CN116254017B - Stretchable composite conductive ink and preparation method thereof - Google Patents

Stretchable composite conductive ink and preparation method thereof Download PDF

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CN116254017B
CN116254017B CN202310450339.0A CN202310450339A CN116254017B CN 116254017 B CN116254017 B CN 116254017B CN 202310450339 A CN202310450339 A CN 202310450339A CN 116254017 B CN116254017 B CN 116254017B
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melting
low
conductive ink
alloy
composite conductive
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CN116254017A (en
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王江新
寇旭
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Sichuan University
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Sichuan University
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/52Electrically conductive inks
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/10Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Conductive Materials (AREA)
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Abstract

The invention discloses stretchable composite conductive ink and a preparation method thereof, and relates to the technical field of electronic material preparation. The stretchable composite conductive ink comprises the following raw materials in parts by weight: 50-75 parts of liquid metal and 25-50 parts of low-melting-point alloy particles. The preparation method comprises the following steps: firstly, preparing low-melting-point alloy particles by ultrasonic treatment; and then uniformly mixing the low-melting-point alloy particles with liquid metal to prepare the stretchable composite conductive ink. According to the invention, the low-melting-point alloy particles are added into the liquid metal, so that the surface tension of the liquid metal is obviously reduced while the good conductivity is ensured, and the prepared stretchable composite conductive ink can directly form conductive patterns on a flexible substrate, has good stretchability and conductivity and can adapt to various deformations. The material of the invention has simple preparation process, low production cost, easy process grasping and easy realization of large-scale production, and has great practical value.

Description

Stretchable composite conductive ink and preparation method thereof
Technical Field
The invention relates to the technical field of electronic material preparation, in particular to stretchable composite conductive ink and a preparation method thereof.
Background
With the rapid development of current science and technology, it has been difficult for conventional rigid electronic devices to meet the needs of people, and flexible electronic devices capable of being in close contact with human bodies and highly fused are gradually moving into the lives of people. The flexible electronic device mainly comprises a flexible matrix and a flexible integrated circuit, and can still normally operate under the deformation of stretching, bending and the like compared with the traditional rigid electronic device, and has good application prospect in the fields of wearable electronic equipment, biomedicine and the like.
Integrated circuits in conventional rigid electronic devices often use high modulus metals such as copper and gold as conductive materials that are prone to cracking during deformation, resulting in circuit failure. Currently, integrated circuits in flexible electronic devices are mostly made of stretchable conductive inks as conductive materials by printing to build conductive paths on flexible substrates. Stretchable conductive ink is a composite material that is both stretchable and conductive. Conventional stretchable conductive inks typically incorporate conductive fillers (e.g., silver nanowires, silver nanoplates, carbon nanotubes, etc.) into elastomeric polymers to build continuous conductive paths within the polymer using the mutual contact between the conductive fillers. The stretchable conductive ink prepared by the method has good binding force with the flexible matrix due to the addition of the polymer, and is beneficial to forming a conductive path on the surface of the flexible matrix; however, it is difficult to maintain stable contact of the conductive filler during the tensile deformation, resulting in poor tensile conductive stability of the circuit; meanwhile, the common conductive filler has higher tensile modulus, and can limit the tensile property of the whole conductive ink.
The liquid metal has excellent conductivity and fluidity, is an excellent stretchable conductive material, and has great application potential in the aspect of flexible integrated circuits. However, the liquid metal has a large surface tension, which hinders wetting of the surface of the flexible substrate, thereby making it difficult to form a stable circuit pattern on the surface of the flexible substrate; meanwhile, the viscosity of the liquid metal is too low, and leakage is liable to occur. In order to solve the above problems, there are researchers that disperse liquid metal into fine particles coated with oxide film by ultrasonic treatment, then print the liquid metal fine particles onto the surface of a flexible substrate by inkjet printing, and then selectively sinter (mechanical sintering, laser sintering) to destroy the oxide film on the surface of the liquid metal, thereby forming a conductive pattern. The method can obtain very fine conductive patterns, and the liquid metal and the surface of the flexible matrix have better binding force, but the method has the advantages of multiple process steps, complex equipment and high manufacturing cost.
Therefore, developing a conductive ink which has high conductivity, stretchability, good binding force with a flexible substrate and can simply construct a circuit on the flexible substrate and a preparation method thereof are the problems which are needed to be solved in the technical field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides stretchable composite conductive ink and a preparation method thereof, and effectively solves the problems that the stretchability and the conductivity of the conventional stretchable conductive ink are difficult to be compatible, and liquid metal is difficult to be directly patterned on the surface of a flexible matrix.
The invention solves the technical problems and adopts the following technical scheme:
the stretchable composite conductive ink comprises the following raw materials in parts by weight: 50-75 parts of liquid metal and 25-50 parts of low-melting-point alloy particles.
Also provided is a method for preparing the stretchable composite conductive ink, comprising the following steps:
(1) Preparation of low-melting-point alloy particles: heating the low-melting-point alloy to be melted, adding the low-melting-point alloy into an organic solvent, carrying out ultrasonic treatment, and then sequentially standing, filtering and drying to obtain low-melting-point alloy particles;
(2) Preparation of stretchable composite conductive ink: and (3) uniformly mixing the liquid metal and the low-melting-point alloy particles prepared in the step (1) to prepare the stretchable composite conductive ink.
Based on the technical scheme, the invention can also be improved as follows:
preferably, in the step (1), the low melting point alloy is indium tin bismuth alloy, indium chromium tin lead bismuth alloy, indium tin lead bismuth alloy, chromium lead bismuth alloy or chromium tin lead bismuth alloy.
Preferably, in the step (1), the low melting point alloy is indium tin bismuth alloy.
Preferably, the mass ratio of indium, tin and bismuth in the indium-tin-bismuth alloy is 50-55:30-35:15-20.
Preferably, the indium, tin and bismuth in the indium tin bismuth alloy have a mass ratio of 51:32.5:16.5.
preferably, the mass ratio of indium, chromium, tin, lead and bismuth in the indium-chromium-tin-lead-bismuth alloy is 18-20:4-6:7-9:20-25:40-50.
Preferably, the mass ratio of indium, chromium, tin, lead and bismuth in the indium-chromium-tin-lead-bismuth alloy is 19:5:8:23:45.
preferably, the mass ratio of indium, tin, lead and bismuth in the indium tin lead bismuth alloy is 20-22:10-15:15-20:47-50.
Preferably, the mass ratio of indium, tin, lead and bismuth in the indium tin lead bismuth alloy is 21:12:18:49.
preferably, the mass ratio of chromium, lead and bismuth in the chromium-lead-bismuth alloy is 5-10:38-42:50-55.
Preferably, the mass ratio of chromium, lead and bismuth in the chromium-lead-bismuth alloy is 8:40:52.
preferably, the mass ratio of chromium, tin, lead and bismuth in the chromium-tin-lead-bismuth alloy is 8-12:10-15:25-30:48-52.
Preferably, the mass ratio of chromium, tin, lead and bismuth in the chromium-tin-lead-bismuth alloy is 10:13:27:50.
preferably, in the step (1), when the low melting point alloy is indium tin bismuth alloy, the alloy is heated to be molten under the condition of 55-65 ℃.
Preferably, in the step (1), when the low melting point alloy is indium tin bismuth alloy, the alloy is heated to be melted at 60 ℃.
Preferably, in the step (1), when the low-melting-point alloy is indium-chromium-tin-lead-bismuth alloy, the alloy is heated to be molten at the temperature of 45-50 ℃.
Preferably, in the step (1), when the low-melting-point alloy is indium-chromium-tin-lead-bismuth alloy, the alloy is heated to be melted at 47 ℃.
Preferably, in the step (1), when the low-melting-point alloy is indium tin lead bismuth alloy, the alloy is heated to be molten at 57-65 ℃.
Preferably, in the step (1), when the low-melting-point alloy is indium-chromium-tin-lead-bismuth alloy, the alloy is heated to be melted at 57 ℃.
Preferably, in the step (1), when the low-melting-point alloy is chromium-lead-bismuth alloy, the alloy is heated to be molten at 92-100 ℃.
Preferably, in the step (1), when the low-melting-point alloy is chromium-lead-bismuth alloy, the alloy is heated to be melted at 92 ℃.
Preferably, in the step (1), when the low-melting-point alloy is chromium-tin-lead-bismuth alloy, the alloy is heated to be molten at the temperature of 70-80 ℃.
Preferably, in the step (1), when the low-melting-point alloy is chromium-tin-lead-bismuth alloy, the alloy is heated to be molten at 70 ℃.
Preferably, in step (1), the organic solvent is ethanol, isopropanol or methanol.
Preferably, in step (1), the organic solvent is ethanol.
Preferably, in step (1), the ultrasonic treatment is performed under heating.
Preferably, in step (1), the heating temperature is the same as the temperature at which the low melting point alloy is melted.
Preferably, in the step (1), the ultrasonic time is 20min, and the ultrasonic power is 500-700W.
Preferably, in the step (1), the mixture is kept stand for 20 to 30 hours.
Preferably, in the step (1), the mixture is dried at the temperature of 40-50 ℃ for 2.5-3.5 hours.
Preferably, in the step (2), the liquid metal is eutectic gallium-indium alloy, and the mass ratio of gallium to indium in the eutectic gallium-indium alloy is 70-80:20-30.
Preferably, in the step (2), the mass ratio of gallium to indium in the eutectic gallium-indium alloy is 75.5:24.5.
preferably, in the step (2), the mass ratio of the liquid metal to the low-melting-point alloy particles prepared in the step (1) is 50-75:25-50.
The invention also provides application of the stretchable composite conductive ink in preparation of flexible electronic devices.
The invention has the following beneficial effects:
1. according to the invention, the low-melting-point alloy particles are mixed in the liquid metal, so that the surface tension of the liquid metal is effectively reduced, the viscosity of the liquid metal is increased, the wetting effect of the liquid metal on the surface of the flexible substrate is improved, and a fine circuit pattern can be constructed on the surface of the flexible substrate through a simple printing process.
2. The stretchable conductive ink provided by the invention has excellent conductivity and stretchability, can ensure good conductive stability in the stretching deformation process, and overcomes the defect of poor conductive stability of the traditional stretchable conductive ink during stretching.
3. The material of the invention has simple preparation process, low production cost, easy process grasping and easy realization of large-scale production, and has great practical value.
Drawings
FIG. 1 is a flow chart of the preparation of the stretchable composite conductive ink of example 1;
FIG. 2 is an SEM image of low-melting alloy particles of example 1;
FIG. 3 is an SEM image of the stretchable composite conductive ink prepared in example 1;
FIG. 4 is a flexible integrated circuit of the stretchable composite conductive ink prepared in example 1;
fig. 5 is a graph showing the comparison of the tensile properties of the tensile composite conductive ink prepared in example 1 before and after the tensile properties.
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
the preparation method of the stretchable composite conductive ink comprises the following steps: (flow chart see FIG. 1)
(1) Heating indium-tin-bismuth alloy (the mass ratio of indium to tin to bismuth is 51:32.5:16.5) at 60 ℃ to melt, adding the alloy into ethanol solution, performing ultrasonic treatment for 20min at 60 ℃ under the conditions of heating and ultrasonic power of 600W, dispersing the alloy into particles, standing for 24h, completely precipitating the alloy particles, filtering, and drying at 45 ℃ for 3h to obtain low-melting-point alloy particles;
(2) Eutectic gallium-indium alloy (the mass ratio of gallium to indium is 75.5:24.5) and the low-melting-point alloy particles prepared in the step (1) are mixed according to the mass ratio of 3:1, stirring and mixing uniformly for multiple times rapidly to obtain the stretchable composite conductive ink.
Example 2:
the preparation method of the stretchable composite conductive ink comprises the following steps:
(1) Heating an indium-tin-bismuth alloy (the mass ratio of indium to tin to bismuth is 55:30:15) at 65 ℃ to melt, adding the alloy into an ethanol solution, performing ultrasonic treatment for 10min at the temperature of 65 ℃ and the ultrasonic power of 700W, dispersing the alloy into particles, standing for 30h, completely precipitating the alloy particles, filtering, and drying at 50 ℃ for 2.5h to obtain low-melting-point alloy particles;
(2) Eutectic gallium-indium alloy (the mass ratio of gallium to indium is 80:20) and the low-melting-point alloy particles prepared in the step (1) are mixed according to the mass ratio of 2:1, stirring and mixing uniformly for multiple times rapidly to obtain the stretchable composite conductive ink.
Example 3:
the preparation method of the stretchable composite conductive ink comprises the following steps:
(1) Heating an indium-tin-bismuth alloy (the mass ratio of indium to tin to bismuth is 50:30:20) at 55 ℃ to melt, adding the alloy into an ethanol solution, performing ultrasonic treatment at 55 ℃ and ultrasonic power of 500W for 10min, dispersing the alloy into particles, standing for 20h, completely precipitating the alloy particles, filtering, and drying at 40 ℃ for 3.5h to obtain low-melting-point alloy particles;
(2) Eutectic gallium-indium alloy (the mass ratio of gallium to indium is 70:30) and the low-melting-point alloy particles prepared in the step (1) are mixed according to the mass ratio of 1:1, stirring and mixing uniformly for multiple times rapidly to obtain the stretchable composite conductive ink.
Example 4:
the preparation method of the stretchable composite conductive ink comprises the following steps:
in the step (2), the mass ratio is 2:1, the remainder was the same as in example 1, to prepare a stretchable composite conductive ink.
Example 5:
the preparation method of the stretchable composite conductive ink comprises the following steps:
in the step (2), the mass ratio is 1:1, the remainder was the same as in example 1, to prepare a stretchable composite conductive ink.
Test examples
1. SEM examination was performed on the low melting point alloy particles and the stretchable composite conductive ink prepared in example 1, respectively, and the results are shown in fig. 2 to 3.
As can be seen from FIG. 2, the low melting point alloy particles prepared according to the present invention have a size of 1-5 microns.
As can be seen from fig. 3, the liquid metal and the low-melting-point alloy particles in the stretchable composite conductive ink prepared by the invention are well combined, and the low-melting-point alloy particles are uniformly dispersed in the liquid metal.
2. The stretchable composite conductive ink prepared in example 1 was patterned on a substrate by stencil printing, and then electronic components (resistors, LEDs, operational amplifiers) were mounted to prepare a flexible integrated circuit, the result of which is shown in fig. 4.
As can be seen from fig. 4, the stretchable composite conductive ink prepared by the present invention can be used to prepare conductive patterns on a flexible substrate by a simple printing process, and is well suited for application to flexible integrated circuits.
3. The stretchable composite conductive ink (3 cm) prepared in example 1 was attached to a flexible substrate and then stretched (20 cm), the results of which are shown in FIG. 5.
As can be seen from FIG. 5, the tensile composite conductive ink prepared by the invention has tight combination with the flexible substrate and stable morphology without generating defects such as cracks under the tensile strain of nearly 600%, which indicates that the tensile composite conductive ink prepared by the invention has excellent combination ability and good tensile property with the flexible substrate.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.

Claims (3)

1. The stretchable composite conductive ink is characterized by comprising the following raw materials in parts by weight: 50-75 parts of liquid metal and 25-50 parts of low-melting-point alloy particles;
the preparation method of the stretchable composite conductive ink comprises the following steps:
(1) Preparation of low-melting-point alloy particles: heating the low-melting-point alloy to be melted, adding the low-melting-point alloy into an organic solvent, carrying out ultrasonic treatment, and then sequentially standing, filtering and drying to obtain low-melting-point alloy particles;
(2) Preparation of stretchable composite conductive ink: uniformly mixing liquid metal and the low-melting-point alloy particles prepared in the step (1) to prepare stretchable composite conductive ink;
in the step (1), the low-melting-point alloy is indium tin bismuth alloy, indium chromium tin lead bismuth alloy, indium tin lead bismuth alloy, chromium lead bismuth alloy or chromium tin lead bismuth alloy;
in the step (1), the organic solvent is ethanol, isopropanol or methanol;
in the step (2), the liquid metal is eutectic gallium-indium alloy, and the mass ratio of gallium to indium in the eutectic gallium-indium alloy is 70-80:20-30.
2. The stretchable composite conductive ink according to claim 1, wherein in step (1), the ultrasonic treatment is performed under heating.
3. The stretchable composite conductive ink according to claim 1, wherein in the step (2), the mass ratio of the liquid metal to the low melting point alloy particles obtained in the step (1) is 50 to 75:25-50.
CN202310450339.0A 2023-04-24 2023-04-24 Stretchable composite conductive ink and preparation method thereof Active CN116254017B (en)

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