CN110060816B - Method for local in-situ electropolymerization of conductive polymer by 3D printing - Google Patents
Method for local in-situ electropolymerization of conductive polymer by 3D printing Download PDFInfo
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- CN110060816B CN110060816B CN201910329717.3A CN201910329717A CN110060816B CN 110060816 B CN110060816 B CN 110060816B CN 201910329717 A CN201910329717 A CN 201910329717A CN 110060816 B CN110060816 B CN 110060816B
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- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
Abstract
The invention discloses a method for 3D printing of a conductive polymer by local in-situ electropolymerization, which comprises the following steps of S100, uniformly mixing a conductive polymer monomer, an additive and a supporting electrolyte for a three-dimensional printer in a solvent to prepare a conductive polymer monomer dispersion liquid; s200, feeding the conductive polymer monomer dispersion liquid into a three-dimensional printer, and applying voltage between a printing head and a conductive substrate; and S300, starting printing, printing the conductive polymer monomer dispersion liquid layer by the printer, and polymerizing the conductive polymer monomer in the printing process to obtain the required conductive polymer product. Meanwhile, the invention has simple process, less working procedures and high production efficiency, is suitable for single-piece or small-batch production, is also suitable for mass 3D printing production of a large number of printers, and has certain application prospect.
Description
Technical Field
The invention belongs to the field of 3D printing (additive manufacturing), and particularly relates to a method for 3D printing of a conductive polymer through local in-situ electropolymerization.
Background
3D printing, also known as additive manufacturing, is a technique for manufacturing three-dimensional products by layer-by-layer printing based on digital models. Due to the unique manufacturing mode and the huge manufacturing potential, the material is widely concerned and researched by a plurality of research institutions and enterprises at home and abroad, and has a certain application in the fields of medical treatment, automobiles, aerospace and the like. 3D printing is also subdivided into many categories for the difference in the printing target and the printing material of 3D printing. The ink direct writing technology has the advantages of wide material selection range, high forming speed, environmental protection, convenience and the like, and has obvious advantages in the printing aspect of micro electronic devices and micro energy storage devices.
However, the subsequent heating treatment after the ink direct writing is finished is one of the main defects of the ink direct writing technology, and particularly for materials such as conductive polymers which are widely used in microelectronic devices and energy storage devices, the sintering process can not only cause certain changes in the volume and shape of a printing component, but also is not beneficial to the precise forming of microelectrodes; meanwhile, the molecular structure of the conductive polymer is damaged by the high sintering temperature, so that the original electrical properties of the conductive polymer are lost or even lost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for locally electropolymerizing a 3D printed conductive polymer in situ, which realizes the printing and polymerization integrated process of the conductive polymer and avoids the subsequent heating treatment of ink direct writing, thereby ensuring the structure and the electrical stability of a direct writing component.
In order to realize the task, the invention adopts the following technical solution:
a method for local in-situ electropolymerization of a conductive polymer for 3D printing comprises the following steps:
s100, uniformly mixing a conductive polymer monomer, an additive and a supporting electrolyte for the three-dimensional printer in a solvent to prepare a conductive polymer monomer dispersion liquid;
s200, feeding the conductive polymer monomer dispersion liquid into a three-dimensional printer, and applying voltage between a printing head and a conductive substrate;
and S300, starting printing, printing the conductive polymer monomer dispersion liquid layer by the printer, and polymerizing the conductive polymer monomer in the printing process to obtain the required conductive polymer product.
As a further improvement of the invention, the conductive polymer monomer is aniline monomer or pyrrole monomer.
As a further improvement of the invention, the additive is a metal oxide, sulfide, nitride, carbon material or binder compounded with a conductive polymer.
As a further improvement of the invention, the supporting electrolyte is an inorganic salt or a protonic acid.
As a further improvement of the invention, the conductive substrate is a metal, a carbon material or a polymer substrate deposited with a metal or a carbon material.
As a further improvement of the invention, the solvent is water or an organic solvent.
As a further improvement of the invention, the applied voltage is in the range of 0-5V.
As a further improvement of the present invention, the conductive polymer monomer dispersion is an aqueous solution of a mixture of pyrrole monomer and hydrochloric acid, an N-methylpyrrolidone solution of a mixture of pyrrole monomer and lithium perchlorate, an N-methylpyrrolidone solution of a mixture of aniline monomer and sulfuric acid, or an aqueous solution of a mixture of aniline monomer and phosphoric acid.
Compared with the prior art, the invention has the following advantages:
the invention utilizes the principle of electropolymerization of the conductive polymer monomer, and applies proper voltage between the printing probe and the substrate to ensure that the ink is electropolymerized simultaneously in the extrusion printing process, thereby realizing the printing and polymerization integrated process of the conductive polymer, avoiding the subsequent heating treatment of ink direct writing, and further ensuring the structure and the electrical stability of the direct writing component. The local electric field between the printing head and the substrate is applied in the three-dimensional printing process, so that the conductive polymer monomer is electropolymerized on the conductive substrate in the printing process, and the post-treatment process required by the three-dimensional printing is avoided. The thermal treatment process of the three-dimensional printing after printing is avoided, so that the conductive polymer can be printed quickly and conveniently, the original high conductivity of the conductive polymer is kept, and the conductive polymer can be widely applied to microelectronic devices or micro energy storage devices. Meanwhile, the invention has simple process, less working procedures and high production efficiency, is suitable for single-piece or small-batch production, is also suitable for mass 3D printing production of a large number of printers, and has certain application prospect.
Drawings
FIG. 1 is a flow chart of a preparation method of the present invention;
fig. 2 raman spectra of aniline before and after printing.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, which are illustrative of the invention and are not to be construed as limiting the invention.
A method for local in-situ electropolymerization of a conductive polymer for 3D printing comprises the following steps:
1. a proper conductive polymer monomer, an additive and a supporting electrolyte are uniformly mixed in a solvent to prepare a solution.
2. Feeding the mixed solution into a three-dimensional printer, and applying a voltage of 0-5V between a printing head and a conductive substrate;
3. according to the printed file, the conductive polymer monomer dispersion liquid is printed layer by a printer, and polymerization occurs in the printing process to obtain the required conductive polymer product.
The conductive polymer monomer comprises, but is not limited to, aniline monomer, pyrrole monomer and the like, and the concentration of the conductive polymer monomer is 0.05-2 mol/L. The additives include, but are not limited to, materials capable of complexing with the conductive polymer such as metal oxides, sulfides, nitrides, carbon materials, and binders for improving printing results. The supporting electrolyte includes, but is not limited to, various inorganic salts (potassium salt, sodium salt, ammonium salt, etc.) and protonic acid (sulfuric acid, phosphoric acid, hydrochloric acid, etc.) at a concentration of 0.1M to 2M. The conductive substrate includes, but is not limited to, metals (gold, silver, platinum, copper, iron, etc.), carbon materials, and forms of depositing the relevant metal or carbon material on a polymer substrate. Such solvents include, without limitation, water and organic solvents such as acetone, acetic acid, dichloroethane, trichloroethane, N-methylpyrrolidone, and the like.
The principle of the invention is as follows: the method for locally electropolymerizing in situ 3D printing the conductive polymer applies a local electric field between a printing head and a substrate in the three-dimensional printing process by utilizing the electropolymerization principle of a conductive polymer monomer, so that the conductive polymer monomer is electropolymerized on the conductive substrate in the printing process, and the post-treatment process required by three-dimensional printing is avoided.
The invention is further described below with reference to the figures and examples. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation. The conductive polymer which can be printed by the method can be polyaniline, polypyrrole, graphene and polyaniline composite materials and the like.
Example 1:
(1) preparing 0.2mol/L aniline monomer and 1.0mol/L phosphoric acid, mixing in an aqueous solution, and uniformly stirring;
(2) selecting glass as a substrate, and depositing gold on the glass as a current collector;
(3) feeding the prepared mixed solution into a printer;
(4) and loading 0.8V voltage between the printing head of the printer and the conductive substrate, and enabling the printer to move according to the printed file to realize printing and polymerization of the aniline monomer, wherein the conductivity of the aniline monomer is 1.4-1.5S/cm.
Example 2:
(1) preparing 0.5mol/L aniline monomer and 1.2mol/L sulfuric acid, mixing in N-methyl pyrrolidone solution, and stirring uniformly;
(2) selecting a graphene film as a current collector;
(3) feeding the prepared mixed solution into a printer;
(4) 3V voltage is loaded between a printing head of the printer and the conductive substrate, the printer is made to move according to a printed file, printing and polymerization of the aniline monomer are achieved, and the conductivity of the aniline monomer is 2.0-2.1S/cm.
Example 3:
(1) preparing 0.1mol/L pyrrole monomer and 0.3mol/L lithium perchlorate, mixing in N-methyl pyrrolidone solution, and stirring uniformly;
(2) selecting a stainless steel sheet as a substrate;
(3) feeding the prepared mixed solution into a printer;
(4) 4.5V voltage is loaded between the printing head of the printer and the conductive substrate, the printer moves according to a printing file, the printing and polymerization of the pyrrole monomer are realized, and the conductivity of the pyrrole monomer is 4.5-4.8S/cm.
Example 4:
(1) preparing 0.1mol/L pyrrole monomer and 0.3mol/L hydrochloric acid, mixing in an aqueous solution, and uniformly stirring;
(2) selecting a stainless steel sheet as a substrate;
(3) feeding the prepared mixed solution into a printer;
(4) 1.0V voltage is loaded between the printing head of the printer and the conductive substrate, the printer is made to move according to the printed file, the printing and polymerization of the pyrrole monomer are realized, and the conductivity of the pyrrole monomer is 5.5-5.8S/cm.
Example 5:
the present embodiment describes the present invention in detail with a specific process for manufacturing a flexible micro supercapacitor:
1) a current collector of gold of the desired shape, 10 μm thick, was deposited using magnetron sputtering.
2) Preparing a graphene oxide aqueous solution with the concentration of 3mg/ml, and adding 0.1M NaCl as an electrolyte.
3) And (3) feeding the electrolyte containing the graphene oxide into a printing and charging barrel, and printing according to a specified program.
4) In the printing process, a voltage of 1V is applied between the current collector and the printing needle head, and the graphene oxide is subjected to local electroreduction.
5) Repeating the steps for 2 to 3 times to obtain the reduced graphene oxide electrode with the thickness of about 10 mu m.
6) The polyvinyl alcohol-phosphoric acid electrolyte was fed into the printer cylinder and the polymer electrolyte solution was printed on the reduced graphene oxide electrode with a thickness of about 10 μm.
7) And after the polymer electrolyte solution is solidified, obtaining the flexible micro super capacitor, wherein the obtained flexible micro super capacitor can be bent at any angle.
The capacity of the device is about 11mF/cm through electrochemical test2After 5000 cycles, the capacity retention was about 90%.
The above-described embodiments are merely illustrative of implementations of the invention that enable persons skilled in the art to make or use the invention, and the description is not limiting. Therefore, the present invention should not be limited to the embodiments shown herein, and all additions and equivalents made to the technical features of the present invention are intended to fall within the scope of the present application.
Claims (3)
1. A method for local in-situ electropolymerization of a conductive polymer for 3D printing is characterized by comprising the following steps:
s100, uniformly mixing a conductive polymer monomer, an additive and a supporting electrolyte for the three-dimensional printer in a solvent to prepare a conductive polymer monomer dispersion liquid;
s200, feeding the conductive polymer monomer dispersion liquid into a three-dimensional printer, and applying voltage between a printing head and a conductive substrate;
s300, printing is started according to the printed file, the conductive polymer monomer dispersion liquid is printed layer by the printer, and the conductive polymer monomer is polymerized in the printing process to obtain a required conductive polymer product;
the conductive polymer monomer is aniline monomer or pyrrole monomer;
the additive is a metal oxide, a sulfide, a nitride, a carbon material or a binder compounded with a conductive polymer;
the supporting electrolyte is inorganic salt or protonic acid;
the conductive polymer monomer dispersion liquid is a mixed aqueous solution of pyrrole monomer and hydrochloric acid, a mixed N-methyl pyrrolidone solution of pyrrole monomer and lithium perchlorate, a mixed N-methyl pyrrolidone solution of aniline monomer and sulfuric acid, or a mixed aqueous solution of aniline monomer and phosphoric acid;
the applied voltage is in the range of 0.8-5V.
2. The method for localized in-situ electropolymerization of 3D printed conductive polymers as claimed in claim 1, wherein the conductive substrate is a metal, carbon material or a polymer substrate deposited with a metal or carbon material.
3. The method for localized in-situ electropolymerization of 3D printed conductive polymers as claimed in claim 1, wherein the solvent is water or an organic solvent.
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| CN102020845B (en) * | 2010-11-25 | 2012-05-23 | 武汉大学 | Preparation method of conductive polyaniline polypyrrole composite membrane |
| CN105295038B (en) * | 2015-11-05 | 2017-07-25 | 天津大学 | The preparation method of electrically conductive polyaniline gel and its application in ultracapacitor |
| US10229769B2 (en) * | 2015-11-20 | 2019-03-12 | Xerox Corporation | Three phase immiscible polymer-metal blends for high conductivty composites |
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