Functional ink suitable for 3D printing and preparation method thereof

Abstract

A functional ink suitable for 3D printing and a preparation method thereof are provided. The ink includes the following components in parts by weight: 0.5-1.5 parts of a regulator, 1-5 parts of a conductive material, 0.1-0.5 parts of a crosslinking agent, 0.1-0.5 parts of a catalyst, and 10-80 parts of a solvent. The prepared functional ink has a self-healing function at room temperature, eliminating the interface resistance between printing layers and improving the mechanical strength between the layers. Moreover, the prepared functional ink has excellent electrical conductivity and a variety of electrical, magnetic, and electrochemical properties, and can be applied in the fields of functional materials and devices such as energy storage, electromagnetic shielding and stress sensing.

Claims

1. A functional ink suitable for 3D printing, comprising the following components in parts by weight: 0.5-1.5 parts of a regulator, 1-5 parts of a conductive material, 0.1-0.5 parts of a crosslinking agent, 0.1-0.5 parts of a catalyst, and 10-80 parts of a solvent; wherein the regulator provides a reversible dynamic intermolecular interaction or a reversible dynamic intramolecular interaction at room temperature; the regulator is at least one selected from the group consisting of chitosan, polyvinyl alcohol, nanocellulose, polyethylene glycol, catechin and tannic acid; the crosslinking agent is one selected from the group consisting of polymaleic acid, citric acid, propane-1,2,3-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, glutaraldehyde, and borate; the catalyst is one selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, phosphomolybdic acid, potassium bisulfate, aluminum chloride, ferric chloride, sodium bisulfate, sodium hypophosphite, sodium acetate, aluminium oxide, silicon dioxide, zinc oxide and titanium dioxide; and wherein the reversible dynamic intermolecular interaction or the reversible dynamic intramolecular interaction is one selected from the group consisting of covalent bonds, hydrogen bonds, and ion coordination bonds.

2. The functional ink according to claim 1, further comprising 0-10 parts of a functional nanomaterial.

3. The functional ink according to claim 1, wherein the conductive material is one selected from the group consisting of a conductive carbon material, a conductive polymer and a conductive metal particle.

4. The functional ink according to claim 2, wherein the functional nanomaterial is at least one selected from the group consisting of a metal oxide, a metal sulfide, a transition metal carbide, a transition metal nitride, an inorganic nonmetallic element, a redox small molecule, a phosphate and a titanate, wherein the metal oxide, the metal sulfide, the transition metal carbide, the transition metal nitride, the inorganic nonmetallic element, the redox small molecule, the phosphate and the titanate have electricity and magnetism properties.

5. The functional ink according to claim 4, wherein the functional nanomaterial is at least one selected from the group consisting of SnO.sub.2, Fe.sub.3O.sub.4, MnO.sub.2, MoS.sub.2, SnS.sub.2, MXenes, TiNx, MoNx, Si, Sn, Viologen, LiFePO.sub.4 and Li.sub.4T.sub.15O.sub.12.

6. A preparation method of the functional ink suitable for the 3D printing comprising the following steps: providing a functional ink suitable for 3D printing, comprising the following components in parts by weight: 0.5-1.5 parts of a regulator, 1-5 parts of a conductive material, 0.1-0.5 parts of a crosslinking agent, 0.1-0.5 parts of a catalyst, and 10-80 parts of a solvent; wherein the regulator provides a reversible dynamic intermolecular interaction or a reversible dynamic intramolecular interaction at room temperature; the regulator is at least one selected from the group consisting of chitosan, polyvinyl alcohol, nanocellulose, polyethylene glycol, catechin and tannic acid; the crosslinking agent is one selected from the group consisting of polymaleic acid, citric acid, propane-1,2,3-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, glutaraldehyde, and borate; the catalyst is one selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, phosphomolybdic acid, potassium bisulfate, aluminum chloride, ferric chloride, sodium bisulfate, sodium hypophosphite, sodium acetate, aluminium oxide, silicon dioxide, zinc oxide and titanium dioxide; and under conditions of 20-35° C. and 8000-30000 r/min, mixing the components, and stirring the components for 20-60 min according to a formulation.

7. The functional ink according to claim 2, wherein the conductive material is one selected from the group consisting of a conductive carbon material, a conductive polymer and a conductive metal particle.

8. The preparation method according to claim 6, wherein the functional ink further comprises 0-10 parts of a functional nanomaterial.

9. The preparation method according to claim 6, wherein the reversible dynamic intermolecular interaction or the reversible dynamic intramolecular interaction is one selected from the group consisting of covalent bonds, hydrogen bonds and ion coordination bonds.

10. The preparation method according to claim 6, wherein the conductive material is one selected from the group consisting of a conductive carbon material, a conductive polymer and a conductive metal particle.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGS. 1A-1F are diagrams demonstrating the self-healing ability for the restoration of mechanical properties and electrical conductivity of a functional ink; where, FIG. 1A is a digital image of a sample subjected to cutting; FIG. 1B is a digital image of it after self-healing; FIG. 1C is is a photo showing functional ink stretching after self-healing to illustrate the robustness of the healed interface; FIG. 1D is a digital image demonstrating the electrical conductivity of the functional ink before the cutting; FIG. 1E is a digital image showing the interface created after cutting reflected by the LED light turned off; and FIG. 1F demonstrates the healed interface and restored electrical conductivity of the functional ink after the self-healing;

(2) FIGS. 2A-2H are images captured from an optical microscope showing the dynamic evolution of the healing interface of the incision made on the functional ink; where, FIG. 2A is an image showing the original sample before the cutting; FIG. 2B is an image showing the incision after the cutting; FIG. 2C shows the sample under healing for 0 s; FIG. 2D shows the sample under-healing for 2 s; FIG. 2E shows the sample under healing for 4 s; FIG. 2F shows the sample under healing for 6 s; FIG. 2G shows the sample under healing for 10 s; and FIG. 2H shows the sample under healing for 20 s;

(3) FIG. 3 is a diagram showing cyclic stability test results of a 3D printed supercapacitor prepared in embodiment 1;

(4) FIGS. 4A-4B are diagrams showing electrochemical performance test results of a 3D printed LiFePO.sub.4lithium-ion battery cathode material prepared in embodiment 2; where, FIG. 4A is a diagram showing a cyclic voltammetry curve of a printed sample at a scanning rate of 0.1 mV/S; and FIG. 4B is a diagram showing a charge/discharge curve of the printed sample at a current density of 100 mA/g;

(5) FIGS. 5A-5B are diagrams showing performance test results of 3D printed electromagnetic shielding samples prepared in embodiment 3; where, FIG. 5A is a diagram showing shielding effect of printed samples with thickness of 0.22 mm and 0.8 mm; and FIG. 5B is a diagram showing an absorption rate curve of a 0.22 mm 3D printed sample at a frequency of 8-12 GHz;

(6) FIG. 6 is a diagram showing a resistance change of a 3D printed stress sensor prepared in embodiment 4 under different compression conditions;

(7) FIG. 7 is a diagram showing a charge/discharge curve of a 3D printed MoS.sub.2 lithium-ion battery anode material prepared in embodiment 5 at a current density of 200 mA/g;

(8) FIG. 8 is a diagram showing a charge/discharge curve of a 3D printed SnO.sub.2 lithium-ion battery anode material prepared in embodiment 6 at a current density of 100 mA/g.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(9) The specific embodiments of the present invention are described below to facilitate those skilled in the art to understand the present invention. However, it should be clear that the present invention is not limited to the scope of specific embodiments. For those ordinarily skilled in the art, these modifications are obvious as long as various modifications are made within the spirit and scope of the present invention as defined and determined by claims, and all inventions and creations utilizing the concepts of the present invention shall fall into the protection scope.

Embodiment 1

(10) A functional ink suitable for 3D printing includes the following components in parts by weight:

(11) 0.6 parts of tannic acid, 1 part of graphene, 0.2 parts of polymaleic acid, 0.2 parts of ferric chloride, and 30 parts of deionized water.

(12) A preparation method of the functional ink is as follows: mixing the above-mentioned components, stirring for 30 min at 25° C. and 20000 r/min to obtain the functional ink.

(13) Performance tests are performed on the prepared functional ink, and test results are shown in FIGS. 1A-1F and FIGS. 2A-2H.

(14) FIGS. 1A-1F and FIGS. 2A-2H are the test results showing the self-healing performance of the prepared functional ink at room temperature. According to the test results in FIGS. 1A-1F and FIGS. 2A-2H, the functional ink prepared by the present invention rapidly completes self-healing that restores mechanical properties and electrical conductivity within 4 s at room temperature, indicating that the functional ink has excellent self-healing performance.

(15) A method of the 3D printing with the functional ink includes the following steps.

(16) (1) The prepared functional ink is housed in a syringe barrel, the ink is extruded from a needle with a diameter of 0.10 mm under a pneumatic pressure of 12 Psi provided from an air-powered dispenser, and the printing is performed at a speed of 6 mm/s according to a preset program to obtain a product with different layers.

(17) (2) The product obtained in step (1) is heated at 170° C. for 45 min, washed with deionized water for several times, and then dried in a vacuum oven at 80° C. for 24 h to obtain a printed sample.

(18) A three-electrode system is adopted to test the capacitance performance of the printed sample, where,

(19) the printed sample is a working electrode, a saturated calomel electrode is a reference electrode, a platinum electrode is a counter electrode, an electrolyte is 1 M sulfuric acid solution, a potential is 0-0.9 V.

(20) FIG. 3 shows a capacity measurement of the prepared printed sample; the printed sample prepared by the present invention maintains more than 90% of the reversible capacity after 5000 cycles; it should be mentioned that, with the increase of printing layers, the gravimetric capacitance of the printed electrode basically remains unchanged, which is otherwise subject to obvious degradation without proper coalescence of the interface. As a result, the areal capacitance of the printed electrodes manage to increase linearly. Therefore, the functional ink prepared by the method of the present invention may be applied to the preparation of a high-performance supercapacitor by 3D printing.

Embodiment 2

(21) A functional ink suitable for 3D printing includes the following components in parts by weight:

(22) 0.8 parts of polyvinyl alcohol, 1 part of a single-walled carbon nanotube, 0.3 parts of borate, 0.3 parts of sulfuric acid, 8 parts of lithium iron phosphate, and 40 parts of deionized water.

(23) A preparation method of the functional ink is as follows: mixing the above-mentioned components, stirring for 45 min at 35° C. and 30000 r/min to obtain the functional ink.

(24) A method of the 3D printing with the functional ink includes the following steps.

(25) (1) The prepared functional ink is housed in a syringe barrel, the ink is extruded from a needle with a diameter of 0.10 mm under a pneumatic pressure of 18 Psi provided from an air-powered dispenser, and the printing is performed at a speed of 8 mm/s according to a preset program.

(26) (2) The product obtained in step (1) is heated at 120° C. for 55 min, washed with deionized water for several times, and then dried in a vacuum oven at 60° C. for 20 h to obtain a printed sample.

(27) The electrochemical performance of a lithium-ion battery of the printed sample is tested:

(28) The printed sample is a working electrode, lithium is a counter electrode, an electrolyte is 1 mol/L lithium hexafluorophosphate, a solvent is a mixture of ethylene carbonate and dimethyl carbonate at a volume ratio of 1:1, a testing potential is 2.5-4.5 V; a scanning rate of a cyclic voltammetry test is 0.1 mV/s, a current density of a constant current charge/discharge test is 100 mA/g, and the results are shown in FIGS. 4A-B.

(29) As mentioned above, the prepared functional ink has a good electrical conductivity and good self-healing performance, and the functional ink allows for continuous and consistent 3D printing at room temperature. As shown in FIGS. 4A-B, FIG. 4A shows typical oxidation and reduction peaks of the electrochemically active material (i.e., lithium iron phosphate) at 3.75 V and 3.25 V of the printed sample prepared by 3D printing at the scanning rate of 0.1 mV/s; FIG. 4B shows that after several cycles of charging/discharging, the coulomb efficiency of the battery electrode is substantially improved, and the electrode provides approximately 150 mAh/g reversible capacity close to theoretical capacity. Therefore, the printed sample prepared by the present invention has excellent electrochemical performance, and the functional ink prepared by the method of the present invention may be applied to the preparation of the lithium-ion battery cathode by 3D printing.

Embodiment 3

(30) A functional ink suitable for 3D printing includes the following components in parts by weight:

(31) 0.8 parts of nanocellulose, 2 parts of poly (3,4-ethylenedioxythiophene), 0.25 parts of propane-1,2,3-tricarboxylic acid, 0.25 parts of sodium hypophosphite, and 50 parts of deionized water.

(32) A preparation method of the functional ink is as follows: mixing the above-mentioned components, stirring for 50 min at 30° C. and 15000 r/min to obtain the functional ink.

(33) A method of 3D printing with the functional ink includes the following steps.

(34) (1)The prepared functional ink is housed in a syringe barrel, the ink is extruded from a needle with a diameter of 0.80 mm under a pneumatic pressure of 15 Psi provided from an air-powered dispenser, and the printing is performed at a speed of 7 mm/s according to a preset program to obtain products with different layers.

(35) (2) The products obtained in step (1) are heated at 150° C. for 50 min, washed with deionized water for several times, and then dried in a vacuum oven at 60° C. for 24 h to obtain printed samples.

(36) A vector network analyzer and a transmission line method are adopted to test the performance of the printed samples, and the results are shown in FIGS. 5A-B.

(37) As mentioned above, the prepared functional ink has a good electrical conductivity and good self-healing performance, and the functional ink allows for continuous and consistent 3D printing at room temperature. As shown in FIGS. 5A-B, FIG. 5A shows that the printed samples with thickness of 0.22 mm and 0.8 mm achieve shielding effectiveness of approximately −60 dB and −70 dB in a range of 8-12 GHz, respectively, when the electromagnetic wave frequency is above 10 GHz, the absorption rate is more than 91% (referring to FIG. 5B). Therefore, the functional ink prepared by the present invention gives the printed samples excellent electromagnetic wave shielding performance and may be applied to the preparation of electromagnetic shielding functional devices.

Embodiment 4

(38) A functional ink suitable for 3D printing includes the following components in parts by weight:

(39) 1.5 parts of catechin, 1.5 parts of silver particles, 0.5 parts of glutaraldehyde, 0.5 parts of hydrochloric acid, and 66.7 parts of ethanol.

(40) A preparation method of the functional ink is as follows: mixing the above-mentioned components, stirring for 40 min at 25° C. and 10000 r/min to obtain the functional ink.

(41) A method of 3D printing with the functional ink includes the following steps.

(42) (1) The prepared functional ink is housed in a syringe barrel, the ink is extruded from a needle with a diameter of 0.60 mm under a pneumatic pressure of 10 Psi provided from an air-powered dispenser, and the printing is performed at a speed of 5 mm/s according to a preset program to obtain a product with different layers.

(43) (2) The product obtained in step (1) is heated at 120° C. for 40 min, washed with deionized water for several times, and then dried in a vacuum oven at 85° C. for 21 h to obtain a printed sample.

(44) The prepared printed sample is embedded in Ecoflex, cured at room temperature for 3 h, then packaged, and the resistance changes under different compression conditions are detected, and the results are shown in FIG. 6.

(45) As mentioned above, the prepared functional ink has a good electrical conductivity and good self-healing performance, and the functional ink allows for continuous and consistent 3D printing at room temperature. The 3D printed sample has a sensitive stress sensing characteristic, and its resistance change is shown in FIG. 6, compression is repeated for 10 times and the resistance is measured for each time. During the cycle, the resistance decreases during compression and achieves stable recovery after stress relaxation. Therefore, the functional ink prepared by the present invention has an excellent stress sensing characteristic, and can be applied to the preparation of a stress sensor.

Embodiment 5

(46) A functional ink suitable for 3D printing includes the following components in parts by weight:

(47) 0.6 parts of chitosan, 3 parts of reduced graphene oxide, 0.4 parts of butane-1,2,3,4-tetracarboxylic acid, 0.4 parts of sodium acetate, 7 parts of molybdenum disulfide, and 60 parts of acetic acid.

(48) The above-mentioned components are mixed, following by stirring for 35 min at 30° C. and 25000 r/min to obtain the functional ink.

(49) A method of 3D printing with the functional ink includes the following steps.

(50) (1) The prepared functional ink is housed in a syringe barrel, the ink is extruded from a needle with a diameter of 0.10 mm under a pneumatic pressure of 20 Psi provided from an air-powered dispenser, and the printing is performed at a speed of 10 mm/s according to a preset program.

(51) (2) The product obtained in step (1) is heated at 180° C. for 50 min, washed with deionized water for several times, and then dried in a vacuum oven at 80° C. for 24 h to obtain a printed sample.

(52) The electrochemical performance of a lithium-ion battery of the printed sample is tested:

(53) The printed sample is a working electrode, lithium is a counter electrode, an electrolyte is 1 mol/L lithium hexafluorophosphate, a solvent is a mixture of ethylene carbonate and dimethyl carbonate at a volume ratio of 1:1, a testing potential is 0.01-3 V; a current density of a constant current charge/discharge test is 200 mA/g, and the results are shown in FIG. 7.

(54) As mentioned above, the prepared functional ink has a good electrical conductivity and good self-healing performance, and the functional ink allows for continuous and consistent 3D printing at room temperature. As shown in FIG. 7, the printed sample prepared by the 3D printing provides approximately 650 mAh/g reversible capacity after a first cycle, indicating that the printed sample prepared by the present invention has excellent electrochemical performance, and the functional ink prepared by the method of the present invention may be applied to the preparation of the lithium-ion battery anode by 3D printing.

Embodiment 6

(55) A functional ink suitable for 3D printing includes the following components in parts by weight:

(56) 1.2 parts of polyethylene glycol, 4 parts of a multi-walled carbon nanotube, 0.5 parts of citric acid, 0.5 parts of phosphomolybdic acid, 9 parts of tin dioxide, and 70 parts of ethanol.

(57) The above-mentioned components are mixed, followed by stirring for 50 min at 30° C. and 22000 r/min to obtain the functional ink.

(58) A method of 3D printing with the functional ink includes the following steps.

(59) (1) The prepared functional ink is housed in a syringe barrel, the ink is extruded from a needle with a diameter of 0.10 mm under a pneumatic pressure of 16 Psi provided from an air-powered dispenser, and the printing is performed at a speed of 8 mm/s according to a preset program.

(60) (2) The product obtained in step (1) is heated at 160° C. for 60 min, washed with deionized water for several times, and then dried in a vacuum oven at 70° C. for 22 h to obtain a printed sample.

(61) The electrochemical performance as a lithium-ion battery anode of the printed sample is tested:

(62) the printed sample is a working electrode, lithium is a counter electrode, an electrolyte is 1 mol/L lithium hexafluorophosphate, a solvent is a mixture of ethylene carbonate and dimethyl carbonate at a volume ratio of 1:1, a testing potential is 0.01-3 V; a current density of a constant current charge/discharge test is 100 mA/g, and the results are shown in FIG. 8.

(63) As mentioned above, the prepared functional ink has a good electrical conductivity and good self-healing performance, and the functional ink allows for continuous and consistent 3D printing at room temperature. As shown in FIG. 8, the coulomb efficiency of the printed sample prepared by 3D printing is greatly improved after a first cycle, and the electrode maintain approximately approximately 500 mAh/g reversible capacity after 5 cycles, indicating that the printed sample prepared by the present invention has excellent electrochemical performance, and the functional ink prepared by the method of the present invention may be applied to the preparation of the lithium-ion battery anode by the 3D printing.