CN116694141A - Printable liquid metal ink and preparation method thereof - Google Patents
Printable liquid metal ink and preparation method thereof Download PDFInfo
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- CN116694141A CN116694141A CN202310774259.0A CN202310774259A CN116694141A CN 116694141 A CN116694141 A CN 116694141A CN 202310774259 A CN202310774259 A CN 202310774259A CN 116694141 A CN116694141 A CN 116694141A
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- liquid metal
- metal ink
- ink
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- hydrochloric acid
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- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000846 In alloy Inorganic materials 0.000 claims abstract description 22
- 239000012802 nanoclay Substances 0.000 claims abstract description 21
- 238000012986 modification Methods 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 18
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- -1 polyethylene copolymer Polymers 0.000 claims abstract description 8
- 239000004698 Polyethylene Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 229920000573 polyethylene Polymers 0.000 claims abstract description 7
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000007639 printing Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000000017 hydrogel Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 5
- 239000002923 metal particle Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 70
- 239000000243 solution Substances 0.000 description 18
- 238000005245 sintering Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229960004050 aminobenzoic acid Drugs 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 4
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 description 2
- 239000012901 Milli-Q water Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 238000003854 Surface Print Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
- C09D11/52—Electrically conductive inks
-
- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses printable liquid metal ink and a preparation method thereof, wherein the preparation method comprises the following steps: 1) Placing gallium-indium alloy in hydrochloric acid with higher concentration to ensure that the hydrochloric acid can completely cover the gallium-indium alloy, and incubating overnight; 2) Washing with absolute ethyl alcohol for three times to ensure that hydrochloric acid is removed completely, adding p-aniline derivatives and nano clay, and mixing until dissolving; 3) Performing ultrasonic modification by using an ultrasonic cell disruption instrument; 4) Washing the liquid metal nano-particles obtained in the step 3) with water; 5) Dissolving polyethylene copolymer in water; 6) Resuspending the liquid metal particles of step 4) with deionized water, followed by mixing with the ink vehicle obtained in step 4) to obtain a liquid metal ink. The invention adopts a physical-chemical combination means to carry out compound modification, and the obtained liquid metal ink has high viscosity and strong adhesive force after being mixed with an ink carrier, and can be effectively adhered on a flexible substrate to form a conductive electrode.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to printable liquid metal ink and a preparation method thereof.
Background
Liquid metal is a new type of conductive ink, which is generally referred to as a low melting point alloy with a melting point below 200 ℃. The liquid metal has a low melting point at room temperature and is liquid at room temperature. Compared with the conventional fluid, the liquid metal has excellent thermal conductivity and electrical conductivity, and a liquid phase temperature range is wide, so that more and more researches are conducted. The room temperature liquid pure metals found in nature include mercury, cesium, strontium and gallium with melting points of-38.87 ℃, 28.65 ℃, 27 ℃ and 29.8 ℃, respectively. Among them, mercury has relatively high volatility, mercury and amalgam have certain toxicity, and residues containing mercury enter ecological cycle and cause harm to human and environment, so the mercury-containing residue should be carefully used. Cesium is an active alkali metal that is easily oxidized in air and reacts strongly with water, while strontium is also an active metal that reacts directly with water and reacts strongly with acids, and strontium is an unstable radioactive element.
Liquid metal ink can be used for printing different surfaces and is one of main raw materials affecting the electrical performance of the flexible electrode, however, the liquid metal ink cannot be directly used for printing the flexible electrode or printing the surface due to the too high surface tension of the liquid metal, so that the application of the liquid metal ink in biological sensing is limited. At present, a common process is to reduce the tension of the surface of gallium indium alloy (melting point is lower than room temperature and is the most common conductive ink) by physical methods such as ultrasonic wave or mechanical stirring, and make it printable. However, in the ultrasonic treatment process, since the liquid metal is also easily oxidized, the oxide on the liquid metal block is broken, a new oxide layer is formed on the liquid metal nano particles, the liquid metal is prevented from being compounded, and the oxide layer formed on the liquid metal is not conductive and stretchable as compared with the liquid metal. Next, an oxide layer (Ga 2 O 3 ) It also readily reacts with water to form rod-like crystals (GaOOH), further degrading the properties of the material. Therefore, in order to improve the performance of the liquid metal ink applied to printing of a flexible electrode or other surface, the growth of oxide should be suppressed. Therefore, there is a need for a simple and feasible method for liquid metal to reduce the effect of oxides on its conductivity and to enable easy printing.
The current method for oxide suppression and functionalization of liquid metal droplets is chemical modification. The thickness of the oxide layer is reduced to 30% by modification of the thiolate molecules, followed by deposition of a layer of LM droplets on the flexible substrateOn the plate and made conductive by a subsequent sintering process. But due to insulated Ga 2 O 3 The oxide layer is continuously formed on the surface of the liquid metal particles, so that even after the solvent is completely volatilized, the circuit without sintering is substantially packed together and insulated from each other by a large number of liquid metal particles, which are encapsulated in Ga 2 O 3 In the oxide layer, and the oxide layer is difficult to remove by simple sintering. Meanwhile, the liquid metal nano particles have low adhesive force, so that the liquid metal nano particles are easy to fall off after being printed and sintered on a flexible substrate or other surfaces.
Thus, ga cannot be completely eliminated due to the use of the present physical and chemical methods 2 O 3 The adverse effects of the oxide layer, which have associated problems, limit the use of liquid metal inks in flexible electrode printing or other surface printing, and thus also limit their use in biosensing.
Disclosure of Invention
The invention provides a preparation method of printable liquid metal ink, which can be used for printing flexible electrodes or other surfaces.
The invention provides a preparation method of liquid metal ink for flexible electrode printing, which comprises the following steps:
1) Placing a proper amount of gallium-indium alloy in hydrochloric acid, covering the gallium-indium alloy with hydrochloric acid, incubating overnight, and removing an oxide layer to obtain a liquid metal solution;
2) Washing the liquid metal solution obtained in the step 1) with absolute ethyl alcohol, washing to remove hydrochloric acid, adding p-aniline derivatives and nanoclay, and mixing until the mixture is dissolved to obtain a mixture;
3) Performing ultrasonic modification on the mixture obtained in the step 2) by using an ultrasonic cell disruption instrument to obtain liquid metal nano particles;
4) Washing the liquid metal nano particles obtained in the step 3) with water, completely removing absolute ethyl alcohol, and obtaining a high-concentration liquid metal solution;
5) Dissolving polyethylene copolymer in water to obtain an ink carrier;
6) Resuspending the high concentration liquid metal solution obtained in step 4) with deionized water, and then mixing with the ink vehicle obtained in step 5) to obtain the liquid metal ink.
Furthermore, the working frequency of the ultrasonic modification in the step 3) is 30%, the ultrasonic switch is circularly carried out for 2s and 2s, and the reaction time is 90-120min.
Further, after the para-aniline derivative and the nanoclay are added in the step 2), the content of the gallium-indium alloy is 90-95wt%, the content of the para-aniline derivative is 4-9wt%, and the content of the nanoclay is 0-1wt%.
Further, after the para-aniline derivative and the nanoclay are added in the step 2), the content of the gallium-indium alloy is 92-95wt%, the content of the para-aniline derivative is 7-9wt%, and the content of the nanoclay is 0.5-1wt%.
Further, the p-aniline derivative is any one or a combination of a plurality of p-aminothiophenol (PATIs), p-aminobenzoic acid (PABA), p-phenylenediamine (PPD) and p-bromophenol (PBA).
Further, the concentration of the hydrochloric acid in the step 1) is 0.5M.
Further, the polyethylene copolymer in the step 5) is any one of polyvinyl alcohol, polyvinylpyrrolidone and polyethyleneimine.
The invention also provides printable liquid metal ink, which is prepared by the preparation method.
The invention also provides a flexible wearable biosensor comprising the printable liquid metal ink.
The invention also provides the use of the printable liquid metal ink described above in the printing of a functional surface, the surface being any one of an electrode, a microfluidic channel, a hydrogel and glass.
The technical scheme of the invention has the beneficial effects that:
1. the invention provides a preparation method of printable liquid metal ink, which is based on a gallium indium alloy-para-aniline derivative system, and the raw materials mainly comprise gallium indium alloy, para-aniline derivatives and nanoclay, wherein the components are definite, the para-aniline derivatives and the nanoclay are added to inhibit the generation of an oxide layer in the ultrasonic process, so that the liquid metal is functionalized, the addition amount of the liquid metal is related to the bonding degree of bond alloy nano particles, and the surface of the liquid metal modified by para-aminobenzoic acid has more carboxyl groups and can be further used as a sensing interface.
2. The invention adopts a physical-chemical combination means to carry out compound modification, the obtained liquid metal ink has high viscosity after being mixed with an ink carrier, strong adhesive force and good wettability with other components, can be effectively adhered on a flexible substrate to form a conductive electrode or used for printing on other surfaces, can be used for printing to obtain the liquid metal flexible electrode with high conductivity and wide applicability, and overcomes the problems in the prior art. The oxide layer can be removed through simple treatment, the connection of the circuit is supported, the hydrophilic performance is better, the printing can be performed on different flexible substrates, the printing can be performed on different surfaces, meanwhile, the ink has better water stability, and the ink can be stored as powder for storage. Meanwhile, functional groups (carboxyl, amino, hydroxyl, sulfhydryl and the like) exist on the surface of the liquid metal ink, so that the liquid metal ink can be further bonded with gold nanoparticles to support biosensing modification, and therefore the liquid metal ink has application potential in biosensing, and provides feasibility for 3D printing flexible wearable biosensing.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments of the present invention will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph of macroscopic and microscopic morphologies of the liquid metal ink prepared in example 1;
FIG. 2 is a graph of macroscopic and microscopic morphologies of the liquid metal ink prepared in comparative example 1;
FIG. 3 is a plot of the macroscopic topography before and after sintering and a plot of the microscopic topography after sintering of an electrode printed using the liquid metal ink prepared in example 1;
FIG. 4 is a graph showing the particle size distribution of the liquid metal ink prepared in example 1;
FIG. 5 is a graph of the microtopography of the lyophilized liquid metal ink prepared in example 1;
FIG. 6 is a graph showing the conductivity measurement results of the lyophilized liquid metal ink prepared in example 1;
FIG. 7 is a graph showing the results of the adhesion test of the liquid metal ink prepared in example 1;
fig. 8 shows the results of conductivity measurements of prepared liquid metal inks modified with different para-aniline derivatives.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. The present invention will be specifically described with reference to the following specific examples.
The embodiment of the invention provides a preparation method of printable liquid metal ink, which comprises the following steps:
1) Placing a proper amount of gallium-indium alloy in hydrochloric acid to ensure that the hydrochloric acid can completely cover the gallium-indium alloy, and incubating overnight to obtain a liquid metal solution, wherein the step can remove an oxide layer;
2) Washing the liquid metal solution obtained in the step 1) with absolute ethyl alcohol for 3 times to ensure that hydrochloric acid is removed completely, adding p-aniline derivatives and nanoclay, and mixing until the p-aniline derivatives and nanoclay are dissolved to obtain a mixture;
3) Performing ultrasonic modification on the mixture obtained in the step 2) by using an ultrasonic cell disruption instrument to obtain liquid metal nano particles;
4) Washing the liquid metal nano particles obtained in the step 3) with water, completely removing absolute ethyl alcohol, and obtaining a high-concentration liquid metal solution;
5) Dissolving polyethylene copolymer in water to obtain an ink carrier;
6) Resuspending the high concentration liquid metal solution obtained in step 4) with deionized water, and then mixing with the ink vehicle obtained in step 5) to obtain the liquid metal ink.
Specifically, the working frequency of the ultrasonic modification in the step 3) is 30%, the ultrasonic switch is circularly carried out for 2s and 2s, and the reaction time is 90-120min.
Specifically, after the para-aniline derivative and the nanoclay are added in the step 2), the content of the gallium-indium alloy is 90-95wt%, the content of the para-aniline derivative is 4-9wt%, and the content of the nanoclay is 0-1wt%.
Preferably, after the para-aniline derivative and the nanoclay are added in the step 2), the content of the gallium-indium alloy is 90 to 95wt%, the content of the para-aniline derivative is 4 to 9wt%, and the amount of the nanoclay added in the step 2) is 0.5 to 1wt%.
Specifically, the p-aniline derivative is any one or a combination of a plurality of p-aminothiophenol (PATIs), p-aminobenzoic acid (PABA), p-phenylenediamine (PPD) and p-bromophenol (PBA).
Specifically, the concentration of the hydrochloric acid in the step 1) is 0.2-0.7M.
Preferably, the concentration of the hydrochloric acid in the step 1) is 0.5M.
Specifically, the polyethylene copolymer in the step 5) is any one of polyvinyl alcohol, polyvinylpyrrolidone and polyethyleneimine.
The embodiment of the invention also provides printable liquid metal ink, which is prepared by the preparation method.
The embodiment of the invention also provides application of the printable liquid metal ink in preparation of the flexible wearable biosensor.
The embodiment of the invention also provides application of the printable liquid metal ink in printing of functional surfaces, wherein the surfaces are electrodes, microfluidic channels, hydrogel, glass and the like.
Materials, reagents, and the like used in the following examples are commercially available, and unless otherwise indicated, the detection methods employed in the following examples are all experimental methods, detection methods, and preparation methods disclosed in the art.
Example 1 liquid Metal ink preparation and storage method
1) Placing gallium-indium alloy in 0.5M hydrochloric acid to ensure that the hydrochloric acid can completely cover the gallium-indium alloy, incubating overnight, and removing an oxide layer to obtain a liquid metal solution;
2) Washing the liquid metal solution obtained in the step 1) with absolute ethyl alcohol, washing for three times to ensure that hydrochloric acid is removed completely, and then adding p-aminobenzoic acid (PABA) and nano clay, wherein the content of gallium-indium alloy is 92wt%, the content of p-aniline derivative is 7wt% and the content of nano clay is 1wt% to be mixed until the mixture is dissolved, so as to obtain a mixture;
3) Carrying out ultrasonic modification on the mixture obtained in the step 2) by using an ultrasonic cell disruption instrument, wherein the working frequency is 30%, the ultrasonic switch is circularly carried out for 2s, and the reaction time is 105min, so as to obtain liquid metal nano particles;
4) Washing the liquid metal nano particles obtained in the step 3) with water, completely removing absolute ethyl alcohol, and obtaining a high-concentration liquid metal solution;
5) Dissolving polyvinylpyrrolidone in water to obtain an ink carrier;
6) Resuspending the high-concentration liquid metal solution obtained in the step 4) by using deionized water, and then mixing the high-concentration liquid metal solution with the ink carrier obtained in the step 5) to obtain liquid metal ink;
7) After the liquid metal ink is subjected to ultrasonic treatment, the liquid metal ink can be stored in absolute ethyl alcohol to carry out subsequent sensing modification for later use; or pre-cooling and freeze-drying at-80 deg.c for 12-36 hr, long term storing and storing.
Comparative example 1 preparation of unmodified liquid Metal ink
1) Placing gallium-indium alloy in 0.5M hydrochloric acid to ensure that the hydrochloric acid can completely cover the gallium-indium alloy, incubating overnight, and removing an oxide layer to obtain a liquid metal solution;
2) Washing the liquid metal solution obtained in the step 1) with absolute ethyl alcohol for three times to ensure that hydrochloric acid is removed cleanly;
3) Carrying out ultrasonic modification on the liquid metal solution obtained in the step 2) by using an ultrasonic cell disruption instrument, wherein the working frequency is 30%, the ultrasonic switch is circularly carried out for 2s, and the reaction time is 105min, so as to obtain liquid metal nano particles;
4) And 3) washing the liquid metal nano particles obtained in the step 3) with water, and completely removing absolute ethyl alcohol to obtain a high-concentration liquid metal solution.
Use of liquid metal inks
The liquid metal ink prepared in the step 6) in the example 1 and the liquid metal ink prepared in the comparative example 1 are photographed by a scanning electron microscope at the same angle and light, and macroscopic morphology is photographed, and the result is shown in fig. 1 and 2; printing an electrode on the surface of a butyronitrile flexible substrate by using the liquid metal ink prepared in the step 6) in the embodiment 1, rubbing to remove an oxide layer, shooting a scanning electron microscope at the same angle and with light, and obtaining a macroscopic morphology before and after electrode sintering and a microscopic morphology after sintering, wherein the left graph in the graph 3 is a macroscopic morphology graph before electrode sintering, the middle graph is a macroscopic morphology graph after electrode sintering, the right graph is a microscopic morphology after electrode sintering, and the surface of the electrode presents certain metal luster after removing the oxide layer as can be seen in the graphs 1-3, and the scanning electron microscope result shows that the printed electrode microscopic morphology is mutually connected nano particles and the particle size is uniform. And the particle size was calculated, and as a result, see fig. 4, it can be seen from fig. 4 that the unmodified gallium indium alloy prepared in comparative example 1 had a particle size of about 1000nm after ultrasonic treatment, and that a larger particle size was also responsible for easy deposition, whereas the particle size of the liquid metal particles modified by the p-aniline derivative was mainly concentrated at 300nm, which indicates that the modification of the p-aniline derivative effectively suppressed the formation of the liquid metal oxide layer, resulting in a reduction in particle size.
The liquid ink prepared in step 6) in example 1 and the liquid metal ink prepared in step 7) in example 1 were left for one week and then were subjected to scanning electron microscopy, and the results are shown in fig. 5, wherein the left image in fig. 5 is a scanning electron microscopy image of the liquid ink prepared in step 6) in example 1, and the right image is a scanning electron microscopy image of the liquid metal ink prepared in freeze-dried after being left for one week, and as can be seen in fig. 5, the microscopic morphology of the freeze-dried liquid metal powder is not obviously different from that of the electrode printed in the ink form after being left for one week, and the particles are relatively uniform, so that the liquid metal ink can be stored as powder for a long time.
The liquid metal ink powder after lyophilization of 7) in example 1 was redissolved with absolute ethanol and deionized water, respectively, and it was observed whether the conductivity stability before and after storage was changed, and as a result, see fig. 6, it can be seen from fig. 6 that the liquid metal ink powder after lyophilization shows similar conductivity to the liquid metal ink powder before lyophilization in both absolute ethanol and deionized water, and shows further improvement in conductivity in aqueous solution, which indicates that the liquid metal ink does not have a great influence on its performance when stored as powder, and the improvement in conductivity of aqueous solution provides a theoretical basis for the novel liquid metal ink using water as a carrier.
Physical and chemical property detection of liquid metal ink:
1. and (3) adhesiveness detection:
the effect of the modifying molecule on contact angle was measured using a JC2000D1 type contact angle meter (Powereach, shanghai). Dispensing 10 μl of the liquid ink prepared in step 6) of example 1 and 10 μl of the unmodified liquid metal ink prepared in comparative example 1 onto two glass slides; placing the slide in an oven at 37 ℃ for 10 minutes to ensure that the sample is completely dry and a film forms on the slide; then, 2. Mu.L of water drop was dropped on the film by an instrument, and the contact angle was collected, and the result was shown in FIG. 7. As can be seen from fig. 7, the contact angle (contact angle is 24 °) of the liquid ink prepared in step 6) in example 1 is reduced compared to the unmodified liquid metal ink prepared in comparative example 1, i.e., the liquid ink exhibits better adhesion after modification of the aniline derivative.
2. And (3) conductivity detection:
electrochemical measurements were performed under the CHI660E system (CH Instruments, inc., shanghai). The reference electrode is an Ag/AgCl electrode, the counter electrode is a Pt electrode, and the working electrode is a GC disk electrode with the diameter of 3 mm. Preparing dry Buehler alumina and Milli-Q waterThe electrode was polished continuously on a micro-cloth pad (Buehler, lake blue, IL). The electrodes were rinsed thoroughly with Milli-Q water and sonicated in Milli-Q water for 1 minute after polishing. All potentials were compared to a silver/silver chloride reference electrode at room temperature. Will contain 0.1M K 3 Fe(CN) 6 、0.1M K 4 Fe(CN) 6 And 0.1M KCl in PBS was used as the electrolyte solution for EIS measurement, and CV was scanned from-0.3V to 1.5V at room temperature. To demonstrate its conductivity, the procedure of example 1 was followed except that other para-aniline derivatives (para-aminothiophenol (PATI), para-phenylene diamine (PPD) and para-bromophenol (PBA)) were modified to demonstrate its enhanced liquid metal conductivity, as shown in FIG. 8. As can be seen from fig. 8, the liquid metal inks all showed good conductivity after various para-aniline derivative modifications, wherein the PDD modified liquid metal inks showed significant conductivity enhancement.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the invention, but any modifications, equivalents, improvements, etc. within the principles of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method of preparing printable liquid metal ink, comprising the steps of:
1) Placing gallium-indium alloy in hydrochloric acid, covering the gallium-indium alloy with hydrochloric acid, and incubating overnight to obtain a liquid metal solution;
2) Washing the liquid metal solution obtained in the step 1) with absolute ethyl alcohol, adding p-aniline derivatives and nanoclay, and mixing until the liquid metal solution is dissolved to obtain a mixture;
3) Performing ultrasonic modification on the mixture obtained in the step 2) by using an ultrasonic cell disruption instrument to obtain liquid metal nano particles;
4) Washing the liquid metal nano particles obtained in the step 3) with water to obtain a high-concentration liquid metal solution;
5) Dissolving polyethylene copolymer in water to obtain an ink carrier;
6) Resuspending the high concentration liquid metal solution obtained in step 4) with deionized water, and then mixing with the ink vehicle obtained in step 5) to obtain the liquid metal ink.
2. The method for preparing liquid metal ink according to claim 1, wherein the working frequency of the ultrasonic modification in the step 3) is 30%, the ultrasonic switch is circularly performed for 2s and 2s, and the reaction time is 90-120min.
3. The method for preparing liquid metal ink according to claim 1, wherein after adding p-aniline derivative and nanoclay in step 2), the content of the gallium indium alloy is 90 to 95wt%, the content of the p-aniline derivative is 4 to 9wt%, and the content of the nanoclay is 0 to 1wt%.
4. The method for preparing liquid metal ink according to claim 3, wherein after adding p-aniline derivative and nanoclay in step 2), the content of the gallium-indium alloy is 92 to 95wt%, the content of the p-aniline derivative is 7 to 9wt%, and the content of the nanoclay is 0.5 to 1wt%.
5. The method for preparing liquid metal ink according to claim 1, wherein the para-aniline derivative is any one or a combination of several of para-aminothiophenol, para-aminobenzoic acid, para-phenylenediamine and para-bromophenol.
6. The method of preparing a liquid metal ink of claim 1, wherein the concentration of hydrochloric acid in step 1) is 0.5M.
7. The method for preparing liquid metal ink according to claim 1, wherein the polyethylene-based copolymer of step 5) is any one of polyvinyl alcohol, polyvinylpyrrolidone and polyethyleneimine.
8. A printable liquid metal ink produced by the production process of any one of claims 1 to 7.
9. A flexible wearable biosensor comprising the printable liquid metal ink of claim 8.
10. Use of a printable liquid metal ink according to claim 8 in the printing of a functional surface, wherein the surface is any one of an electrode, a microfluidic channel, a hydrogel and glass.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107452436A (en) * | 2017-07-04 | 2017-12-08 | 云南科威液态金属谷研发有限公司 | A kind of liquid metal electric slurry and preparation method thereof |
| CN110240830A (en) * | 2018-03-09 | 2019-09-17 | 国家纳米科学中心 | The conductive ink of sintering certainly, preparation method and application based on liquid metal particle |
| CN112538290A (en) * | 2020-10-19 | 2021-03-23 | 浙江大学 | Self-sintering liquid metal ink and preparation method and application thereof |
| US20230159771A1 (en) * | 2021-01-14 | 2023-05-25 | Korea Advanced Institute Of Science And Technology | Method of manufacturing non-sintered liquid metal ink |
-
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- 2023-06-28 CN CN202310774259.0A patent/CN116694141A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107452436A (en) * | 2017-07-04 | 2017-12-08 | 云南科威液态金属谷研发有限公司 | A kind of liquid metal electric slurry and preparation method thereof |
| CN110240830A (en) * | 2018-03-09 | 2019-09-17 | 国家纳米科学中心 | The conductive ink of sintering certainly, preparation method and application based on liquid metal particle |
| CN112538290A (en) * | 2020-10-19 | 2021-03-23 | 浙江大学 | Self-sintering liquid metal ink and preparation method and application thereof |
| US20230159771A1 (en) * | 2021-01-14 | 2023-05-25 | Korea Advanced Institute Of Science And Technology | Method of manufacturing non-sintered liquid metal ink |
Non-Patent Citations (1)
| Title |
|---|
| 于馨等: "单宁酸修饰镓铟合金导电油墨的制备及性能研究", 北京服装学院学报, vol. 42, no. 2, 30 June 2022 (2022-06-30), pages 21 - 26 * |
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