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone, methyl butanone, and the like. Isobutyl ketone, chlorobenzene, dichlorobenzene, methylene chloride, pentane, hexane, octane, benzene, toluene, xylene, chloroform, carbon tetrachloride, trichloroethylene, tetrachloroethylene, trichloropropane , dichloroethane, kerosene, petroleum ether, one or more.
  10. 根据权利要求8所述的金属纳米线的纯化方法，其特征在于，所述金属纳米线为金、银、铜、铁、铝、镍、锡及其氧化物的纳米线。 The method for purifying metal nanowires according to claim 8, wherein the metal nanowires are nanowires of gold, silver, copper, iron, aluminum, nickel, tin and their oxides.
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