CN115636968A - Flexible electronic film containing nano functional coating, preparation method thereof and recycling method of nano functional coating - Google Patents
Flexible electronic film containing nano functional coating, preparation method thereof and recycling method of nano functional coating Download PDFInfo
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- CN115636968A CN115636968A CN202211342456.7A CN202211342456A CN115636968A CN 115636968 A CN115636968 A CN 115636968A CN 202211342456 A CN202211342456 A CN 202211342456A CN 115636968 A CN115636968 A CN 115636968A
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Abstract
The invention provides a flexible electronic film containing a nano-functional coating, a preparation method thereof and a recovery method of the nano-functional coating, wherein the flexible electronic film comprises the following components: the flexible substrate is coated with pre-coating liquid and PEDOT, namely PSS nano functional coating in sequence; the pre-coating liquid comprises the components of glycerin, or a mixed solution of glycerin and ethylene glycol, or a mixed solution of glycerin and ethanol, or a mixed solution of glycerin and methanol. And (3) putting the flexible electronic film bubble containing the nano functional coating in water at the temperature of 20-35 ℃, separating the PEDOT (PSS) nano functional coating from the flexible substrate, and recovering to obtain the nano functional coating. The flexible electronic film not only keeps the functions of a flexible electronic device, but also can realize the complete recovery of a nano functional coating.
Description
Technical Field
The invention belongs to the field of flexible electronics, and relates to a flexible electronic film containing a nano-functional coating, a preparation method of the flexible electronic film and a recovery method of the nano-functional coating.
Background
In recent years, with the continuous development of the field of flexible electronics, various flexible electronic products are being promoted, and therefore, environmental protection problems such as recycling, reusing, and degradability of various flexible electronic products become important points of industrial attention. At present, the preparation of environment-friendly flexible electronic products generally needs to coat nanometer functional materials such as metal nanowires, graphene, PEDOT, PSS and the like on the surface of a degradable flexible substrate to form a functional coating, so that the flexible electronic products have the functions of being bendable and the like on one hand, and on the other hand, when waste products are directly discarded, the influence on the environment can be reduced to a certain extent due to the fact that the substrate is made of the degradable material.
Although the existing environment-friendly flexible electronic products adopt cellulose, polyvinyl alcohol and the like as degradable flexible base materials, researches on the recovery of nano-functional coatings, particularly the recovery of nano-functional coatings prepared from PEDOT (PolyEthyl Ether-vinyl Ether) and PSS (PolyEthylenediamine). The reason is that the manufactured PEDOT/PSS material is aqueous solution, and when the PEDOT/PSS material is coated on the surface of the degradable substrate, the PEDOT/PSS nano-particles inevitably permeate the surface of the degradable substrate. In addition, after the nano PEDOT PSS is coated, a certain stacking structure can be formed between the PEDOT PSS, for example, the specific structure between nano materials can be damaged by adopting the traditional method for recycling, and the recycling process can involve complex processes of separation of the nano materials from a substrate, filtration and redispersion of the nano materials and the like. There is therefore a need to develop a simple process which at the same time allows for the degradation of the substrate material and the easy recovery of the nano-functional coating.
Disclosure of Invention
In order to solve the problem of difficult recovery of nano functional materials, the invention provides a flexible electronic film containing a nano functional coating, a preparation method thereof and a recovery method of the nano functional coating.
The invention is realized by the following technical scheme:
a flexible electronic film comprising a nano-functional coating, comprising: the flexible substrate is coated with pre-coating liquid and PEDOT, namely PSS nano functional coating in sequence;
the precoating liquid comprises the components of glycerin, or a mixed solution of glycerin and glycol, or a mixed solution of glycerin and ethanol, or a mixed solution of glycerin and methanol.
Preferably, the content of glycerol in the mixed solution of glycerol and ethylene glycol is 50wt% to 80wt%, the content of glycerol in the mixed solution of glycerol and ethanol is 30wt% to 70wt%, and the content of glycerol in the mixed solution of glycerol and methanol is 20wt% to 90wt%.
Preferably, the flexible substrate is a degradable flexible substrate.
Further, the flexible substrate is a gelatin-based flexible substrate.
The preparation method of the flexible electronic film containing the nano-functional coating comprises the following steps:
and spin-coating the pre-coating solution and the PEDOT (PSS) pretreatment solution on the surface of the flexible substrate in sequence, and drying to obtain the flexible electronic film containing the PEDOT (PSS) nano functional coating.
Preferably, the preparation method of the flexible substrate comprises the following steps: and dissolving gelatin powder in water, and drying the obtained solution to form a film to obtain the flexible substrate.
Preferably, the preparation method of the PEDOT/PSS pretreatment solution comprises the following steps: and the PEDOT PSS solution is obtained by diluting with one or more of methanol, glycol and ethanol.
The method for recycling the nano functional coating in the flexible electronic film containing the nano functional coating is characterized in that the flexible electronic film containing the nano functional coating is soaked in water at the temperature of 20-35 ℃, the PEDOT, namely the PSS nano functional coating, is separated from the flexible substrate, and the nano functional coating is obtained by recycling.
Preferably, the recovered nano-functional coating is reused by adopting a transfer printing mode.
Compared with the prior art, the invention has the following beneficial effects:
according to the flexible electronic film, the surface of a flexible substrate is coated with the pre-coating solution, and then coated with the PEDOT, namely PSS nano functional coating, so that the device can be used as a flexible transparent electrode, or can be assembled with an electrolyte and the like to prepare a flexible electrochromic device, and the functions of the flexible electronic device are retained. The glycerol in the precoating liquid can generate strong hydrogen bonding with PEDOT and PSS and has a high content on the surface of the flexible substrate, so that the action force between the PEDOT and the PSS and the glycerol is stronger than that between the PEDOT and the PSS and the flexible substrate, the action force between the PEDOT and the PSS and the flexible substrate is effectively isolated, and the PEDOT and PSS coating cannot penetrate into the flexible substrate so as to keep the integrity of the PEDOT and PSS coating.
The preparation method is simple, the raw materials are easy to obtain, and the preparation method is suitable for wide application.
After the flexible electronic film is soaked in water, the PEDOT/PSS coating can completely fall off and be recycled due to the integrity of the PEDOT/PSS coating and the difference between the expansion rates of the flexible substrate and the PEDOT/PSS coating. The invention combines the flexible electronic device with interface regulation and control, and can realize the functions of the flexible electronic device and the complete recovery of the PEDOT/PSS coating. The recovered PEDOT PSS coating can be reused by adopting a transfer method and the like.
Detailed Description
For a further understanding of the invention, reference will now be made to the following examples, which are provided to illustrate further features and advantages of the invention, and are not intended to limit the scope of the invention as set forth in the following claims.
The invention relates to a flexible electronic film containing a nano-functional coating, which comprises: the flexible substrate is coated with the pre-coating liquid and the PEDOT, namely the PSS nano functional coating in sequence.
The flexible substrate is a degradable flexible substrate, such as a gelatin-based flexible substrate. The pre-coating liquid comprises the components of glycerin, or a mixed solution of glycerin and glycol (the content of the glycerin is 50wt% -80 wt%), or a mixed solution of the glycerin and ethanol (the content of the glycerin is 30wt% -70 wt%), or a mixed solution of the glycerin and methanol (the content of the glycerin is 20wt% -90 wt%).
The invention relates to a preparation method of a flexible electronic film containing a nano functional coating, which comprises the following steps:
dissolving gelatin powder in ultrapure water, and drying the solution to form a film to obtain a flexible substrate;
and spin-coating the pre-coating solution and PEDOT (PolyEthyleneEther phosphate), namely PSS (PolyEthyleneEther phosphate) pretreatment solution on the surface of the flexible substrate in sequence, and drying to obtain the flexible electronic film containing the nano functional coating.
Among them, the PEDOT: PSS pretreatment solution is preferably a PEDOT: PSS solution diluted to a content of 0.3wt% by 1wt% of the PEDOT. For example, diluting a PEDOT/PSS solution with methanol and ethylene glycol to obtain a PEDOT/PSS pretreatment solution; wherein the volume ratio of methanol, ethylene glycol and PEDOT to PSS solution is 1.
In addition, PSS, which is a nano-functional material adopted by the invention, can be mixed with nano-functional materials such as metal nanowires and graphene, so that the functionality of the prepared flexible electronic device is further improved.
The invention relates to a method for recovering a nano functional coating of a flexible electronic film containing the nano functional coating, which comprises the following steps: after the flexible electronic film bubble containing the nano functional coating is placed in water at normal temperature (20-35 ℃) for 60 minutes, the PEDOT (PSS) film can be separated from the flexible substrate, and the nano functional coating is obtained.
The recycled nano functional coating can be reused by transfer printing and other modes, so that the PEDOT/PSS film is reused.
Example 1
Pouring and drying 10wt% of gelatin solution to form a film, selecting glycerol as precoating solution, spin-coating on the surface of the prepared gelatin film, diluting a CLEVIOS PH1000 type PEDOT: PSS solution with methanol and ethylene glycol (the volume ratio of the methanol to the ethylene glycol to the PEDOT: PSS solution is 1. And finally, soaking the prepared device in normal-temperature water for 1 hour, and performing a PEDOT/PSS film separation experiment.
Example 2
After a 10wt% gelatin solution is poured and dried to form a film, glycerol/methanol (with the glycerol content of 50 wt%) is selected as a precoating solution and is spin-coated on the surface of the prepared gelatin film, a PEDOT: PSS solution of CLEVIOS PH1000 type is diluted by methanol and ethylene glycol (the volume ratio of the methanol to the ethylene glycol to the PEDOT: PSS solution is 1. And finally, soaking the prepared device in normal-temperature water for 1 hour, and performing a PEDOT/PSS film separation experiment.
Example 3
The ingredients in the precoating liquid in example 2 were adjusted to: glycerol/methanol (glycerol content 65 wt%) was used as a precoating solution, and the procedure was the same as in example 2.
Example 4
The ingredients in the precoating liquid in example 2 were adjusted to: glycerol/methanol (glycerol content 80% by weight) was used as a precoating solution, and the procedure was as in example 2.
Example 5
After a 10wt% gelatin solution is poured and dried to form a film, glycerol/ethanol (the content of the glycerol is 30 wt%) is selected as a precoating solution and is spin-coated on the surface of the prepared gelatin film, a PEDOT: PSS solution of CLEVIOS PH1000 type is diluted by methanol and ethylene glycol (the volume ratio of the methanol to the ethylene glycol to the PEDOT: PSS solution is 1. And finally, soaking the prepared device in normal-temperature water for 1 hour, and performing a PEDOT/PSS film separation experiment.
Example 6
The ingredients in the precoating liquid in example 5 were adjusted to: glycerol/ethanol (glycerol content 50 wt%) was used as the precoating solution, and the procedure was the same as in example 5.
Example 7
The ingredients in the precoating liquid in example 5 were adjusted to: glycerol/ethanol (glycerol content 80% by weight) was used as the precoating liquid, and the procedure was the same as in example 5.
Example 8
After a 10wt% gelatin solution is poured and dried to form a film, glycerol and glycerol/ethylene glycol (the content of the glycerol is 20 wt%) are selected as precoating liquid to be spin-coated on the surface of the prepared gelatin film, a PEDOT: PSS solution of CLEVIOS PH1000 type is diluted by methanol and ethylene glycol (the volume ratio of the methanol to the ethylene glycol to the PEDOT: PSS solution is 1. And finally, soaking the prepared device in normal-temperature water for 1 hour to perform a separation experiment of the PEDOT (polymer ethylene terephthalate)/PSS (patterned sapphire substrate) film.
Example 9
The ingredients in the precoating liquid in example 8 were adjusted to: glycerol/ethylene glycol (glycerol content 55% by weight) was used as a precoating solution, and the procedure was as in example 8.
Example 10
The ingredients in the precoating liquid in example 8 were adjusted to: glycerol/ethylene glycol (90% by weight glycerol) was used as a precoating solution, and the procedure was as in example 8.
Comparative example 1 is a PEDOT: PSS/gelatin film without the addition of a precoating solution.
The specific experiment is carried out in water at 30 ℃, and after 60 minutes, the separation condition of PEDOT/PSS nano functional coatings in each example and comparative example is observed, and the specific experiment results are shown in Table 1.
Table 1 pedot
As can be seen from Table 1, in comparative example 1, the PEDOT/PSS/gelatin film without the precoating solution is not separated at all through a separation experiment of 60 minutes. In the embodiments 1-10, the added precoating liquid component can effectively realize the separation of PEDOT-PSS nano functional coatings, and the effect is obvious. In addition, glycerol is used as a plasticizer, and the dosage of glycerol increases the flexibility of the substrate, and can be adjusted according to the using scene of the device. Although the functional coating can be separated from the methanol, ethanol, and ethylene glycol at a certain ratio, the kind and amount of the organic solvent in the precoating liquid have a certain influence on the properties such as conductivity of the functional coating, and therefore, the components of the precoating liquid can be adjusted as needed.
Claims (9)
1. A flexible electronic film comprising a nano-functional coating, comprising: the flexible substrate is coated with pre-coating liquid and PEDOT, namely PSS nano functional coating in sequence;
the precoating liquid comprises the components of glycerin, or a mixed solution of glycerin and glycol, or a mixed solution of glycerin and ethanol, or a mixed solution of glycerin and methanol.
2. The flexible electronic film having a nano-functional coating according to claim 1, wherein the content of glycerol in the mixed solution of glycerol and ethylene glycol is 50 to 80wt%, the content of glycerol in the mixed solution of glycerol and ethanol is 30 to 70wt%, and the content of glycerol in the mixed solution of glycerol and methanol is 20 to 90wt%.
3. The flexible electronic film containing a nano-functional coating of claim 1, wherein the flexible substrate is a degradable flexible substrate.
4. The flexible electronic film containing a nano-functional coating according to claim 3, wherein the flexible substrate is a gelatin-based flexible substrate.
5. The method of preparing a flexible electronic film containing a nano-functional coating according to any one of claims 1 to 4, comprising:
and sequentially spin-coating the pre-coating solution and the PEDOT (PSS) pretreatment solution on the surface of the flexible substrate, and drying to obtain the flexible electronic film containing the PEDOT (PSS) nano functional coating.
6. The method for preparing a flexible electronic film containing a nano-functional coating according to claim 5, wherein the method for preparing the flexible substrate comprises: and dissolving gelatin powder in water, and drying the obtained solution to form a film to obtain the flexible substrate.
7. The method for preparing a flexible electronic film containing a nano-functional coating according to claim 5, wherein the PEDOT PSS pretreatment solution is prepared by the following steps: and the PEDOT PSS solution is obtained by diluting with one or more of methanol, glycol and ethanol.
8. The method for recycling the nano-functional coating from the flexible electronic film with the nano-functional coating as claimed in any one of claims 1 to 4, wherein the flexible electronic film bubble with the nano-functional coating is immersed in water at a temperature of 20 to 35 ℃, and the PEDOT/PSS nano-functional coating is separated from the flexible substrate and recycled to obtain the nano-functional coating.
9. The method for recycling the nano-functional coating in the flexible electronic film containing the nano-functional coating as claimed in claim 8, wherein the recycled nano-functional coating is reused by transferring.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130027213A (en) * | 2011-09-07 | 2013-03-15 | 연세대학교 산학협력단 | Modified pedot:pss with organic solvent and organic solar cells using it |
| CN110372898A (en) * | 2019-07-05 | 2019-10-25 | 江西科技师范大学 | A kind of preparation method of transparent high conductive organic flexible PEDOT:PSS film |
| CN112216419A (en) * | 2020-09-24 | 2021-01-12 | 浙江工业大学 | Normal-temperature low-pressure transfer printing method for flexible conductive film |
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- 2022-10-31 CN CN202211342456.7A patent/CN115636968A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130027213A (en) * | 2011-09-07 | 2013-03-15 | 연세대학교 산학협력단 | Modified pedot:pss with organic solvent and organic solar cells using it |
| CN110372898A (en) * | 2019-07-05 | 2019-10-25 | 江西科技师范大学 | A kind of preparation method of transparent high conductive organic flexible PEDOT:PSS film |
| CN112216419A (en) * | 2020-09-24 | 2021-01-12 | 浙江工业大学 | Normal-temperature low-pressure transfer printing method for flexible conductive film |
Non-Patent Citations (1)
| Title |
|---|
| RONG XUE ET AL.: "Fabrication of Flexible Electrochromic Devices with Degradable and Fully Recyclable Features", ACS BIOMATER. SCI. ENG., vol. 8, no. 3, pages 1320 * |
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