WO2016095520A1 - 纳米氧化铜的制备方法以及金属基油墨的印刷方法 - Google Patents

纳米氧化铜的制备方法以及金属基油墨的印刷方法 Download PDF

Info

Publication number
WO2016095520A1
WO2016095520A1 PCT/CN2015/084688 CN2015084688W WO2016095520A1 WO 2016095520 A1 WO2016095520 A1 WO 2016095520A1 CN 2015084688 W CN2015084688 W CN 2015084688W WO 2016095520 A1 WO2016095520 A1 WO 2016095520A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
copper oxide
nano
dispersion
alcohol
Prior art date
Application number
PCT/CN2015/084688
Other languages
English (en)
French (fr)
Inventor
孙蓉
朱朋莉
陈良
Original Assignee
中国科学院深圳先进技术研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中国科学院深圳先进技术研究院 filed Critical 中国科学院深圳先进技术研究院
Publication of WO2016095520A1 publication Critical patent/WO2016095520A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks

Definitions

  • the invention relates to a preparation method of nano copper oxide and a printing method of a metal base ink using the obtained nano copper oxide.
  • Nano-sized copper oxide particles due to their small size effect, macroscopic quantum tunneling effect, surface effect, volume effect, will show unique performance, showing special characteristics in light absorption, electrochemistry, catalytic reaction, energy storage materials, etc.
  • the physical and chemical properties make it more widely used.
  • monodisperse small-sized copper oxide is difficult to prepare, and the method is troublesome, and it is often required to prepare in a small amount under an organic solvent or a high-temperature and high-pressure reaction condition.
  • Nano-silver conductive inks are limited in their development due to their high price and silver migration. Copper inks are excellent in electrical conductivity and cost less than silver. Nano-Cu-based conductive inks can replace traditional chemical etching (or laser etching) or electroplating processes, not only can significantly reduce costs, but also can print green electronically, which is for printed circuit boards. (PCB), electronic tags (RFID), touch screens, membrane switches, solar cells, LED/OLED and many other industries and fields have demonstrated significance, enabling these industries to realize the traditional etching, electroplating process and green environmental protection in electronic circuit technology. The transformation of printed electronic technology has greatly improved the technical level of the industry.
  • a method for preparing nano copper oxide comprising the following steps:
  • the first dispersion liquid and the second dispersion liquid are mixed, and the reaction is stirred under reflux at 100 ° C to 180 ° C for 10 min to 60 min, and the obtained reaction liquid is separated to retain a solid, and the solid is nanometer copper oxide.
  • the copper source is copper hydroxide, copper chloride, copper sulfate, basic copper carbonate, copper citrate, copper acetate or copper acetylacetonate.
  • the concentration of the copper source in the first dispersion is from 0.01 mol/L to 1 mol/L.
  • the operation of disposing the first dispersion liquid by using a copper source is: adding the copper source to the first solvent, and refluxing at 100 ° C to 180 ° C for 10 min to 60 min to obtain the first dispersion. liquid.
  • the first solvent is an alcohol-water mixture; the alcohol in the alcohol-water mixture is selected from the group consisting of methanol, ethanol, butanol, cyclohexanol, isopropanol, ethylene glycol, and diacetate. At least one of ethylene glycol and glycerin, the water in the aqueous alcohol mixture is deionized water.
  • the strong base is potassium hydroxide or sodium hydroxide.
  • the solvent of the second dispersion is a second solvent, and the second solvent is a mixture of alcohol and water;
  • the alcohol in the aqueous alcohol mixture is selected from at least one of anhydrous methanol, ethanol, butanol, cyclohexanol, isopropanol, ethylene glycol, diethylene glycol, and glycerin, the alcohol
  • the water in the water mixture is deionized water.
  • the concentration of the strong base in the second dispersion is from 0.02 mol/L to 2 mol/L.
  • a method for printing a metal-based ink comprising the steps of:
  • the obtained nano-copper oxide is configured as an ink, it is printed on a substrate, and a printed pattern having good conductivity is obtained by reduction in a low-temperature atmosphere or photoreduction.
  • the ink is an oily ink or an aqueous ink that is printed on the substrate by inkjet printing, silkscreening or microgravure.
  • the reduction temperature is 150 ° C to 300 ° C
  • the reducing atmosphere is at least one of hydrogen, carbon monoxide, hydrogen sulfide, and methane.
  • the reducing beam in the photoreduction operation, is ultraviolet light or yellow light, or The reducing beam is a laser.
  • the method for preparing the nanometer copper oxide is prepared by mixing a first dispersion liquid containing a copper source and a second dispersion liquid containing a strong base, and stirring and reacting at 100 ° C to 180 ° C for 10 min to 60 min, thereby obtaining a dispersing property. Nano-copper oxide particles.
  • FIG. 1 is a flow chart of a method for preparing nano-copper oxide according to an embodiment
  • FIG. 2 is a flow chart showing a method of printing a metal-based ink according to an embodiment
  • Example 3 is a TEM image of the nano-copper oxide particles prepared in Example 1;
  • Example 4 is an XRD spectrum of the nano-copper oxide particles prepared in Example 2.
  • a method for preparing nano-copper oxide according to an embodiment shown in FIG. 1 includes the following steps:
  • the copper source may be copper hydroxide (Cu(OH) 2 ), copper chloride (CuCl 2 .2H 2 O), copper sulfate (CuSO 4 ⁇ 5H 2 O), basic copper carbonate (Cu 2 (OH) 2 CO 3 ), copper citrate (C 6 H 6 CuO 7 ), copper acetate (Cu(CH 3 COO) 2 ⁇ H 2 O) or copper acetylacetonate (Cu(C 5 H 7 O 2 ) 2 ).
  • the concentration of the copper source in the first dispersion is from 0.01 mol/L to 1 mol/L.
  • the operation of disposing the first dispersion liquid by using a copper source is: adding a copper source to the first solvent, and refluxing at 100 ° C to 180 ° C for 10 min to 60 min to obtain a first dispersion liquid.
  • the first solvent is selected to be an alcohol-water mixture
  • the alcohol in the alcohol-water mixture is selected from the group consisting of methanol, ethanol, butanol, cyclohexanol, isopropanol, ethylene glycol, diethylene glycol, and glycerin.
  • At least one of the water in the alcohol-water mixture is deionized water.
  • the volume ratio of alcohol to water in the aqueous alcohol mixture is from 1:4 to 4:1.
  • the alcohol-water mixture can better disperse the copper source and facilitate the dispersion of the obtained nano-copper oxide.
  • the strong base can be potassium hydroxide or sodium hydroxide.
  • the concentration of the strong base in the second dispersion is 0.02 mol/L to 2 mol/L.
  • the operation of disposing the second dispersion liquid with a strong base is carried out by adding a strong base solid to the second solvent and stirring uniformly at room temperature to obtain a second dispersion liquid.
  • the solvent of the second dispersion is a second solvent, and the second solvent is a mixture of alcohol and water.
  • the alcohol in the aqueous alcohol mixture is selected from the group consisting of at least one of anhydrous methanol, ethanol, butanol, cyclohexanol, isopropanol, ethylene glycol, diethylene glycol and glycerin, in an aqueous alcohol mixture
  • the water is deionized water.
  • the volume ratio of alcohol to water in the aqueous alcohol mixture is from 1:4 to 4:1.
  • the first solvent is the same as the second solvent.
  • the preparation method of the nanometer copper oxide particles adopts a high-temperature reflux combined with an alcohol-water mixed solvent, so that the copper source can be well dispersed, and the obtained nano copper oxide has high dispersibility.
  • the preparation method of the nanometer copper oxide particles is simple, the prepared nanometer copper oxide particles are easy to separate, the reaction conditions are relatively mild, the reaction time is short, the preparation efficiency is high, the equipment requirements are low, and the requirements of “green chemistry” are met. .
  • the prepared nanometer copper oxide has good dispersibility and can be directly separated, and the ink can be directly prepared, and is convenient to use.
  • the prepared nano copper oxide particles avoid the problem of oxidation of the nano copper, and the particle size of the nano copper oxide particles is small, about 5 to 50 nm.
  • the printing method of the metal-based ink according to an embodiment shown in FIG. 2 includes the following steps:
  • S200 After disposing the nano-copper oxide obtained by S100 into ink, printing on a substrate, and obtaining a printed pattern having good conductivity by low-temperature atmosphere reduction or photoreduction.
  • the mass fraction of nano-copper oxide in the ink is 5%-80%, and the solvent of the ink is selected according to the configuration of common oil-based and water-based inks.
  • the oily system selects toluene, xylene, diethyl ether, etc.
  • the aqueous system is Water, alcohol, polyol, low boiling ester, and the like are selected.
  • Commonly used additives are: polyvinyl alcohol, PVDF, cellulose acetate and the like.
  • the ink may be composed of nano-copper oxide and a solvent in a mass ratio of 1 : 0.5 to 2.
  • the substrate can be selected from commonly used substrates, and generally can be PI, PE or PP.
  • the ink can be printed on the substrate by inkjet printing, silk screen or micro-gravure.
  • the reduction temperature is 150 ° C to 300 ° C
  • the reducing atmosphere is at least one of hydrogen, carbon monoxide, hydrogen sulfide, and methane.
  • the reduction beam is ultraviolet light or yellow light, or the reduction beam is a laser light.
  • potassium hydroxide 0.02 mol was added to 100 mL of deionized water, and stirred at room temperature to obtain a potassium hydroxide dispersion.
  • the KOH dispersion was added to a copper source dispersion, and the reaction was stirred under reflux at 100 ° C for 10 minutes to obtain a rapidly precipitated nano copper oxide.
  • the nano-copper oxide particle solution is separated in a centrifuge and dried to obtain nano-copper oxide particles for printing electrons.
  • the pattern was printed by an inkjet printing method, and calcination was carried out at 150 ° C using a reducing gas hydrogen gas to obtain a printed pattern having good conductivity.
  • Example 3 is a TEM image of the nano-copper oxide particles prepared in Example 1. It can be seen from FIG. 3 that the nanometer cuprous oxide prepared in Example 1 has a particle diameter of about 7 nm and good dispersibility.
  • the KOH dispersion was added to a copper source dispersion, and the reaction was stirred under reflux at 120 ° C for 40 minutes to obtain a rapidly precipitated nano copper oxide.
  • the nano-copper oxide particle solution is separated in a centrifuge and dried to obtain nano-copper oxide particles for printing electrons.
  • the pattern was printed by silk screen printing, and calcination was carried out at 300 ° C using a reducing gas carbon monoxide to obtain a printed pattern having good conductivity.
  • Example 4 is an XRD spectrum of the nano-copper oxide particles prepared in Example 2. It can be seen from FIG. 3 that the XRD peak of the nano-copper oxide particles prepared in Example 2 conforms to the standard spectrum of copper oxide, and no other impurities exist.
  • the KOH dispersion was added to the copper source dispersion A, and the reaction was stirred under reflux at 180 ° C for 10 minutes to obtain a rapidly precipitated nano copper oxide.
  • the nano-copper oxide particle solution is separated in a centrifuge and dried to obtain nano-copper oxide particles for printing electrons.
  • the pattern was printed by a micro-gravure method, and calcination was carried out at 150 ° C using a reducing gas hydrogen sulfide to obtain a printed pattern having good conductivity.
  • potassium hydroxide 0.002 mol was added to 100 mL of ethylene glycol, and stirred at room temperature to obtain a potassium hydroxide dispersion.
  • the KOH dispersion was added to a copper source dispersion, and the reaction was stirred at a high temperature reflux of 180 ° C for 60 minutes to obtain a rapidly precipitated nano copper oxide.
  • the nano-copper oxide particle solution is separated in a centrifuge and dried to obtain nano-copper oxide particles for printing electrons.
  • the pattern was printed by inkjet printing, and calcination was carried out at 300 ° C using a reducing gas methane to obtain a printed pattern having good conductivity.
  • potassium hydroxide 0.02 mol was added to 100 mL of diethylene glycol, and stirred at room temperature to obtain a potassium hydroxide dispersion.
  • the KOH dispersion was added to a copper source dispersion, and the reaction was stirred under reflux at 120 ° C for 10 minutes to obtain a rapidly precipitated nano copper oxide.
  • the nano-copper oxide particle solution is separated in a centrifuge and dried to obtain nano-copper oxide particles for printing electrons.
  • the pattern is printed by silk screen printing, and the laser is used for photoreduction to obtain a printed pattern having good conductivity.
  • the KOH dispersion was added to a copper source dispersion, and the reaction was stirred under reflux at 120 ° C for 60 minutes to obtain a rapidly precipitated nano copper oxide.
  • the nano-copper oxide particle solution is separated in a centrifuge and dried to obtain nano-copper oxide particles for printing electrons.
  • the pattern is printed by a micro-gravure method, and the light is reduced by ultraviolet light to obtain a printed pattern having good conductivity.
  • potassium hydroxide 0.002 mol was added to 100 mL of ethylene glycol, and stirred at room temperature to obtain a potassium hydroxide dispersion.
  • the KOH dispersion was added to a copper source dispersion, and the reaction was stirred at 140 ° C for 10 minutes under reflux to obtain a rapidly precipitated nano copper oxide.
  • the nano-copper oxide particle solution is separated in a centrifuge and dried to obtain nano-copper oxide particles for printing electrons.
  • the pattern is printed by inkjet printing, and the yellow light is used for photoreduction to obtain a printed pattern having good conductivity.
  • potassium hydroxide 0.02 mol was added to 50 mL of ethylene glycol and 50 mL of deionized water, and stirred at room temperature to obtain a potassium hydroxide dispersion.
  • the KOH dispersion was added to a copper source dispersion, and the reaction was stirred under reflux at 140 ° C for 60 minutes to obtain a rapidly precipitated nano copper oxide.
  • the nano-copper oxide particle solution is separated in a centrifuge and dried to obtain a nanometer for printing electrons. Copper oxide particles.
  • the pattern was printed by silk screen printing, and calcination was carried out at 150 ° C using a reducing gas carbon monoxide to obtain a printed pattern having good conductivity.
  • the KOH dispersion was added to a copper source dispersion, and the reaction was stirred under reflux at 160 ° C for 10 minutes to obtain a rapidly precipitated nano copper oxide.
  • the nano-copper oxide particle solution is separated in a centrifuge and dried to obtain nano-copper oxide particles for printing electrons.
  • the pattern was printed by a micro-gravure method, and calcination was carried out at 150 ° C using a reducing gas of hydrogen and methane to obtain a printed pattern having good conductivity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Conductive Materials (AREA)

Abstract

提供一种纳米氧化铜的制备方法，包括如下步骤：采用铜源配置第一分散液；采用强碱配置第二分散液；以及将第一分散液和第二分散液混合，于100℃～180℃下回流搅拌反应10min～60min，得到的反应液经过分离后保留固体，即为纳米氧化铜。还提供一种采用上述制得的纳米氧化铜的金属基油墨的印刷方法。

Description

纳米氧化铜的制备方法以及金属基油墨的印刷方法 技术领域
本发明涉及一种纳米氧化铜的制备方法，以及采用制得的纳米氧化铜的金属基油墨的印刷方法。
背景技术
纳米氧化铜颗粒，由于其小尺寸效应，宏观量子隧道效应、表面效应、体积效应的影响，将会显现出独特的性能，在光吸收、电化学、催化反应、储能材料等方面表现出特殊的物化性能，使其应用领域更加广泛。但是，单分散的小尺寸氧化铜制备困难，方法麻烦，常需要有机溶剂或高温高压反应条件下才能微量制备。
在金属基油墨中，纳米银导电油墨水因其价格高和银迁移等缺陷，发展受到一定限制。铜油墨导电性优良，并且成本比银低，纳米铜基导电油墨代替传统的化学蚀刻(或激光蚀刻)或电镀工艺，不仅能显著降低成本而且可以绿色环保的印制电子，这对于印刷电路板(PCB)、电子标签(RFID)、触摸屏、薄膜开关、太阳能电池、LED/OLED等诸多行业和领域具有示范意义，使这些行业在电子电路技术方面实现从传统的蚀刻、电镀工艺向绿色环保的印制电子工艺的转变，大幅度提升行业技术水平。
然而，小尺寸铜不仅难以制备而且易氧化，因此一般需要先制备纳米氧化铜。
发明内容
基于此，有必要提供一种纳米氧化铜的制备方法，以及采用制得的纳米氧化铜的金属基油墨的印刷方法。
一种纳米氧化铜的制备方法，包括如下步骤：
采用铜源配置第一分散液；
采用强碱配置第二分散液；以及
将所述第一分散液和所述第二分散液混合，于100℃～180℃下回流搅拌反应10min～60min，得到的反应液经过分离后保留固体，所述固体即为纳米氧化铜。
在一个实施例中，所述铜源为氢氧化铜、氯化铜、硫酸铜、碱式碳酸铜、柠檬酸铜、醋酸铜或乙酰丙酮铜。
在一个实施例中，所述第一分散液中所述铜源的浓度为0.01mol/L～1mol/L。
在一个实施例中，所述采用铜源配置第一分散液的操作为：将所述铜源加入第一溶剂中，于100℃～180℃下回流搅拌10min～60min，得到所述第一分散液。
在一个实施例中，所述第一溶剂为醇水混合液；所述醇水混合液中的醇选自甲醇、乙醇、丁醇、环己醇、异丙醇、乙二醇、一缩二乙二醇和丙三醇中的至少一种，所述醇水混合液中的水为去离子水。
在一个实施例中，所述强碱为将氢氧化钾或氢氧化钠。
在一个实施例中，所述第二分散液的溶剂为第二溶剂，所述第二溶剂为醇水混合液；
所述醇水混合液中的醇选自无水甲醇、乙醇、丁醇、环己醇、异丙醇、乙二醇、一缩二乙二醇和丙三醇中的至少一种，所述醇水混合液中的水为去离子水。
在一个实施例中，所述第二分散液中所述强碱的浓度为0.02mol/L～2mol/L。
一种金属基油墨的印刷方法，包括如下步骤：
采用上述的纳米氧化铜的制备方法制备纳米氧化铜；以及
将得到的所述纳米氧化铜配置成墨水后，印制在承印基材上，经低温气氛还原或光还原的方式得到获得具有良好导电性的印制图形。
在一个实施例中，所述墨水为油性墨水或水性墨水，所述墨水通过喷墨打印、丝印或微凹版的方式印制在所述承印基材上。
在一个实施例中，所述低温气氛还原的操作中，还原温度为150℃～300℃，还原气氛为氢气、一氧化碳、硫化氢和甲烷中的至少一种。
在一个实施例中，所述光还原的操作中，还原光束为紫外光或黄光，或者 还原光束为激光。
这种纳米氧化铜的制备方法通过含有铜源的第一分散液和含有强碱的第二分散液混合，于100℃～180℃下回流搅拌反应10min～60min，能够制得分散性较好的纳米氧化铜颗粒。
附图说明
图1为一实施方式的纳米氧化铜的制备方法的流程图；
图2为一实施方式的金属基油墨的印刷方法的流程图；
图3为实施例1制备得到的纳米氧化铜颗粒的TEM图片；
图4为实施例2制备得到的纳米氧化铜颗粒的XRD谱图。
具体实施方式
下面主要结合附图及具体实施例对铁氧体粉体的制造方法作进一步详细的说明。
如图1所示的一实施方式的纳米氧化铜的制备方法，包括如下步骤：
S10、采用铜源配置第一分散液。
铜源可以为氢氧化铜(Cu(OH)2)、氯化铜(CuCl2·2H2O)、硫酸铜(CuSO4·5H2O)、碱式碳酸铜(Cu2(OH)2CO3)、柠檬酸铜(C6H6CuO7)、醋酸铜(Cu(CH3COO)2·H2O)或乙酰丙酮铜(Cu(C5H7O2)2)。
第一分散液中铜源的浓度为0.01mol/L～1mol/L。
S10中，采用铜源配置第一分散液的操作为：将铜源加入第一溶剂中，于100℃～180℃下回流搅拌10min～60min，得到第一分散液。
第一溶剂选为为醇水混合液，醇水混合液中的醇选自甲醇、乙醇、丁醇、环己醇、异丙醇、乙二醇、一缩二乙二醇和丙三醇中的至少一种，醇水混合液中的水为去离子水。
优选的，醇水混合液中的醇和水的体积比为1∶4～4∶1。
醇水混合液能够使铜源较好地分散，有利于制得的纳米氧化铜的分散。
S20、采用强碱配置第二分散液。
强碱可以为将氢氧化钾或氢氧化钠。
第二分散液中强碱的浓度为0.02mol/L～2mol/L。
S20中，采用强碱配置第二分散液的操作为：将强碱固体加入第二溶剂中，于室温下搅拌均匀，得到第二分散液。
第二分散液的溶剂为第二溶剂，第二溶剂为醇水混合液。
醇水混合液中的醇选自无水甲醇、乙醇、丁醇、环己醇、异丙醇、乙二醇、一缩二乙二醇和丙三醇中的至少一种，醇水混合液中的水为去离子水。
优选的，醇水混合液中的醇和水的体积比为1∶4～4∶1。
本实施方式中，第一溶剂与第二溶剂相同。
S30、将S10得到的第一分散液和S20得到的第二分散液混合，于100℃～180℃下回流搅拌反应10min～60min，得到的反应液经过分离后保留固体，固体即为纳米氧化铜。
这种纳米氧化铜颗粒的制备方法采用高温回流结合醇水混合型溶剂，能够使铜源较好地分散，制得的纳米氧化铜的分散性较高。
这种纳米氧化铜颗粒的制备方法工艺简单，制得的纳米氧化铜颗粒分散性好易分离，反应条件相对温和，反应时间短，制备效率高，对设备要求低，符合“绿色化学“的要求。
制备得到的纳米氧化铜分散性好易分离，可直接配制油墨，使用方便。
制备得到的纳米氧化铜颗粒避免了纳米铜的氧化问题，且纳米氧化铜颗粒的粒径较小，约为5～50nm左右。
如图2所示的一实施方式的金属基油墨的印刷方法，包括如下步骤：
S100、采用上述的纳米氧化铜的制备方法制备纳米氧化铜。
S200、将S100得到的纳米氧化铜配置成墨水后，印制在承印基材上，经低温气氛还原或光还原的方式得到获得具有良好导电性的印制图形。
墨水中纳米氧化铜的质量分数为5％～80％，墨水的溶剂按照常用的油性、水性墨水的配置选择，如油性体系则选择甲苯、二甲苯、乙醚等，水性体系则 选择水、醇、多元醇、低沸点的酯等。常用的助剂有：聚乙烯醇、PVDF、醋酸纤维素等。
本实施方式中，墨水可以为纳米氧化铜和溶剂按照质量比为1∶0.5～2配置而成。
承印基材选择常用基材即可，一般可以为PI、PE或PP。墨水可以通过喷墨打印、丝印或微凹版的方式印制在承印基材上。
低温气氛还原的操作中，还原温度为150℃～300℃，还原气氛为氢气、一氧化碳、硫化氢和甲烷中的至少一种。
光还原的操作中，还原光束为紫外光或黄光，或者还原光束为激光。
下面为具体实施例。
实施例1
将0.01mol醋酸铜加入100mL无水乙醇中，于100℃下回流搅拌，搅拌均匀得到铜源分散液。
将0.02mol氢氧化钾加入100mL去离子水中，于室温搅拌均匀得到氢氧化钾分散液。
将KOH分散液加入铜源分散液中，于100℃下回流搅拌反应10分钟，得到快速沉淀纳米氧化铜。
将纳米氧化铜颗粒溶液于离心机中分离，烘干后得到用于印刷电子的纳米氧化铜颗粒。
将得到的纳米氧化铜配制成油性油墨后，采用喷墨打印方式印制图形，使用还原性气体氢气在150℃下进行焙烧得到导电性良好的印制图形。
图3为实施例1制备得到的纳米氧化铜颗粒的TEM图片。由图3可看出，实施例1制备得到的纳米氧化亚铜的粒径为7nm左右，且分散性较好。
实施例2
将0.01mol氯化铜加入100mL乙二醇中，于120℃下回流搅拌，搅拌均匀 得到铜源分散液。
将0.002mol氢氧化纳加入100mL无水乙醇中，于室温搅拌均匀得到氢氧化钾分散液。
将KOH分散液加入铜源分散液中，于120℃下回流搅拌反应40分钟，得到快速沉淀纳米氧化铜。
将纳米氧化铜颗粒溶液于离心机中分离，烘干后得到用于印刷电子的纳米氧化铜颗粒。
将得到的纳米氧化铜配制成水性油墨后，采用丝印的方式印制图形，使用还原性气体一氧化碳在300℃下进行焙烧得到导电性良好的印制图形。
图4为实施例2制备得到的纳米氧化铜颗粒的XRD谱图。由图3可看出，实施例2制备得到的纳米氧化铜颗粒的XRD峰值符合氧化铜的标准谱图，没有其他杂质的存在。
实施例3
将0.01mol氢氧化铜加入100mL一缩二乙二醇中，于180℃下回流搅拌，搅拌均匀得到铜源分散液。
将0.2mol氢氧化钾加入100mL无水乙醇中，于室温搅拌均匀得到氢氧化钾分散液。
将KOH分散液加入铜源分散液A中，于180℃下回流搅拌反应10分钟，得到快速沉淀纳米氧化铜。
将纳米氧化铜颗粒溶液于离心机中分离，烘干后得到用于印刷电子的纳米氧化铜颗粒。
将得到的纳米氧化铜配制成油性油墨后，采用微凹版的方式印制图形，使用还原性气体硫化氢在150℃下进行焙烧得到导电性良好的印制图形。
实施例4
将0.001mol硫酸铜加入100mL去离子水中，于180℃下回流搅拌，搅拌均 匀得到铜源分散液。
将0.002mol氢氧化钾加入100mL乙二醇中，于室温搅拌均匀得到氢氧化钾分散液。
将KOH分散液加入铜源分散液中，于高温回流180℃下搅拌反应60分钟，得到快速沉淀纳米氧化铜。
将纳米氧化铜颗粒溶液于离心机中分离，烘干后得到用于印刷电子的纳米氧化铜颗粒。
将得到的纳米氧化铜配制成水性油墨后，采用喷墨打印的方式印制图形，使用还原性气体甲烷在300℃下进行焙烧得到导电性良好的印制图形。
实施例5
将0.001mol碱式碳酸铜加入50mL无水乙醇和50mL去离子水中，于120℃下回流搅拌，搅拌均匀得到铜源分散液。
将0.02mol氢氧化钾加入100mL一缩二乙二醇中，于室温搅拌均匀得到氢氧化钾分散液。
将KOH分散液加入铜源分散液中，于120℃下回流搅拌反应10分钟，得到快速沉淀纳米氧化铜。
将纳米氧化铜颗粒溶液于离心机中分离，烘干后得到用于印刷电子的纳米氧化铜颗粒。
将得到的纳米氧化铜配制成油性油墨后，采用丝印的方式印制图形，使用激光进行光还原得到导电性良好的印制图形。
实施例6
将0.001mol柠檬酸铜加入100mL无水乙醇中，于120℃下回流搅拌，搅拌均匀得到铜源分散液。
将0.2mol氢氧化钾加入50mL无水乙醇和50mL去离子水中，于室温搅拌均匀得到氢氧化钾分散液。
将KOH分散液加入铜源分散液中，于120℃下回流搅拌反应60分钟，得到快速沉淀纳米氧化铜。
将纳米氧化铜颗粒溶液于离心机中分离，烘干后得到用于印刷电子的纳米氧化铜颗粒。
将得到的纳米氧化铜配制成水性油墨后，采用微凹版的方式印制图形，使用紫外光进行光还原得到导电性良好的印制图形。
实施例7
将0.1mol乙酰丙酮铜加入50mL无水乙醇和50mL去离子水中，于140℃下回流搅拌，搅拌均匀得到铜源分散液。
将0.002mol氢氧化钾加入100mL乙二醇中，于室温搅拌均匀得到氢氧化钾分散液。
将KOH分散液加入铜源分散液中，于140℃下回流搅拌反应10分钟，得到快速沉淀纳米氧化铜。
将纳米氧化铜颗粒溶液于离心机中分离，烘干后得到用于印刷电子的纳米氧化铜颗粒。
将得到的纳米氧化铜配制成油性油墨后，采用喷墨打印的方式印制图形，使用黄光进行光还原得到导电性良好的印制图形。
实施例8
将0.1mol醋酸铜加入100mL去离子水中，于140℃下回流搅拌，搅拌均匀得到铜源分散液。
将0.02mol氢氧化钾加入50mL乙二醇和50mL去离子水中，于室温搅拌均匀得到氢氧化钾分散液。
将KOH分散液加入铜源分散液中，于140℃下回流搅拌反应60分钟，得到快速沉淀纳米氧化铜。
将纳米氧化铜颗粒溶液于离心机中分离，烘干后得到用于印刷电子的纳米 氧化铜颗粒。
将得到的纳米氧化铜配制成水性油墨后，采用丝印的方式印制图形，使用还原性气体一氧化碳在150℃下进行焙烧得到导电性良好的印制图形。
实施例9
将0.1mol醋酸铜加入50mL无水乙醇和50mL去离子水中，于140℃下回流搅拌，搅拌均匀得到铜源分散液。
将0.2mol氢氧化钾加入50mL无水乙醇和50mL去离子水中，于室温搅拌均匀得到氢氧化钾分散液。
将KOH分散液加入铜源分散液中，于160℃下回流搅拌反应10分钟，得到快速沉淀纳米氧化铜。
将纳米氧化铜颗粒溶液于离心机中分离，烘干后得到用于印刷电子的纳米氧化铜颗粒。
将得到的纳米氧化铜配制成油性油墨后，采用微凹版的方式印制图形，使用还原性气体氢气和甲烷混合气中在150℃下进行焙烧得到导电性良好的印制图形。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (12)

  1. 一种纳米氧化铜的制备方法，其特征在于，包括如下步骤：
    采用铜源配置第一分散液；
    采用强碱配置第二分散液；以及
    将所述第一分散液和所述第二分散液混合，于100℃～180℃下回流搅拌反应10min～60min，得到的反应液经过分离后保留固体，所述固体即为纳米氧化铜。
  2. 如权利要求1所述的纳米氧化铜的制备方法，其特征在于，所述铜源为氢氧化铜、氯化铜、硫酸铜、碱式碳酸铜、柠檬酸铜、醋酸铜或乙酰丙酮铜。
  3. 如权利要求1或2所述的纳米氧化铜的制备方法，其特征在于，所述第一分散液中所述铜源的浓度为0.01mol/L～1mol/L。
  4. 如权利要求1所述的纳米氧化铜的制备方法，其特征在于，所述采用铜源配置第一分散液的操作为：将所述铜源加入第一溶剂中，于100℃～180℃下回流搅拌10min～60min，得到所述第一分散液。
  5. 如权利要求4所述的纳米氧化铜的制备方法，其特征在于，所述第一溶剂为醇水混合液；所述醇水混合液中的醇选自甲醇、乙醇、丁醇、环己醇、异丙醇、乙二醇、一缩二乙二醇和丙三醇中的至少一种，所述醇水混合液中的水为去离子水。
  6. 如权利要求1所述的纳米氧化铜的制备方法，其特征在于，所述强碱为将氢氧化钾或氢氧化钠。
  7. 如权利要求1所述的纳米氧化铜的制备方法，其特征在于，所述第二分散液的溶剂为第二溶剂，所述第二溶剂为醇水混合液；
    所述醇水混合液中的醇选自无水甲醇、乙醇、丁醇、环己醇、异丙醇、乙二醇、一缩二乙二醇和丙三醇中的至少一种，所述醇水混合液中的水为去离子水。
  8. 如权利要求1所述的纳米氧化铜的制备方法，其特征在于，所述第二分散液中所述强碱的浓度为0.02mol/L～2mol/L。
  9. 一种金属基油墨的印刷方法，其特征在于，包括如下步骤：
    采用权利要求1～8中任一项所述的纳米氧化铜的制备方法制备纳米氧化铜；以及
    将得到的所述纳米氧化铜配置成墨水后，印制在承印基材上，经低温气氛还原或光还原的方式得到获得具有良好导电性的印制图形。
  10. 如权利要求9所述的金属基油墨的印刷方法，其特征在于，所述墨水为油性墨水或水性墨水，所述墨水通过喷墨打印、丝印或微凹版的方式印制在所述承印基材上。
  11. 如权利要求9所述的金属基油墨的印刷方法，其特征在于，所述低温气氛还原的操作中，还原温度为150℃～300℃，还原气氛为氢气、一氧化碳、硫化氢和甲烷中的至少一种。
  12. 如权利要求9所述的金属基油墨的印刷方法，其特征在于，所述光还原的操作中，还原光束为紫外光或黄光，或者还原光束为激光。
PCT/CN2015/084688 2014-12-18 2015-07-21 纳米氧化铜的制备方法以及金属基油墨的印刷方法 WO2016095520A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410795800.7A CN104528801A (zh) 2014-12-18 2014-12-18 纳米氧化铜的制备方法以及金属基油墨的印刷方法
CN201410795800.7 2014-12-18

Publications (1)

Publication Number Publication Date
WO2016095520A1 true WO2016095520A1 (zh) 2016-06-23

Family

ID=52844496

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/084688 WO2016095520A1 (zh) 2014-12-18 2015-07-21 纳米氧化铜的制备方法以及金属基油墨的印刷方法

Country Status (2)

Country Link
CN (1) CN104528801A (zh)
WO (1) WO2016095520A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10626021B2 (en) 2017-03-31 2020-04-21 Honda Motor Co., Ltd. Method of making metal and metal oxide nanoparticles

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104528801A (zh) * 2014-12-18 2015-04-22 中国科学院深圳先进技术研究院 纳米氧化铜的制备方法以及金属基油墨的印刷方法
CN105086626A (zh) * 2015-08-25 2015-11-25 桐城市福润包装材料有限公司 一种纳米氧化铜喷墨墨水配方
CN105858709A (zh) * 2016-03-25 2016-08-17 辽宁石油化工大学 一种制备纳米氧化铜的方法
CN108585021B (zh) * 2018-07-16 2020-02-21 河北工业大学 一种氧化铜介孔纳米片的制备方法
CN111239203B (zh) * 2018-11-29 2022-05-17 中国科学院大连化学物理研究所 一种氧化铜薄膜的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101547567A (zh) * 2008-03-28 2009-09-30 富葵精密组件(深圳)有限公司 导电线路的制作方法
CN102320644A (zh) * 2011-08-17 2012-01-18 金川集团有限公司 一种制备氧化铜粉的方法
CN102549086A (zh) * 2009-09-16 2012-07-04 日立化成工业株式会社 印刷法用油墨以及用于该油墨的金属纳米粒子、以及布线、电路基板、半导体封装
CN102951671A (zh) * 2012-10-22 2013-03-06 洛阳师范学院 一种氧化铜纳米粒子的制备方法
CN104528801A (zh) * 2014-12-18 2015-04-22 中国科学院深圳先进技术研究院 纳米氧化铜的制备方法以及金属基油墨的印刷方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104003433A (zh) * 2014-04-30 2014-08-27 上海应用技术学院 一种纳米氧化铜材料的制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101547567A (zh) * 2008-03-28 2009-09-30 富葵精密组件(深圳)有限公司 导电线路的制作方法
CN102549086A (zh) * 2009-09-16 2012-07-04 日立化成工业株式会社 印刷法用油墨以及用于该油墨的金属纳米粒子、以及布线、电路基板、半导体封装
CN102320644A (zh) * 2011-08-17 2012-01-18 金川集团有限公司 一种制备氧化铜粉的方法
CN102951671A (zh) * 2012-10-22 2013-03-06 洛阳师范学院 一种氧化铜纳米粒子的制备方法
CN104528801A (zh) * 2014-12-18 2015-04-22 中国科学院深圳先进技术研究院 纳米氧化铜的制备方法以及金属基油墨的印刷方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHU, JUNWU: "Study on the Preparation, Property and Application of Microstructure-controlled Metal Oxide Nanocrystals", CHINESE DOCTORAL DISSERTATIONS & MASTERS THESES FULL-TEXT DATABASE (DOCTOR), ENGINEERING SCIENCE AND TECHNOLOGY, no. 7, 15 November 2015 (2015-11-15), pages 17 and 23 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10626021B2 (en) 2017-03-31 2020-04-21 Honda Motor Co., Ltd. Method of making metal and metal oxide nanoparticles

Also Published As

Publication number Publication date
CN104528801A (zh) 2015-04-22

Similar Documents

Publication Publication Date Title
WO2016095520A1 (zh) 纳米氧化铜的制备方法以及金属基油墨的印刷方法
Rezaul Karim et al. Photoelectrocatalytic reduction of carbon dioxide to methanol using CuFe2O4 modified with graphene oxide under visible light irradiation
Yang et al. Ultrasound-spray deposition of multi-walled carbon nanotubes on NiO nanoparticles-embedded perovskite layers for high-performance carbon-based perovskite solar cells
Chang et al. Preparation, characterization and reaction mechanism of a novel silver-organic conductive ink
CN103332678A (zh) 石墨烯及石墨烯-氧化物复合物的制备方法
US20060093892A1 (en) Catalyst for fuel cell, method for preparing the same, and membrane-electrode assembly and fuel cell system comprising same
CN107245727A (zh) 一种多孔磷化钴纳米线催化剂的制备方法
CN106268953A (zh) 一种氧化石墨烯和含铈配位聚合物的棒状多孔复合材料及其制备方法
Liang et al. Ferric iron reduction reaction electro-Fenton with gas diffusion device: A novel strategy for improvement of comprehensive efficiency in electro-Fenton
JP2006260844A (ja) 燃料電池電極用触媒、燃料電池電極、膜電極接合体および燃料電池
CN101931081A (zh) 电化学还原二氧化碳制甲醇的空气扩散电极制备方法
CN105754414B (zh) 一种导电纳米铜墨水及其制备方法
Niu et al. Innovating e-waste recycling: From waste multi-layer ceramic capacitors to NbPb codoped and ag-Pd-Sn-Ni loaded BaTiO3 nano-photocatalyst through one-step ball milling process
CN106450590A (zh) 一种铜/氮双掺杂的多孔纤维状碳材料、制备方法及其应用
Li et al. Conductivity and foldability enhancement of Ag patterns formed by PVAc modified Ag complex inks with low-temperature and rapid sintering
JP2017179551A (ja) ニッケル粒子、導電性ペースト、内部電極及び積層セラミックコンデンサ
CN102583559A (zh) 一种微米级α-MnO2空心球的制备方法
KR101401571B1 (ko) 전도성 이온 잉크 조성물, 그 제조방법 및 이를 이용한 고전도성 패턴 또는 막의 형성방법
CN106366769A (zh) 一种抗氧化纳米铜导电墨水及其制备方法和印刷应用
Prajapati et al. Unravelling the redox behaviour of a carbon nitride polymer-based ternary heterostructure for CO 2 photoreduction promoted by amine coupling
Chang et al. Fabrication of In (OH) 3–In2S3–Cu2O nanofiber for highly efficient photocatalytic hydrogen evolution under blue light LED excitation
WO2012133239A1 (ja) カーボンナノチューブ・カーボンナノホーン複合体、カーボンナノチューブ・カーボンナノホーン複合体の製造方法および用途
CN109382097B (zh) 一种微乳液法制备铂铱钌复合纳米颗粒的方法
KR101621125B1 (ko) 연료전지 촉매용 탄소-금속-금속 산화물 복합체의 제조방법 및 이를 이용한 연료전지 촉매용 탄소-금속-금속 산화물 복합체
CN103722179B (zh) 用于导电油墨的纳米铜浆的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15869031

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 03.11.2017)

122 Ep: pct application non-entry in european phase

Ref document number: 15869031

Country of ref document: EP

Kind code of ref document: A1