WO2020147567A1 - 一种适用于3d打印的功能墨水及其制备方法 - Google Patents

一种适用于3d打印的功能墨水及其制备方法 Download PDF

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WO2020147567A1
WO2020147567A1 PCT/CN2019/129799 CN2019129799W WO2020147567A1 WO 2020147567 A1 WO2020147567 A1 WO 2020147567A1 CN 2019129799 W CN2019129799 W CN 2019129799W WO 2020147567 A1 WO2020147567 A1 WO 2020147567A1
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functional ink
parts
functional
printing
ink suitable
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PCT/CN2019/129799
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English (en)
French (fr)
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张楚虹
康文彬
曾丽
凌尚文
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四川大学
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Priority to US17/420,722 priority Critical patent/US11530331B2/en
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    • 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
    • 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
    • B33Y70/00—Materials specially adapted for 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
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/21—Ink jet for multi-colour printing
    • B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
    • 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
    • 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
    • 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
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • 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
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • 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
    • C09D11/08—Printing inks based on natural resins
    • 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
    • C09D11/10—Printing inks based on artificial resins
    • 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
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C09D11/14—Printing inks based on carbohydrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • 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
    • B33Y80/00—Products made by additive manufacturing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of 3D printing, and specifically relates to a functional ink suitable for 3D printing and a preparation method thereof.
  • 3D printing technology also known as additive manufacturing technology, is a method that is diametrically opposed to traditional material processing methods. It is based on 3D model data and is manufactured layer by layer by adding materials. Its advantage is that it can be constructed with any specified shape. The complex structure realizes the rapid and efficient molding of the three-dimensional structure. Due to its unique characteristics of dimensionality reduction and rapid layer-by-layer processing, 3D printing offers unlimited possibilities for next-generation manufacturing technology and is a frontier development direction supported by the national "13th Five-Year Plan". 3D printing technology has developed rapidly in the preparation of structural materials in recent years, but it is difficult to make breakthroughs in the application of processing functional devices with special properties.
  • Direct ink writing technology has the advantages of wide selection of printing materials, room temperature printing, simple process, low cost, etc., and it is a 3D printing processing technology with great application potential that can be used to prepare complex functional devices.
  • the functional ink is the key to determining its processability and the final performance of the printed functional device, and it is also the biggest difficulty in the direct ink writing 3D printing process.
  • the current publicly available technology for preparing 3D printable functional inks has the following problems: 1. It is difficult to prepare a 3D printable conductive ink with uniform composition; 2. The content of active substances in the ink is low, and the performance of the printed molding device is poor; 3. Layer by layer printing The interlayer force is weak, the interface resistance is large, and the device performance decays rapidly as the number of layers increases.
  • the present invention provides a functional ink suitable for 3D printing and a preparation method thereof, which can effectively solve the problem that the existing ink does not have a self-healing function at room temperature, and the mechanical properties of printed products are poor. , The problem of large interface resistance.
  • a functional ink suitable for 3D printing including the following components by weight:
  • the polymer regulator can provide reversible dynamic interactions between molecules or within molecules at room temperature.
  • the reversible dynamic interaction is realized by a reversible dynamic bond
  • the reversible dynamic bond is a covalent bond, a hydrogen bond or an ionic coordination bond.
  • the polymer regulator is one or more of chitosan, polyvinyl alcohol, nanocellulose, polyethylene glycol, catechin, or tannic acid.
  • the conductive material is a conductive carbon material, a conductive polymer, or a conductive metal particle.
  • crosslinking agent is polymaleic acid, citric acid, 1,2,3-tricarboxylic acid propane, 1,2,3,4-tetracarboxylic butane, glutaraldehyde or borate.
  • the catalyst is sulfuric acid, hydrochloric acid, phosphoric acid, phosphomolybdic acid, potassium hydrogen sulfate, aluminum chloride, ferric chloride, sodium hydrogen sulfate, sodium hypophosphite, sodium acetate, aluminum oxide, silicon dioxide, zinc oxide or titanium dioxide.
  • functional nanomaterials are metal oxides, metal sulfides, transition metal carbides, transition metal nitrides, inorganic non-metallic elements, small molecules with redox properties, phosphates or titanates with different functions such as electricity and magnetism.
  • metal oxides metal sulfides, transition metal carbides, transition metal nitrides, inorganic non-metallic elements, small molecules with redox properties, phosphates or titanates with different functions such as electricity and magnetism.
  • the functional nanomaterial is one of SnO 2 , Fe 3 O 4 , MnO 2 , MoS 2 , SnS 2 , MXenes, TiNx, MoNx, Si, Sn, Viologen, LiFePO 4 or Li 4 Ti 5 O 12 or Many kinds.
  • the solvent is water, ionic liquid, acetic acid, urea, thiourea, N,N-dimethylacetamide, dimethylsulfoxide, dimethylacetamide or N-methylmorphine .
  • the above-mentioned preparation method of functional ink suitable for 3D printing includes the following steps:
  • step (2) Heat the product obtained in step (1) for 30-100 minutes at 120-200°C, then wash the sample and dry it at 50-100°C for 12-30 hours.
  • step (2) is 40-60 min.
  • drying temperature in step (2) is 60-90°C; the drying time is 20-24h.
  • the ink prepared by the invention has a self-healing function at room temperature. Therefore, during 3D printing, the spontaneous self-healing effect of the ink at room temperature can eliminate the interface resistance between the printing layers, increase the interaction force between the layers, and effectively improve the pass
  • the electrical, magnetic and electrochemical properties of the functional device prepared by the ink printing can eliminate the interface resistance between the printing layers, increase the interaction force between the layers, and effectively improve the pass.
  • the cross-linking reaction between the polymer chains in the formula is promoted to improve the mechanical stability of the printed product.
  • the ink prepared by the present invention has excellent conductivity, self-repair and multiple functions, and can be widely used in the fields of energy storage, electromagnetic shielding, stress sensing and other functional devices.
  • Figure 1 is a self-healing test diagram of the mechanical properties and electrical conductivity of the functional ink; among them, Figure 1a is a schematic diagram after cutting; Figure 1b is a schematic diagram after self-healing healing; Figure 1c is a schematic diagram of functional ink stretching after self-healing healing Figure 1d is the conductivity detection diagram of the functional ink when it is not cut; Figure 1e is the conductivity detection diagram of the functional ink after cutting; Figure 1f is the conductivity detection diagram of the functional ink after self-healing;
  • Figure 2 is a dynamic evolution of the healing effect of functional ink incision light microscope; among them, Figure 2a is the uncut detection image; Figure 2b is the detection image after cutting; Figure 2c is the detection image when healing 0s; Figure 2d is the healing image Figure 2e is the detection diagram at 4s; Figure 2f is the detection diagram at 6s; Figure 2c is the detection diagram at 10s; Figure 2h is the detection diagram at 20s;
  • FIG. 3 is a diagram of the cycle stability test results of the 3D printed supercapacitor prepared in Example 1;
  • Figure 4 is a graph showing the electrochemical performance test results of the 3D printed LiFePO 4 lithium ion battery cathode material prepared in Example 2.
  • Figure 4a is the cyclic voltammetry curve of the printed sample at a scanning rate of 0.1mV/s;
  • Figure 4b is the printing The charge and discharge curve of the sample at a current density of 100mA/g;
  • Figure 5 is the performance test results of the 3D printed electromagnetic shielding samples prepared in Example 3; among them, Figure 5a is the shielding effect test of the printed samples with thicknesses of 0.22mm and 0.8mm; Figure 5b is the 0.22mm 3D printed samples 8-12GHz frequency Lower absorption curve;
  • Example 6 is a schematic diagram of resistance changes of the 3D printed stress sensor prepared in Example 4 under different compression conditions
  • FIG. 7 is a charge and discharge curve of the 3D printed MoS 2 lithium ion battery negative electrode material prepared in Example 5 at a current density of 200 mA/g;
  • Example 8 is a charge-discharge curve of the 3D printed SnO 2 lithium ion battery negative electrode material prepared in Example 6 at a current density of 100 mA/g.
  • a functional ink suitable for 3D printing including the following components by weight:
  • the preparation method of the above functional ink the above components are mixed, and then stirred for 30 minutes under the conditions of 25° C. and 20000 r/min to prepare the functional ink.
  • FIGS. 1 and 2 are the self-repairing performance test results of the prepared functional ink at room temperature. According to the test results of Figs. 1a ⁇ f and 2a ⁇ h, it can be seen that the functional ink prepared by the present invention is within 4s at room temperature. It can quickly complete the self-repair of mechanical properties and electrical conductivity, indicating that it has excellent self-repair properties.
  • the method of 3D printing using this functional ink includes the following steps:
  • step (2) Heat the sample obtained in step (1) at 170°C for 45 minutes, wash it with deionized water several times, and then dry it in a vacuum oven at 80°C for 24 hours to obtain a printed sample.
  • a three-electrode system was used to test the capacitance performance of the printed samples prepared above, where:
  • the printed sample is the working electrode, the saturated calomel electrode is the reference electrode, the platinum electrode is the counter electrode, the electrolyte is 1M sulfuric acid solution, and the potential is 0-0.9V;
  • Figure 3 shows the capacity detection of the printed sample prepared by the present invention.
  • the printed sample prepared by the present invention can maintain a reversible capacity greater than 90% after 5000 cycles; and more importantly, as the number of printed layers increases, the printed electrode weight ratio The capacity remains basically unchanged but the area specific capacity increases linearly. This indicates that the functional ink prepared by the method of the present invention can be used for the preparation of supercapacitors through 3D printing.
  • a functional ink suitable for 3D printing including the following components by weight:
  • the method for preparing the above functional ink includes the following steps:
  • the method of 3D printing using this functional ink includes the following steps:
  • step (2) Heat the sample obtained in step (1) at 120°C for 55 minutes, wash it with deionized water several times, and then dry it in a vacuum oven at 60°C for 20 hours to obtain a printed sample.
  • the printed sample is the working electrode, lithium is the counter electrode, the electrolyte is 1mol/L lithium hexafluorophosphate, the solvent is ethylene carbonate: dimethyl carbonate with a volume ratio of 1:1, and the test potential is 2.5-4.5V; cyclic voltammetry tested The scan rate is 0.1mV/s, and the current density of the constant current charge and discharge test is 100mA/g. The results are shown in Figure 4.
  • the prepared functional ink has good conductivity and self-healing properties, and can be continuously and stably 3D printed at room temperature; as shown in Figure 4, Figure 4a shows the printed sample prepared by 3D printing at 0.1mV/s scanning The typical oxidation and reduction peaks of electrochemically active material lithium iron phosphate appear at 3.75V and 3.25V, respectively; Figure 4b shows that after multiple cycles of charge and discharge, the coulombic efficiency of the battery is greatly improved and can provide approximately 150mAh/g close to the theoretical capacity Reversible capacity; indicates 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 can be used for the preparation of lithium-ion batteries through 3D printing.
  • a functional ink suitable for 3D printing including the following components by weight:
  • the method for preparing the above functional ink includes the following steps:
  • the method of 3D printing using this functional ink includes the following steps:
  • step (2) Heat the sample obtained in step (1) at 150°C for 50 minutes, wash it with deionized water several times, and then dry it in a vacuum oven at 60°C for 24 hours to obtain a printed sample.
  • the prepared functional ink has good conductivity and self-healing properties, and can be continuously and stably 3D printed at room temperature; as shown in Figure 5, Figure 5a shows the printed samples with thicknesses of 0.22mm and 0.8mm in 8 The shielding effectiveness of about -60dB and -70dB can be achieved in the range of ⁇ 12GHz, respectively. When the electromagnetic wave frequency is above 10GHz, the absorption rate exceeds 91% (see Figure 5b). This shows that the functional ink prepared by the present invention has The printed sample has excellent electromagnetic wave shielding performance and can be used for the preparation of electromagnetic shielding functional devices.
  • a functional ink suitable for 3D printing including the following components by weight:
  • the method for preparing the above functional ink includes the following steps:
  • the method of 3D printing using this functional ink includes the following steps:
  • step (2) Heat the sample obtained in step (1) at 120°C for 40 minutes, wash it with deionized water several times, and then dry it in a vacuum oven at 85°C for 21 hours to obtain a printed sample.
  • the prepared functional ink has good electrical conductivity and self-healing properties, and can be continuously and stably 3D printed at room temperature; 3D printed samples have sensitive low-pressure stress induction characteristics, and their resistance changes are shown in Figure 6, repeated compression 10 And measure the resistance of each time. During the cycle, the resistance shows a decreasing trend during compression and realizes a stable recovery after stress relaxation. This shows that the functional ink prepared by the present invention has excellent stress sensing characteristics and can be used To stabilize the intensity of the stress received by the sensitive indicator, which can be used to prepare a stress sensor.
  • a functional ink suitable for 3D printing including the following components by weight:
  • chitosan 3 parts by weight of reduced graphene oxide, 0.4 parts by weight of 1,2,3,4-tetracarboxylic butane, 0.4 parts by weight of sodium acetate, 7 parts of molybdenum disulfide, and 60 parts by weight of acetic acid.
  • the above components are mixed, and then stirred for 35 minutes under the conditions of 30°C and 25000 r/min to prepare the functional ink.
  • the method of 3D printing using this functional ink includes the following steps:
  • step (2) Heat the sample obtained in step (1) at 180°C for 50 minutes, wash it with deionized water several times, and then dry it in a vacuum oven at 80°C for 24 hours to obtain a printed sample.
  • the printed sample is the working electrode, lithium is the counter electrode, the electrolyte is 1mol/L lithium hexafluorophosphate, the solvent is ethylene carbonate: dimethyl carbonate with a volume ratio of 1:1, and the test potential is 0.01-3V; constant current charge and discharge test The current density is 200 mA/g, and the result is shown in Figure 7.
  • the prepared functional ink has good conductivity and self-healing properties, and can be continuously and stably 3D printed at room temperature; as shown in Figure 7, the printed sample prepared by 3D printing can provide about 650mAh after the first week of circulation
  • the reversible capacity of /g indicates 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 can be used for the preparation of lithium ion batteries by means of 3D printing.
  • a functional ink suitable for 3D printing including the following components by weight:
  • the method of 3D printing using this functional ink includes the following steps:
  • step (2) Heat the sample obtained in step (1) at 160°C for 60 minutes, wash it with deionized water several times, and then dry it in a vacuum oven at 70°C for 22 hours to obtain a printed sample.
  • the printed sample is the working electrode, lithium is the counter electrode, the electrolyte is 1mol/L lithium hexafluorophosphate, the solvent is ethylene carbonate: dimethyl carbonate with a volume ratio of 1:1, and the test potential is 0.01-3V; constant current charge and discharge test The current density is 100mA/g.
  • the result is shown in Figure 8.
  • the prepared functional ink has good conductivity and self-healing properties, and can be continuously and stably 3D printed at room temperature; as shown in Figure 8, the coulombic efficiency of the printed sample prepared by 3D printing is greatly improved after the first week of circulation. And maintained a reversible capacity of about 500mAh/g after 5 weeks of circulation, indicating that the printed samples prepared by the present invention have excellent electrochemical performance, and the functional ink prepared by the method of the present invention can be used for lithium ion by 3D printing. Preparation of batteries.

Abstract

一种适用于3D打印的功能墨水及其制备方法。该墨水包括以下重量份的组分：高分子调节剂0.5～1.5份、导电材料1～5份、交联剂0.1～0.5份、催化剂0.1～0.5份，以及溶剂10～80份。制备得到的功能墨水在室温下具有自修复功能，可消除打印层间界面电阻，提高层间力学强度，且具有优良的导电性和多种电、磁、电化学性能，可用于储能、电磁屏蔽、应力传感等功能材料和器件领域。

Description

一种适用于3D打印的功能墨水及其制备方法 技术领域
本发明属于3D打印技术领域，具体涉及一种适用于3D打印的功能墨水及其制备方法。
背景技术
3D打印技术，又称增材制造(additive manufacturing)技术，是一种与传统材料加工方法截然相反的、基于三维模型数据、通过增加材料逐层制造的方式，其优势在于可以构筑具有任意指定形状的复杂结构，实现立体结构的快速、高效成型。由于其独特的降维、快速逐层加工特性，3D打印为下一代制造技术提供了无限可能，是国家“十三五规划纲要”重点扶持的前沿发展方向。3D打印技术近年来在结构材料制备方面发展迅速，然而在加工具有特殊性能的功能器件的应用上却难有突破。只能打印形状、难打印功能是3D打印行业急需解决的世界性难题。现有3D打印技术主要包括熔融沉积成型(Fused Deposition Modeling，FDM)、选择性激光烧结(Selective Laser Melting，SLM)、立体平板印刷(Stereolithography，SLA)和直接油墨书写(Direct Ink Writing，DIW)等。直接油墨书写技术因具备打印材料选择广、可室温打印、工艺简便、成本低廉等优点，是一种极具应用潜力的可用于制备复杂功能器件的3D打印加工技术。而功能墨水是决定其加工性和打印功能器件最终性能的关键，也是直接墨水书写式3D打印加工工艺的最大难点。
目前制备可3D打印功能墨水现有公开技术存在以下问题：1.制备可3D打印的成分均匀的导电墨水难度大；2.墨水中活性物质含量低，打印成型器件性能差；3.逐层打印层间作用力弱，界面电阻大，器件性能随层数增加迅速衰减。
发明内容
针对现有技术中的上述不足，本发明提供一种适用于3D打印的功能墨水及其制备方法，可有效解决现有墨水在室温下不具备自修复功能，打印得到的产品层间力学性能差、界面电阻大的问题。
为实现上述目的，本发明解决其技术问题所采用的技术方案是：
一种适用于3D打印的功能墨水，包括以下重量份的组分：
高分子调节剂0.5～1.5份、导电材料1～5份、交联剂0.1～0.5份、催化剂0.1～0.5份，以及溶剂10～80份；
所述高分子调节剂能够在室温下提供分子间或分子内可逆动态相互作用。
进一步地，还包括功能纳米材料0～10份。
进一步地，可逆动态相互作用是通过可逆动态键来实现的，该可逆动态键为共价键、氢键或离子配位键。
进一步地，高分子调节剂为壳聚糖、聚乙烯醇、纳米纤维素类、聚乙二醇、儿茶素或单宁酸中的一种或多种。
进一步地，导电材料为导电碳材料、导电高分子或导电金属颗粒。
进一步地，交联剂为聚马来酸、柠檬酸、1,2,3-三羧酸丙烷、1,2,3,4-四羧酸丁烷、戊二醛或硼酸盐。
进一步地，催化剂为硫酸、盐酸、磷酸、磷钼酸、硫酸氢钾、氯化铝、氯化铁、硫酸氢钠、次磷酸钠、醋酸钠、氧化铝、二氧化硅、氧化锌或二氧化钛。
进一步地，功能纳米材料为具有电、磁等不同功能的金属氧化物、金属硫化物、过渡金属碳化物、过渡金属氮化物、无机非金属单质、氧化还原属性小分子、磷酸盐或钛酸盐中的一种或多种。
进一步地，功能纳米材料为SnO 2、Fe 3O 4、MnO 2、MoS 2、SnS 2、MXenes、TiNx、MoNx、Si、Sn、Viologen、LiFePO 4或Li 4Ti 5O 12中的一种或多种。
进一步地，溶剂为水、离子液体、乙酸、尿素类、硫脲类、N,N-二甲基乙酰胺类、二甲基亚砜类、二甲基乙酰胺类或N-甲基吗啡类。
上述适用于3D打印的功能墨水的制备方法，包括以下步骤：
在20～35℃、8000～30000r/min的条件下，按配方将各组分混合搅拌20～60min即可。
采用该适用于3D打印的功能墨水进行3D打印的具体过程为：
(1)将制备得到的功能墨水装入3D打印机中的气动式喷射阀中，然后以5～10mm/s的速度运行点胶机；
(2)于120～200℃的条件下，加热步骤(1)所得产物30～100min，然后洗涤样品后在50～100℃的条件下干燥12～30h即可。
进一步地，步骤(2)中加热时间为40～60min。
进一步地，步骤(2)中干燥温度为60～90℃；干燥时间为20～24h。
本发明的有益效果为：
1、在配方中添加有在室温下能提供分子间或分子内可逆动态相互作用的高分子调节剂，该高分子调节剂在室温下即可发生可逆成键反应或分子间动态相互作用，使得本发明制备得到的墨水在室温下即具有自修复功能，由此，在进行3D打印时，通过墨水室温自发自修复作用可消除打印层间界面电阻，增大层间相互作用力，有效提升了通过该墨水打印制备得到的功能器件的电、磁和电化学等性能。
2、在交联剂的作用下，促使配方中的高分子链间发生交联反应，提升打印制品的机械稳定性。
3、根据所要制备的产品的实际需求，选择不同性质的功能纳米材料，能够制备得到具有不同功能和用途的功能墨水。
4、本发明制备得到的墨水具有优良的导电性、自修复性和多种功能性，可广泛用于储能、电磁屏蔽、应力传感等功能器件领域。
附图说明
图1为功能墨水的机械性能和导电性能的自修复测试图；其中，图1a为切割后的示意图；图1b为自修复愈合后的示意图；图1c为自修复愈合后的功能墨水拉伸示意图；图1d为未切割时功能墨水的导电性能检测图；图1e为切割后的功能墨水的导电性能检测图；图1f为自修复愈合后的功能墨水的导电性能检测图；
图2为功能墨水切口愈合效果的动态演变光镜图；其中，图2a为未切割时的检测图；图2b为切割后的检测图；图2c为愈合0s时的检测图；图2d为愈合2s时的检测图；图2e为愈合4s时的检测图；图2f为愈合6s时的检测图；图2c为愈合10s时的检测图；图2h为愈合20s时的检测图；
图3为实施例1制备得到的3D打印超级电容器的循环稳定性检测结果图；
图4为实施例2制备得到的3D打印LiFePO 4锂离子电池正极材料电化学性能检测结果图；其中，图4a为打印样品在0.1mV/s扫描速率下的循环伏安曲线；图4b为打印样品在100mA/g电流密度下充放电曲线；
图5为实施例3制备得到的3D打印电磁屏蔽样品性能检测结果；其中，图5a为厚度为0.22mm和0.8mm的打印样品屏蔽效果检测图；图5b为0.22mm 3D打印样品8-12GHz频率下吸收率曲线；
图6为实施例4制备得到的3D打印应力传感器在不同压缩条件下的电阻变化示意图；
图7为实施例5制备得到的3D打印MoS 2锂离子电池负极材料在200mA/g电流密度下充放电曲线；
图8为实施例6制备得到的3D打印SnO 2锂离子电池负极材料在100mA/g电流密度下充放电曲线。
具体实施方式
下面对本发明的具体实施方式进行描述，以便于本技术领域的技术人员理解本发明，但应该清楚，本发明不限于具体实施方式的范围，对本技术领域的普通技术人员来讲，只要各种变化在所附的权利要求限定和确定的本发明的精神和范围内，这些变化是显而易见的，一切利用本发明构思的发明创造均在保护之列。
实施例1
一种适用于3D打印的功能墨水，包括以下重量份的组分：
单宁酸0.6份、石墨烯1份、聚马来酸0.2份、氯化铁0.2以及去离子水30份。
上述功能墨水的制备方法：将上述组分混合，然后在25℃、20000r/min的条件下，搅拌30min，即可制备得到功能墨水。
对制备得到的功能墨水进行性能检测，其检测结果见图1～2；
其中，图1和图2为制备得到的功能墨水在室温下的自修复性能检测结果，通过图1a～f和图2a～h的检测结果可知，本发明制备得到的功能墨水在室温下4s内即可迅速完成机械性能和导电性能的自修复，表明其具有优异的自修复性能。
采用该功能墨水进行3D打印的方法，包括以下步骤：
(1)将制备得到的功能墨水装入气动式喷射阀中，墨水在胶阀控制器提供的12Psi压力下从直径为0.10mm的针头中挤出，在点胶机上以6mm/s的速度按照预设的程序进行打印，得到不同层数的产物；
(2)于170℃加热步骤(1)所得样品45min，并用去离子水洗涤多次，然后再在80℃的真空烘箱中干燥24h即可得打印样品。
采用三电极体系测试上述制备得到的打印样品的电容性能，其中：
打印样品为工作电极，饱和甘汞电极为参比电极，铂电极为对电极，电解液为1M硫酸溶液，电位为0-0.9V；
图3为制备得到的打印样品容量检测，本发明制备得到的打印样品可在5000次循环后保持大于90％的可逆容量；而更为重要的是，随着打印层数增加，打印电极重量比容量基本保持不变但是面积比容量线性增加。由此表明，通过本发明方法制备的功能墨水能够通过3D打印的方式用于进行超级电容器的制备。
实施例2
一种适用于3D打印的功能墨水，包括以下重量份的组分：
聚乙烯醇0.8份、单壁碳纳米管1份、硼酸盐0.3份、二氧化钛0.3份、磷酸铁锂8份，以及去离子水40份。
上述功能墨水的制备方法，包括以下步骤：
将上述组分混合，然后在35℃、30000r/min的条件下，搅拌45min，即可制备得到功能墨水。
采用该功能墨水进行3D打印的方法，包括以下步骤：
(1)将制备得到的功能墨水装入气动式喷射阀中，墨水在胶阀控制器提供的18Psi压力下从直径为0.10mm的针头中挤出，在点胶机上以8mm/s的速度按照预设的程序进行打印；
(2)于120℃加热步骤(1)所得样品55min，并用去离子水洗涤多次，然后再在60℃的真空烘箱中干燥20h即可得打印样品。
检测打印样品的锂离子电池电化学性能：
打印样品为工作电极，锂为对电极，电解液为1mol/L六氟磷酸锂，溶剂为体积比为1：1的碳酸乙烯酯：碳酸二甲酯，测试电位为2.5-4.5V；循环伏安测试的扫描速率为0.1mV/s，恒电流充放电测试的电流密度为100mA/g，其结果见图4。
如前所述，制备功能墨水具有良好的导电性和自修复性能，可在室温下连续稳定3D打印；如图4所示，图4a为通过3D打印制备得到的打印样品在0.1mV/s扫描速率下分别于3.75V与3.25V出现电化学活性物质磷酸铁锂典型的氧化与还原峰；图4b为经过多周充放电循环，电池库仑效率大幅提升并可提供接近理论容量的约150mAh/g可逆容量；表明通过本发明制备得到的打印样品具有优异的电化学性能，通过本发明方法制备的功能墨水能够通过3D打印的方式用于进行锂离子电池的制备。
实施例3
一种适用于3D打印的功能墨水，包括以下重量份的组分：
纳米纤维素0.8份、聚(3,4-乙烯二氧噻吩)2份、1,2,3-三羧酸丙烷0.25份、次磷酸钠0.25份，以及去离子水50份。
上述功能墨水的制备方法，包括以下步骤：
将上述组分混合，然后在30℃、15000r/min的条件下，搅拌50min，即可制备得到功能墨水。
采用该功能墨水进行3D打印的方法，包括以下步骤：
(1)将制备得到的功能墨水装入气动式喷射阀中，墨水在胶阀控制器提供的15Psi压力下从直径为0.80mm的针头中挤出，在点胶机上以7mm/s的速度按照预设的程序进行打印，得到不同层数的样品；
(2)于150℃加热步骤(1)所得样品50min，并用去离子水洗涤多次，然 后再在60℃的真空烘箱中干燥24h即可得打印样品。
利用矢量网络分析仪，采用传输线法测量打印样品性能，其结果见图5。
如前所述，制备功能墨水具有良好的导电性和自修复性能，可在室温下连续稳定3D打印；如图5所示，其中，图5a为厚度为0.22mm和0.8mm的打印样品在8～12GHz范围内可分别实现约-60dB和-70dB的屏蔽效能，当电磁波频率在10GHz以上时，吸收率超过91％(见图5b)，由此说明，本发明制备得到的功能墨水，赋予了打印样品优良的电磁波屏蔽性能，能够用于电磁屏蔽功能器件的制备。
实施例4
一种适用于3D打印的功能墨水，包括以下重量份的组分：
儿茶素1.5份、银1.5份、戊二醛0.5份、盐酸0.5份，以及乙醇66.7份。
上述功能墨水的制备方法，包括以下步骤：
将上述组分混合，然后在25℃、10000r/min的条件下，搅拌40min，即可制备得到功能墨水。
采用该功能墨水进行3D打印的方法，包括以下步骤：
(1)将制备得到的功能墨水装入气动式喷射阀中，墨水在胶阀控制器提供的10Psi压力下从直径为0.60mm的针头中挤出，在点胶机上以5mm/s的速度按照预设的程序进行打印，得到不同层数的样品；
(2)于120℃加热步骤(1)所得样品40min，并用去离子水洗涤多次，然后再在85℃的真空烘箱中干燥21h即可得打印样品。
将制备得到的打印样品嵌入Ecoflex中，在室温下固化3h，然后进行封装，并检测不同压缩条件下的电阻变化，其结果见图6。
如前所述，制备功能墨水具有良好的导电性和自修复性能，可在室温下连 续稳定3D打印；3D打印样品具有敏感的低压应力感应特征，其电阻变化如图6所示，重复压缩10次并测量每一次的电阻，循环周期内，电阻在压缩时呈降低趋势，并在应力松弛后实现稳定回复，由此表明，本发明制备得到的功能墨水具有优良的应力传感特征，可以用来稳定敏感指示受到的应力强度，能够用于制备应力传感器。
实施例5
一种适用于3D打印的功能墨水，包括以下重量份的组分：
壳聚糖0.6重量份，还原氧化石墨烯3重量份，1,2,3,4-四羧酸丁烷0.4重量份，醋酸钠0.4重量份，二硫化钼7份，乙酸60重量份。
将上述组分混合，然后在30℃、25000r/min的条件下，搅拌35min，即可制备得到功能墨水。
采用该功能墨水进行3D打印的方法，包括以下步骤：
(1)将制备得到的功能墨水装入气动式喷射阀中，墨水在胶阀控制器提供的20Psi压力下从直径为0.10mm的针头中挤出，在点胶机上以10mm/s的速度按照预设的程序进行打印；
(2)于180℃加热步骤(1)所得样品50min，并用去离子水洗涤多次，然后再在80℃的真空烘箱中干燥24h即可得打印样品。
检测打印样品的锂离子电池电化学性能：
打印样品为工作电极，锂为对电极，电解液为1mol/L六氟磷酸锂，溶剂为体积比为1：1的碳酸乙烯酯：碳酸二甲酯，测试电位为0.01-3V；恒电流充放电测试的电流密度为200mA/g，其结果见图7。
如前所述，制备功能墨水具有良好的导电性和自修复性能，可在室温下连续稳定3D打印；如图7所示，通过3D打印制备得到的打印样品可在首周循环 后提供约650mAh/g的可逆容量，表明通过本发明制备得到的打印样品具有优异的电化学性能，通过本发明方法制备的功能墨水能够通过3D打印的方式用于进行锂离子电池的制备。
实施例6
一种适用于3D打印的功能墨水，包括以下重量份的组分：
聚乙二醇1.2份、多壁碳纳米管4份、柠檬酸0.5份、磷钼酸0.5份、二氧化锡9份，以及乙醇70份。
将上述组分混合，然后在30℃、22000r/min的条件下，搅拌50min，即可制备得到功能墨水。
采用该功能墨水进行3D打印的方法，包括以下步骤：
(1)将制备得到的功能墨水装入气动式喷射阀中，墨水在胶阀控制器提供的16Psi压力下从直径为0.10mm的针头中挤出，在点胶机上以8mm/s的速度按照预设的程序进行打印；
(2)于160℃加热步骤(1)所得样品60min，并用去离子水洗涤多次，然后再在70℃的真空烘箱中干燥22h即可得打印样品。
检测打印样品的锂离子电池电化学性能：
打印样品为工作电极，锂为对电极，电解液为1mol/L六氟磷酸锂，溶剂为体积比为1：1的碳酸乙烯酯：碳酸二甲酯，测试电位为0.01-3V；恒电流充放电测试的电流密度为100mA/g。其结果见图8。
如前所述，制备功能墨水具有良好的导电性和自修复性能，可在室温下连续稳定3D打印；如图8所示，通过3D打印制备得到的打印样品首周循环后库仑效率大幅提升，并在循环5周后维持约500mAh/g的可逆容量，表明通过本发明制备得到的打印样品具有优异的电化学性能，通过本发明方法制备的功能墨水能 够通过3D打印的方式用于进行锂离子电池的制备。

Claims (10)

  1. 一种适用于3D打印的功能墨水，其特征在于，包括以下重量份的组分：
    高分子调节剂0.5～1.5份、导电材料1～5份、交联剂0.1～0.5份、催化剂0.1～0.5份，以及溶剂10～80份；
    所述高分子调节剂能够在室温下提供分子间或分子内可逆动态相互作用。
  2. 根据权利要求1所述的适用于3D打印的功能墨水，其特征在于，还包括功能纳米材料0～10份。
  3. 根据权利要求1所述的适用于3D打印的功能墨水，其特征在于，所述可逆动态相互作用为共价键、氢键或离子配位键。
  4. 根据权利要求1或2所述的适用于3D打印的功能墨水，其特征在于，所述高分子调节剂为壳聚糖、聚乙烯醇、纳米纤维素类、聚乙二醇、儿茶素或单宁酸中的一种或多种。
  5. 根据权利要求1或2所述的适用于3D打印的功能墨水，其特征在于，所述导电材料为导电碳材料、导电高分子或导电金属颗粒。
  6. 根据权利要求1或2所述的适用于3D打印的功能墨水，其特征在于，所述交联剂为聚马来酸、柠檬酸、1,2,3-三羧酸丙烷、1,2,3,4-四羧酸丁烷、戊二醛或硼酸盐。
  7. 根据权利要求1或2所述的适用于3D打印的功能墨水，其特征在于，所述催化剂为硫酸、盐酸、磷酸、磷钼酸、硫酸氢钾、氯化铝、氯化铁、硫酸氢钠、次磷酸钠、醋酸钠、氧化铝、二氧化硅、氧化锌或二氧化钛。
  8. 根据权利要求2所述的适用于3D打印的功能墨水，其特征在于，所述功能纳米材料为具有电、磁性能的金属氧化物、金属硫化物、过渡金属碳化物、过渡金属氮化物、无机非金属单质、氧化还原属性小分子、磷酸盐或钛酸盐中的一种或多种。
  9. 根据权利要求8所述的适用于3D打印的功能墨水，其特征在于，所述功能纳米材料为SnO 2、Fe 3O 4、MnO 2、MoS 2、SnS 2、MXenes、TiNx、MoNx、Si、Sn、Viologen、LiFePO 4或Li 4Ti 5O 12中的一种或多种。
  10. 权利要求1～9任一项所述的适用于3D打印的功能墨水的制备方法，其特征在于，包括以下步骤：
    在20～35℃、8000～30000r/min的条件下，按配方将各组分混合搅拌20～60min即可。
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