CN109130168B - Preparation method of direct-writing high-flexibility organic electrode - Google Patents

Preparation method of direct-writing high-flexibility organic electrode Download PDF

Info

Publication number
CN109130168B
CN109130168B CN201810825755.3A CN201810825755A CN109130168B CN 109130168 B CN109130168 B CN 109130168B CN 201810825755 A CN201810825755 A CN 201810825755A CN 109130168 B CN109130168 B CN 109130168B
Authority
CN
China
Prior art keywords
writing
electrode
organic electrode
power supply
current power
Prior art date
Legal status (The legal status 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 status listed.)
Active
Application number
CN201810825755.3A
Other languages
Chinese (zh)
Other versions
CN109130168A (en
Inventor
陈彩凤
钱继龙
廖林晨
蔡飞翔
王安东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu University
Original Assignee
Jiangsu University
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 Jiangsu University filed Critical Jiangsu University
Priority to CN201810825755.3A priority Critical patent/CN109130168B/en
Publication of CN109130168A publication Critical patent/CN109130168A/en
Application granted granted Critical
Publication of CN109130168B publication Critical patent/CN109130168B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • 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
    • C09D11/16—Writing inks

Abstract

The invention belongs to the field of piezoelectric film material preparation, and relates to a preparation method of a direct-writing high-flexibility organic electrode; the method comprises the following specific steps: firstly, creating a piezoelectric film 3D model and carrying out slicing processing; then weighing the multi-walled carbon nanotube, mixing the multi-walled carbon nanotube with the N-methylformamide solution, and performing ultrasonic dispersion uniformly to obtain a precursor solution; adding polyaniline, polyvinylidene fluoride and acetone, and carrying out sealed ultrasonic treatment until the polyaniline, the polyvinylidene fluoride and the acetone are completely dissolved to obtain writing ink; finally, setting a writing flow and a writing process, and starting a writing program to obtain the organic electrode; the direct writing preparation method of the organic electrode can obtain the high-conductivity and high-flexibility organic electrode on the basis of ensuring smooth printing; and moreover, the shape and the pattern which cannot be obtained by the traditional technology can be directly written through the flexible design of the writing track, the writing track program is controllable, the electrode size is more accurate, and the application prospect is wide.

Description

Preparation method of direct-writing high-flexibility organic electrode
Technical Field
The invention belongs to the field of electrode material preparation, and particularly relates to a preparation method of a direct-writing high-flexibility organic electrode.
Background
With the large number of applications of flexible sensors, capacitors and the like in the field of artificial intelligence, electrodes have been developed vigorously as components necessary for transmission of electrical signals. At present, the electrode suitable for the high-flexibility intelligent thin-film device is prepared by the common methods such as a physical vapor deposition method, an evaporation method, a chemical vapor deposition method, a sol-gel spin coating method, a hydrothermal method and screen printing.
The sputtering deposition is to prepare sputtered target material atoms into a film electrode on a substrate by using a deposition or adsorption mode. The preparation process of evaporation and deposition is that the electrode material is directly evaporated and sublimated under certain pressure and temperature, and the gaseous substance is gradually deposited on the substrate to form the electrode. The chemical vapor deposition method is to separate particles from a gas phase through a series of chemical reactions of a material in a gas state and deposit the particles on a substrate, and has complex operation process and strict control on temperature and time.
When the electrode is prepared by adopting an ion sputtering method, evaporation deposition and chemical vapor deposition, the thickness of the electrode is uniform, but the requirements on experimental equipment and environment are high, the operation is complex, and the bonding force between the thicker electrode and a substrate is poor, so that the electrode is easy to loosen, and the performance of a device is unstable.
The spin-coating method adopts different metal conductive liquids to spin-coat the outer surface of the film, so that the thickness of a spin-coated electrode is not easy to control, and the repeatability is unstable; the screen printing is to print a specific pattern on the surface of an object by using the conductive paste to pass through the hollow part on the screen printing plate. The screen printing can prepare electrodes with various patterns and is simple to operate. But it is difficult to ensure high dimensional accuracy.
The electrodes can be prepared by the methods, but the problems of expensive raw materials, poor dimensional precision, complex operation and the like generally exist. Moreover, most of the metal materials are used as conductive materials, and the compatibility of the metal materials and film base materials such as high polymers, inorganic materials and the like is poor. Under the action of external force, the deformation of the matrix can bring about the deformation of the electrode, even if the metal electrode with excellent ductility is used, microcracks can appear in the electrode, the resistance is increased, the conductivity is influenced, and the microcracks gradually increase along with the increase of the deformation times to cause the final loosening of the electrode, so that the stability of the electrode is influenced.
The direct writing method is a novel high-tech printing technology in a 3D printing mode and is a multiplication product of the 3D printing technology. The method has designability, electrodes with various structures can be directly written on a substrate through the control of a writing program, the requirement on a preparation process is relatively low, and the dimensional precision of a product is extremely high; the organic electrode has high elasticity, good compatibility with the substrate and deformation along with the deformation of the substrate, can be used as an ideal electrode material of a flexible sensing or driving device, and has very wide application prospect in the field of constructing intelligent devices.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of a direct-writing high-flexibility organic electrode, which comprises the following specific steps:
(1) 3D modeling is carried out on the needed electrode shape by adopting Soildworks, and the electrode model is sliced by adopting Crua software;
(2) preparing writing ink: weighing a multi-walled carbon nanotube according to a proportion, mixing the multi-walled carbon nanotube with a N-methyl formamide (DMF) solution, and ultrasonically dispersing until the mixture is uniform to obtain a precursor solution; adding Polyaniline (PANI) into the precursor solution, performing ultrasonic dispersion, then adding polyvinylidene fluoride (PVDF) and acetone, and performing sealed ultrasonic to obtain writing ink;
(3) setting a writing flow and a writing process; the writing device comprises a needle tube, a writing needle head, a bottom plate, an XYZ three-axis moving mechanism and a high-voltage direct-current power supply; absorbing the writing ink in the step (2) by using a needle tube in the writing process, assembling a writing needle head, connecting the positive pole of a high-voltage direct-current power supply with the needle head, and connecting the negative pole of the high-voltage direct-current power supply with a copper plate at the lower part of a bottom plate; fixing the needle tube, adjusting the distance between the needle head and the bottom plate, adjusting the voltage of the high-voltage direct-current power supply, and starting a writing program to finish to obtain the organic electrode.
Preferably, the parameters of the slice in the step (1) are as follows: the moving speed is 30mm/s, the slice thickness is 0.01mm, and the number of printing layers is 50-100.
Preferably, the amount of the multi-walled carbon nanotubes in the step (2) is 0wt% to 0.05 wt%.
Preferably, the N-methylformamide in the step (2) is used in an amount of 68-81 wt%.
Preferably, the dosage of the polyaniline in the step (2) is 6wt% to 15 wt%.
Preferably, the polyvinylidene fluoride in the step (2) is used in an amount of 4-8 wt%.
Preferably, the acetone used in step (2) is 9 wt%.
Preferably, the volume of the sucked printing ink in the step (3) is 3 mL.
Preferably, the distance between the needle head and the bottom plate in the step (3) is 1-5 mm.
Preferably, the voltage of the high-voltage direct-current power supply in the step (3) is 2-9 kV.
Has the advantages that:
(1) the preparation method of the organic electrode provided by the invention can obtain the high-conductivity and high-flexibility organic electrode on the basis of ensuring smooth printing, and the organic electrode material is soft and tough and has the conductivity of 2.1S/m.
(2) Compared with the current common electrode preparation method, the invention has the following advantages: firstly, the shape and the pattern which cannot be obtained by the traditional technology can be directly written through the flexible design of the writing track; moreover, the number of writing layers is adjustable, the writing track program is controllable, and the size of the electrode is more accurate.
(3) Compared with the metal raw materials commonly used as electrodes, the polyaniline material used in the invention has low price, thus saving the cost of raw materials; the organic conductive material prepared by compounding polyaniline and polyvinylidene fluoride has the characteristics of high elasticity and high flexibility, has good compatibility with a matrix, is not easy to peel and loosen, and can deform along with the deformation of a flexible substrate.
Drawings
Fig. 1 is a schematic diagram of a direct writing apparatus.
Fig. 2 shows the SEM morphology of the polyaniline organic electrode prepared in example 2.
FIG. 3 is SEM morphology of polyaniline organic electrode containing 0.05wt% multi-walled carbon nanotubes prepared in example 5.
FIG. 4 is an IR spectrum of an organic electrode, wherein (a) is a polyaniline organic electrode containing 0.05wt% multi-walled carbon nanotubes prepared in example 5; (b) the polyaniline organic electrode prepared in example 2.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments and drawings, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1:
using Soildworks software to establish a 20mm × 20mm × 0.5mm thin-film electrode 3D model, and adopting Cura software to slice the established 3D model, wherein the slicing parameters are as follows: the layer thickness is 0.01mm, the printing layer number is 50 layers, the needle point moving speed is set to be 30mm/s, and the motion trail is non-woven fabric weaving. Weighing 0.6 g of conductive polyaniline, dissolving in 8.1g of N-methylformamide, carrying out sealed ultrasonic dispersion for 3 hours, weighing 0.4 g of polyvinylidene fluoride and 0.9 g of acetone, adding into the PANI solution, and carrying out sealed ultrasonic dispersion for 3 hours to prepare printing ink containing 6wt% of PANI, 4wt% of PVDF and 9wt% of acetone; 3 mL of printing ink is sucked by an injector, and a needle head is assembled; connecting the positive pole of a high-voltage direct-current power supply with a needle head, connecting the negative pole of the high-voltage direct-current power supply with a copper plate at the lower part of a bottom plate, fixing a needle tube, wiping liquid drops at the front end of the needle head completely after adjusting the distance between the needle head and the bottom plate to be 3 mm, adjusting the high-voltage direct-current power supply to be 4 kV, starting a writing device until the writing is finished to obtain an organic electrode, wherein the thin-film electrode is soft and flexible, and the conductivity of the-5 S/m。
Example 2:
using Soildworks software to establish a film electrode 3D model with the diameter of 20mm and the circular thickness of 1mm, and adopting Cura software to slice the established 3D model, wherein the slicing parameters are as follows: the layer thickness is 0.01mm, the printing layer number is 100 layers, the moving speed of the needle point is set to be 30mm/s, and the motion track is set to be a concentric circle. Weighing 1.5 g of conductive polyaniline, dissolving in 6.8 g of N-methylformamide (DMF), carrying out sealed ultrasonic dispersion for 3 h, weighing 0.8 g of polyvinylidene fluoride and 0.9 g of acetone, adding into the PANI solution, and carrying out sealed ultrasonic dispersion for 3 h to prepare printing ink containing 15wt% of PANI, 8wt% of PVDF and 9wt% of acetone; absorbing 3 mL of printing ink by using an injector, assembling a needle head, connecting a positive electrode of a high-voltage direct current power supply with the needle head, connecting a negative electrode of the high-voltage direct current power supply with a copper plate at the lower part of a bottom plate, fixing a needle tube, adjusting the distance between the needle head and the bottom plate to be 3 mm, wiping liquid drops at the front end of the needle head, adjusting the high-voltage direct current power supply to be 4 kV, starting a writing device until the writing is finished, and obtaining an organic electrode, wherein the conductivity of the organic electrode is-4 S/m。
Example 3:
using Soildworks software to establish a film electrode 3D model with the diameter of 20mm and the circular thickness of 1mm, and adopting Cura software to slice the established 3D model, wherein the slicing parameters are as follows: the layer thickness is 0.01mm, the printing layer number is 100 layers, the moving speed of the needle point is set to be 30mm/s, and the motion track is set to be a concentric circle. Weighing 1.0 g of conductive polyaniline, dissolving in 7.5 g N-methylformamide (DMF), carrying out sealed ultrasonic dispersion for 3 h, weighing 0.6 g of polyvinylidene fluoride and 0.9 g of acetone, adding into the PANI solution, and carrying out sealed ultrasonic dispersion for 3 h to prepare printing ink containing 10wt% of PANI, 6wt% of PVDF and 9wt% of acetone; 3 mL of printing ink is sucked by a syringe, a needle head is assembled, the positive pole of a high-voltage direct current power supply is connected with the needle head, and the negative pole of the high-voltage direct current power supply is connected with a copper plate at the lower part of a bottom plate. And fixing the needle tube, and wiping liquid drops at the front end of the needle head completely after the distance between the debugging needle head and the bottom plate is 1 mm. Adjusting the high-voltage DC power supply to 2 kV, starting the writing device until the writing is finished to obtain the organic electrode, wherein the electrode film has accurate size and high flexibility, and the electrode conductivity is 9.7 multiplied by 10-5 S/m。
Example 4:
3D models of the interdigital electrodes are built by using Soildworks software, the built 3D models are sliced by using Cura software, and the slicing parameters are as follows: the layer thickness is 0.01mm, the printing layer number is 50 layers, the moving speed is 30mm/s, and the motion track is in a reciprocating mode. Weighing 1.5 g of conductive Polyaniline (PANI) to be dissolved in 7.2 g of N-methylformamide, carrying out sealed ultrasonic dispersion for 3 h, weighing 0.4 g of polyvinylidene fluoride (PVDF) and 0.9 g of acetone to be added into the PANI solution, carrying out sealed ultrasonic dispersion for 3 h, and preparing the printing ink containing 15wt% of PANI, 4wt% of PVDF and 9wt% of acetone. 3 mL of the printing ink was aspirated with a syringe, and a needle was fitted. The positive pole of the high voltage direct current power supply is connected with the needle head, and the negative pole of the high voltage direct current power supply is connected with the copper plate at the lower part of the bottom plate, as shown in figure 1. Fix the needle tubing, after the distance between debugging syringe needle and the bottom plate is 5mm, clean syringe needle front end liquid drop, adjust high voltage direct current power supply and be 9 kV, start the 3D printer and carry out electrode film's printing, obtain organic electrode, this electrode film size is accurate, has higher pliability, and the conductivity of electrode is 8.4 x 10-2S/m。
Example 5:
after a 20mm × 20mm × 1mm square electrode thin film 3D model is established by using Soildworks software, the established 3D model is sliced by using Cura software, and the slicing parameters are as follows: the layer thickness is 0.01mm, the printing layer number is 100 layers, the moving speed is 30mm/s, and the motion trail is non-woven fabric weaving. Weighing 0.005 g of multi-walled carbon nanotube, dispersing in 7.195 g N-methyl formamide (DMF), ultrasonically dispersing for 2 h, weighing 1.5 g of PANI, dissolving in the precursor, ultrasonically dispersing for 3 h, weighing 0.4 g of polyvinylidene fluoride (PVDF) and 0.9 g of acetone, adding into the PANI solution, sealing and ultrasonically dispersing for 3 h, and preparing the printing ink containing 15wt% of PANI, 4wt% of PVDF, 0.05wt% of multi-walled carbon nanotube and 9wt% of acetone. 3 mL of the printing ink was aspirated with a syringe, and a needle was fitted. The positive pole of the high-voltage direct current power supply is connected with the needle head, and the negative pole of the high-voltage direct current power supply is connected with the copper plate at the lower part of the bottom plate. Fixing the needle tube, wiping liquid drops at the front end of the needle head after the distance between the debugging needle head and the bottom plate is 3 mm, adjusting a high-voltage direct-current power supply to be 4 kV, starting a 3D printer to print an electrode film to obtain an organic electrode, wherein the conductivity of the electrode is 2.1S/m.
FIG. 1 is a simplified diagram of the writing process of the present invention, in which the writing device is composed of a syringe filled with writing ink, a writing needle tip, a bottom plate, an XYZ three-axis moving mechanism and a DC high-voltage power supply.
Fig. 2 shows the SEM morphology of the Polyaniline (PANI) organic electrode prepared in example 2, which has a uniform fibrous structure, a dense structure, and good flexibility.
FIG. 3 is SEM morphology of polyaniline organic electrode containing 0.05wt% multi-walled carbon nanotubes prepared in example 5. The surface appearance is changed from a fibrous structure into a blocky rod-shaped structure, the resistivity of the material is reduced, the conductivity is increased, and the conductivity of the electrode is 2.1S/m.
FIG. 4 is an IR spectrum of an organic electrode, wherein (a) is a polyaniline organic electrode containing 0.05wt% multi-walled carbon nanotubes prepared in example 5; (b) the polyaniline organic electrode prepared in example 2; in the figure, the length of the light beam is 3400--1Obviously shows the characteristic absorption peak of polyaniline, and the enhancement effect on the multi-wall carbon nano-tubeWith the use of the catalyst, the intensity of each characteristic peak was increased as shown in (a) and was set at 830cm -1And 1500cm -1There is a first order vibration of the graphitic carbon.

Claims (2)

1. A preparation method of a direct writing type high-flexibility organic electrode is characterized by comprising the following steps:
(1) 3D modeling is carried out on the needed electrode shape by adopting Soildworks, and the electrode model is sliced by adopting Crua software; the parameters of the slices are: the moving speed is 30mm/s, the slice thickness is 0.01mm, and the number of printing layers is 50-100;
(2) preparing writing ink: weighing a multi-walled carbon nanotube according to a proportion, mixing the multi-walled carbon nanotube with an N-methylformamide solution, and ultrasonically dispersing until the mixture is uniform to obtain a precursor solution; adding polyaniline into the precursor solution, performing ultrasonic dispersion, then adding polyvinylidene fluoride and acetone, and performing sealed ultrasonic treatment until the polyaniline is completely dissolved to obtain writing ink; the using amount of the multi-wall carbon nano tube is 0.05 wt%; the dosage of the N-methylformamide is 68 to 81 weight percent; the dosage of the polyaniline is 6 to 15 weight percent; the usage amount of the polyvinylidene fluoride is 4-8 wt%; the amount of the acetone is 9 wt%;
(3) setting a writing flow and a writing process; the writing device comprises a needle tube, a writing needle head, a bottom plate, an XYZ three-axis moving mechanism and a high-voltage direct-current power supply; absorbing the writing ink prepared in the step (2) by using a needle tube in the writing process, assembling a writing needle head, connecting the positive pole of a high-voltage direct-current power supply with the needle head, and connecting the negative pole of the high-voltage direct-current power supply with a copper plate at the lower part of a bottom plate; fixing the needle tube, adjusting the distance between the needle head and the bottom plate, adjusting the voltage of a high-voltage direct-current power supply, and starting a writing program to finish to obtain an organic electrode; the distance between the needle head and the bottom plate is 1-5 mm; the voltage of the direct-current power supply is 2-9 kV.
2. The method for preparing a directly-writable highly flexible organic electrode according to claim 1, wherein the volume of the writing ink sucked in the step (3) is 3 mL.
CN201810825755.3A 2018-07-25 2018-07-25 Preparation method of direct-writing high-flexibility organic electrode Active CN109130168B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810825755.3A CN109130168B (en) 2018-07-25 2018-07-25 Preparation method of direct-writing high-flexibility organic electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810825755.3A CN109130168B (en) 2018-07-25 2018-07-25 Preparation method of direct-writing high-flexibility organic electrode

Publications (2)

Publication Number Publication Date
CN109130168A CN109130168A (en) 2019-01-04
CN109130168B true CN109130168B (en) 2020-11-20

Family

ID=64798957

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810825755.3A Active CN109130168B (en) 2018-07-25 2018-07-25 Preparation method of direct-writing high-flexibility organic electrode

Country Status (1)

Country Link
CN (1) CN109130168B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11901705B2 (en) 2021-07-22 2024-02-13 Federal-Mogul Ignition Gmbh Electrode tip assembly for a spark plug and method of manufacturing the same
CN115165165B (en) * 2022-06-24 2023-05-23 深圳深南电燃机工程技术有限公司 High-sensitivity flexible pressure sensor

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101429336A (en) * 2008-10-30 2009-05-13 上海应用技术学院 Process for producing carbon nano-tube/polyaniline conductive composite material
CN102719927A (en) * 2012-07-04 2012-10-10 青岛大学 Preparation method of polyvinylidene fluoride (PVDF)/carbon nanotube composite nanofibers
CN103612391A (en) * 2013-11-13 2014-03-05 西安交通大学 Three-dimensional (3D) printing method of micro-nano structure based on near-field electrostatic spinning
CN204658952U (en) * 2015-03-16 2015-09-23 东莞劲胜精密组件股份有限公司 A kind of 3D printing equipment
CN106182785A (en) * 2016-09-05 2016-12-07 西北工业大学 A kind of device and method utilizing alternating current spinning to realize 3 D-printing micro-nano structure
WO2018085936A1 (en) * 2016-11-10 2018-05-17 Polyvalor, Limited Partnership Piezoelectric composite, ink and ink cartridge for 3d printing, bifunctional material comprising the piezoelectric composite, manufacture and uses thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101429336A (en) * 2008-10-30 2009-05-13 上海应用技术学院 Process for producing carbon nano-tube/polyaniline conductive composite material
CN102719927A (en) * 2012-07-04 2012-10-10 青岛大学 Preparation method of polyvinylidene fluoride (PVDF)/carbon nanotube composite nanofibers
CN103612391A (en) * 2013-11-13 2014-03-05 西安交通大学 Three-dimensional (3D) printing method of micro-nano structure based on near-field electrostatic spinning
CN204658952U (en) * 2015-03-16 2015-09-23 东莞劲胜精密组件股份有限公司 A kind of 3D printing equipment
CN106182785A (en) * 2016-09-05 2016-12-07 西北工业大学 A kind of device and method utilizing alternating current spinning to realize 3 D-printing micro-nano structure
WO2018085936A1 (en) * 2016-11-10 2018-05-17 Polyvalor, Limited Partnership Piezoelectric composite, ink and ink cartridge for 3d printing, bifunctional material comprising the piezoelectric composite, manufacture and uses thereof

Also Published As

Publication number Publication date
CN109130168A (en) 2019-01-04

Similar Documents

Publication Publication Date Title
CN109130168B (en) Preparation method of direct-writing high-flexibility organic electrode
Luo et al. Flexible piezoelectric pressure sensor with high sensitivity for electronic skin using near-field electrohydrodynamic direct-writing method
CN108963069B (en) Preparation method of 3D printed polyvinylidene fluoride piezoelectric film
CN105196550B (en) A kind of multiple dimensioned 3D printing device of more materials of single nozzle and its method of work
CN106273497B (en) A kind of more Material cladding 3D printers and its working method and application
CN102051651A (en) Preparation method of graphene film
CN104698041B (en) Ethanol sensor based on nano structure of zinc oxide and preparation method thereof
CN101042977B (en) Carbon nanotube field emission type electron source and its manufacturing method
CN109686836B (en) Preparation method for 3D printing of polyvinylidene fluoride piezoelectric film under uniform electric field
CN103839608A (en) Method for manufacturing conductive graphene film through ink-jet printing
CN112924060B (en) Flexible pressure sensor and preparation method thereof
CN104358029A (en) Method and device for preparing micro-nano corrugated structure by electrostatic spinning
CN108225620A (en) A kind of flexible touch sensation sensor with multi-layer structure and preparation method thereof
CN104851515B (en) A kind of preparation method of conductive film
CN112254630A (en) Flexible wearable sensor with high sensitivity and high deformation range and preparation method thereof
CN101847459A (en) Composite carbon nanotube conductive thin film and preparation method and preparation device thereof
CN107492455A (en) A kind of preparation method of all solid state Ehrhardt flexible miniature ultracapacitor
CN102191573B (en) Mass production nanofiber electrospinning device
CN109003745A (en) A kind of preparation method of highly conductive graphene flexible electrode
CN100454474C (en) Method for preparing field emission display cathode and ZnO nanowire cathode
CN107792847A (en) The method that arc discharge method prepares graphene
CN113881286A (en) Water-based MXene ink-jet printing conductive ink and preparation method and application thereof
CN107665996B (en) Three-dimensional porous nickel hollow fiber electrode material, preparation method and battery based on electrode
CN108335955B (en) graphene-based field emission cold cathode and preparation method thereof
CN110357088A (en) A kind of method and application preparing graphene oxide based on gelatin

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant