CN112992422B - Preparation method of copper-gold alloy nanowire flexible transparent conductive film - Google Patents
Preparation method of copper-gold alloy nanowire flexible transparent conductive film Download PDFInfo
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- CN112992422B CN112992422B CN202110169586.4A CN202110169586A CN112992422B CN 112992422 B CN112992422 B CN 112992422B CN 202110169586 A CN202110169586 A CN 202110169586A CN 112992422 B CN112992422 B CN 112992422B
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Abstract
The invention discloses a preparation method of a copper-gold alloy nanowire flexible transparent conductive film, and belongs to the technical field of flexible transparent conductive films. The invention solves the problem that the poor electrochemical stability of the existing copper nanowire hinders the application of the copper nanowire in a flexible electrochemical device. According to the invention, the copper-gold alloy nanowire is prepared by introducing the gold element into the copper nanowire in an electrochemical manner, so that the electrochemical stability of the flexible transparent conductive film of the copper nanowire is effectively improved, and the electrochemical corrosion is resisted. In addition, the mode of preparing the copper nanowire conductive network and then introducing gold atoms to prepare the copper-gold alloy nanowire network provided by the invention is more convenient and faster than the mode of preparing the copper-gold alloy nanowires and then preparing the copper-gold alloy nanowire conductive network by a liquid phase reduction method in the prior art, the uniformity of the product is higher, the connection performance of the joint can be improved, and the conductivity of the transparent conductive film is improved.
Description
Technical Field
The invention relates to a preparation method of a copper-gold alloy nanowire flexible transparent conductive film, and belongs to the technical field of flexible transparent conductive films.
Background
The transparent conductive film is an indispensable important component in electrochemical devices such as electrochromic devices, transparent energy storage devices and the like. In recent years, with the continuous progress of flexible and wearable electronics, these electrochemical devices are also in need of flexibility. Currently, indium tin oxide is the most widely used transparent conductive thin film material, but the indium tin oxide is relatively brittle and is difficult to meet the requirement of flexibility. Copper nanowires are considered to be one of the most potential materials to replace ITO to prepare flexible transparent conductive thin films due to their excellent mechanical flexibility, low cost and good photoelectric properties, but their poor electrochemical stability hinders their further application in flexible electrochemical devices. In addition, the loose lap joints between the copper nanowires can also lead to poor conductivity of the flexible transparent conductive film, so that it is necessary to provide a method capable of effectively improving the electrochemical stability of the copper nanowire transparent conductive film.
Disclosure of Invention
The invention provides a preparation method of a copper-gold alloy nanowire flexible transparent conductive film, aiming at solving the technical problems.
The technical scheme of the invention is as follows:
a preparation method of a copper-gold alloy nanowire flexible transparent conductive film comprises the following steps:
coating copper nanowire ink on the surface of a flexible substrate, and drying to obtain a transparent conductive film;
and step two, taking the transparent conductive film obtained in the step one as a cathode, taking a graphite electrode as an anode, and electrifying two ends of the electrode in the electrolyte to obtain the copper-gold alloy nanowire electrode.
Further, in the first step, the flexible substrate is PET, PVC, PU or PDMS.
Further, the copper nanowire ink is obtained by dispersing copper nanowires in a solvent.
Further, the solvent is n-hexane, isopropanol, ethanol or water.
Further, the method for coating the copper nanowire ink on the surface of the flexible substrate in the first step comprises the following steps: and coating the copper nanowire ink on the surface of the flexible substrate by adopting a vacuum filtration method.
Further, in the first step, the drying temperature is 90-110 ℃, and the drying time is 6-8 min.
Further, in the second step, the electrolyte contains 5-15mmol/L HAuCl 4 And 0.2-0.3mol/L H 2 SO 4 。
Further, the current density in the second step is 18-22mA/cm 2 。
Further, the electrifying time in the step two is 8-12 s.
The invention has the following beneficial effects: according to the invention, the copper-gold alloy nanowire is prepared by introducing the gold element into the copper nanowire in an electrochemical manner, so that the electrochemical stability of the flexible transparent conductive film of the copper nanowire is effectively improved, and the electrochemical corrosion is resisted. The method provided by the invention is characterized in that the copper nanowire conductive network is prepared firstly, then gold atoms are introduced into the copper nanowire network in an electrochemical mode to prepare the copper-gold alloy flexible transparent conductive film, and compared with the existing method of preparing the copper-gold alloy nanowire by a liquid phase reduction method and then preparing the copper-gold alloy nanowire conductive network, the method provided by the invention is more convenient and faster, and the uniformity of the product is higher. In addition, the invention also has the following advantages:
(1) the electrochemical stability of the transparent conductive film prepared by the invention is improved, and when the transparent conductive film is applied to flexible electrochemical devices such as electrochromism and super capacitors, the pure copper nanowire transparent conductive film can be rapidly damaged when being used as an anode, but the copper-gold alloy transparent conductive film can stably work.
(2) Compared with the mode of firstly preparing the copper-gold alloy nanowire by a liquid phase reduction method and then preparing the copper-gold alloy nanowire conductive network in the prior art, the mode of firstly preparing the copper-nanowire conductive network and then introducing gold atoms to prepare the copper-gold alloy nanowire network provided by the invention can improve the connection performance of a joint and simultaneously improve the conductivity of the transparent conductive film.
Drawings
FIG. 1 is an SEM photograph of the copper-gold alloy nanowire electrode obtained in example 1 at the position of a nanowire;
FIG. 2 is the distribution diagram of the elements of the Cu-Au alloy nanowire electrode obtained in example 1;
FIG. 3 is a comparative diagram of electrochemical stability of the flexible transparent conductive thin film of copper nanowires and the flexible transparent conductive thin film of copper-gold alloy nanowires;
fig. 4a is an SEM photograph of inter-nanowire junctions of the copper nanowire flexible transparent conductive thin film obtained in comparative example 1;
fig. 4b is an SEM photograph of the inter-nanowire junction of the cu-au alloy nanowire electrode obtained in example 1.
Detailed Description
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional and commercially available to those skilled in the art.
Example 1:
(1) and coating the copper nanowire ink dispersed in the normal hexane on the surface of a flexible PET substrate by adopting a vacuum filtration method, then placing the obtained flexible transparent conductive film of the copper nanowires on a heating platform at 100 ℃, and drying and heating for 7min to obtain the transparent conductive film.
(2) The prepared concentration is 10mM HAuCl 4 ，0.25M H 2 SO 4 And (3) an electrolyte.
(3) Taking the flexible transparent conductive film of the copper nanowire as an anode and the graphite electrode as a cathode, electrifying the two ends of the electrodes, wherein the current density is 10mA/cm 2 And electrifying for 10s to obtain the copper-gold alloy nanowire flexible transparent conductive film.
Microstructure characterization is carried out on the nanowires of the flexible transparent conductive film made of the copper-gold alloy nanowires obtained in example 1, an SEM (scanning electron microscope) picture is shown in figure 1, and element distribution is shown in figure 2. As can be seen from fig. 1 and 2, the nanowires of the flexible transparent conductive thin film made of copper nanowires according to this embodiment are copper-gold nanowires having alloy components, and the areas of the copper element and the gold element of the copper-gold alloy nanowires are completely overlapped.
Comparative example 1:
and coating the copper nanowire ink dispersed in the normal hexane on the surface of a flexible PET substrate by adopting a vacuum filtration method, then placing the obtained flexible transparent conductive film of the copper nanowires on a heating platform at 100 ℃, and drying and heating for 7min to obtain the flexible transparent conductive film of the copper nanowires.
And (3) performance characterization:
the electrochemical stability of the flexible transparent conductive film of copper nanowires obtained in comparative example 1 and the flexible transparent conductive film of copper-gold alloy nanowires obtained in example 1 was verified, and the results are shown in FIG. 3 at 1M H 2 SO 4 In an electrochemical corrosion test, the flexible transparent conductive film of the copper nanowire obtained in the comparative example 1 loses response rapidly, and the flexible transparent conductive film of the copper-gold alloy nanowire obtained in the example 1 maintains stable signal response.
The nanowire joints of the flexible transparent conductive film of copper nanowires obtained in comparative example 1 and the flexible transparent conductive film of copper-gold alloy nanowires obtained in example 1 are respectively subjected to microscopic characterization, and the results are respectively shown in fig. 4a and 4b, which shows that the copper nanowires of the flexible transparent conductive film of copper nanowires obtained in comparative example 1 are loose lap joints, while the copper nanowires of the flexible transparent conductive film of copper-gold alloy nanowires obtained in example 1 are connected.
Claims (6)
1. A preparation method of a copper-gold alloy nanowire flexible transparent conductive film is characterized by comprising the following steps:
coating copper nanowire ink on the surface of a flexible substrate, and drying to obtain a transparent conductive film;
step two, taking the transparent conductive film obtained in the step one as a cathode, taking a graphite electrode as an anode, and electrifying two ends of the electrode in an electrolyte to obtain a copper-gold alloy nanowire electrode;
the electrolyte in the second step contains 5-15mmol/L HAuCl 4 And 0.2 to 0.3mol/L H 2 SO 4 ；
The current density in the second step is 18-22mA/cm 2 ；
And the electrifying time in the second step is 8-12 s.
2. The method for preparing the copper-gold alloy nanowire flexible transparent conductive film as claimed in claim 1, wherein the flexible substrate in the first step is PET, PVC, PU or PDMS.
3. The method for preparing the copper-gold alloy nanowire flexible transparent conductive film as claimed in claim 1, wherein the copper nanowire ink is obtained by dispersing copper nanowires in a solvent.
4. The method for preparing the copper-gold alloy nanowire flexible transparent conductive film as claimed in claim 3, wherein the solvent is n-hexane, isopropanol, ethanol or water.
5. The method for preparing the copper-gold alloy nanowire flexible transparent conductive film as claimed in claim 1, wherein the method for coating the copper nanowire ink on the surface of the flexible substrate in the first step comprises the following steps: and coating the copper nanowire ink on the surface of the flexible substrate by adopting a vacuum filtration method.
6. The preparation method of the copper-gold alloy nanowire flexible transparent conductive film as claimed in claim 1, wherein in the first step, the drying temperature is 90-110 ℃ and the drying time is 6-8 min.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104616728A (en) * | 2015-01-26 | 2015-05-13 | 河南大学 | Nanometer cable transparent conducting thin film with copper inner core and preparation method thereof |
| KR20150092405A (en) * | 2014-02-03 | 2015-08-13 | 가부시키가이샤 가네카 | Transparent conductive films and method of preparing the same, and electronic devices compringe thereof |
| JP2018005166A (en) * | 2016-07-08 | 2018-01-11 | 株式会社リコー | Electrochromic device |
| CN208270897U (en) * | 2018-05-08 | 2018-12-21 | 东旭科技集团有限公司 | Flexible electro-chromic device |
| CN208637157U (en) * | 2018-06-27 | 2019-03-22 | 宁波山功新材料科技有限公司 | A kind of foldable flexible transparent conductive film |
| CN110824804A (en) * | 2019-12-16 | 2020-02-21 | 哈尔滨工业大学 | Flexible electrochromic film and preparation method thereof |
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2021
- 2021-02-07 CN CN202110169586.4A patent/CN112992422B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150092405A (en) * | 2014-02-03 | 2015-08-13 | 가부시키가이샤 가네카 | Transparent conductive films and method of preparing the same, and electronic devices compringe thereof |
| CN104616728A (en) * | 2015-01-26 | 2015-05-13 | 河南大学 | Nanometer cable transparent conducting thin film with copper inner core and preparation method thereof |
| JP2018005166A (en) * | 2016-07-08 | 2018-01-11 | 株式会社リコー | Electrochromic device |
| CN208270897U (en) * | 2018-05-08 | 2018-12-21 | 东旭科技集团有限公司 | Flexible electro-chromic device |
| CN208637157U (en) * | 2018-06-27 | 2019-03-22 | 宁波山功新材料科技有限公司 | A kind of foldable flexible transparent conductive film |
| CN110824804A (en) * | 2019-12-16 | 2020-02-21 | 哈尔滨工业大学 | Flexible electrochromic film and preparation method thereof |
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