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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- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000010146 3D printing Methods 0.000 title claims abstract description 19
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 53
- 238000007639 printing Methods 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 26
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 9
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229920000307 polymer substrate Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 238000010923 batch production Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910021389 graphene Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- H—ELECTRICITY
- 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
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- Manufacturing & Machinery (AREA)
- Developing Agents For Electrophotography (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
本发明公开了一种局域原位电聚合3D打印导电聚合物的方法，S100，将三维打印机用导电聚合物单体、添加剂及支持电解质在溶剂中均匀混合，配置成导电聚合物单体分散液；S200，将导电聚合物单体分散液送入三维打印机中，并在打印头和导电基底之间施加电压；S300，开始打印，导电聚合物单体分散液被打印机逐层打印，导电聚合物单体在打印过程中发生聚合，得到所需的导电聚合物产品。同时本发明的工艺简单、工序少、生产效率高，既适合单件或小批量生产，也适合大量打印机同时进行大批量3D打印生产，具有一定的应用前景。
The invention discloses a method for local in-situ electropolymerization 3D printing conductive polymer. S100, the conductive polymer monomer, additives and supporting electrolyte for 3D printer are uniformly mixed in a solvent, and the conductive polymer monomer is configured to disperse liquid; S200, the conductive polymer monomer dispersion liquid is sent into the 3D printer, and a voltage is applied between the print head and the conductive substrate; S300, printing starts, the conductive polymer monomer dispersion liquid is printed layer by layer by the printer, and the conductive polymerization The monomers are polymerized during the printing process to obtain the desired conductive polymer product. At the same time, the invention has simple process, few procedures and high production efficiency, is suitable for single-piece or small-batch production, and is suitable for large-scale 3D printing production at the same time by a large number of printers, and has certain application prospects.
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 | Preparation method of conductive polyaniline gel and its application in supercapacitor |
| US10229769B2 (en) * | 2015-11-20 | 2019-03-12 | Xerox Corporation | Three phase immiscible polymer-metal blends for high conductivty composites |
| CN108428566A (en) * | 2018-01-23 | 2018-08-21 | 浙江工业大学 | A kind of high efficiency preparation method of the planar miniature electrode of super capacitor of interdigital structure |
| CN109575673B (en) * | 2019-01-14 | 2020-11-17 | 四川大学 | Functional ink suitable for 3D printing and preparation method thereof |
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