A method of 3D printing a three-dimensional aerogel

Abstract

The application discloses a method for 3D printing three-dimensional aerogel, and belongs to the technical field of 3D printing and controllable preparation of conductive polymer PEDOT:PSS. The method uses a PEDOT:PS aqueous solution as raw material, and realizes 3D printing of PEDOT:PSS by adopting a solidification bath auxiliary mode. The preparation method has the advantages of simple equipment, convenient operation, mild conditions, low cost and easy process amplification, and the prepared three-dimensional PEDOT:PSS has high quality and good performance, and has important application prospects in the fields of super capacitors, lithium batteries and sensors.

Description

Technical Field

[0001] This invention relates to a method for 3D printing three-dimensional aerogels, and particularly to a technique for the controllable preparation of polymeric PEDOT:PSS aerogels. The prepared PEDOT:PSS aerogels exhibit high quality and good performance, and have significant application prospects in fields such as supercapacitors, lithium batteries, and sensors. Background Technology

[0002] Existing methods for 3D printing conductive polymer PEDOT:PSS involve freeze-drying a commercially available PEDOT:PSS solution, then dispersing it in a mixture of dimethyl sulfoxide and water (DMSO:H2O volume ratio 85:15) to form a high-concentration 3D printing ink, which is then directly printed using an extrusion 3D printer. This method can only print high-concentration 3D printing ink and cannot achieve the printing of low-concentration PEDOT:PSS aerogels. Summary of the Invention

[0003] The purpose of this invention is to provide a method for 3D printing conductive polymer PEDOT:PSS. This method can directly generate three-dimensional PEDOT:PSS of various shapes from computer graphics data without the need for machining or any molds, thereby greatly improving productivity and reducing production costs. Compared with traditional technologies, it reduces costs by eliminating the production line and significantly reduces material waste.

[0004] Another objective of this invention is to provide a method for preparing PEDOT:PSS aerogel, which uses a low-concentration PEDOT:PSS aqueous solution as a raw material to achieve additive manufacturing of PEDOT:PSS aerogel.

[0005] The technical problem solved by this invention is achieved by the following technical solution.

[0006] This invention provides a method for 3D printing three-dimensional aerogels. The printing method involves placing the extrusion component of a 3D printer in a coagulation bath during printing. After the raw material liquid is extruded through the extrusion component of the 3D printer, it enters the coagulation bath to form the aerogel, which is then freeze-dried to obtain the three-dimensional aerogel. The raw material liquid contains 0.5–100 mg / mL of a conductive polymer. The coagulation bath contains a hydrophobic substance, and the density of the coagulation bath is less than or equal to 0.80 g / cm³ and less than or equal to 1 g / cm³. 3 .

[0007] Optionally, the solidification bath has a solidification point of <5°C.

[0008] Optionally, the hydrophobic substance is a hydrophobic lipid.

[0009] Optionally, the volume content of the hydrophobic substance in the coagulation bath is 50% to 100%;

[0010] Optionally, the hydrophobic lipid is selected from at least one of phenyl acetate, methyl benzoate, butyl acetate, and ethyl acetate.

[0011] Optionally, the coagulation bath may also contain an organic solvent.

[0012] Optionally, the volume content of the organic solvent in the coagulation bath is 15% to 50%;

[0013] Optionally, the organic solvent is selected from alkane solvents and / or ether solvents;

[0014] Optionally, the alkane solvent is cyclohexane;

[0015] Optionally, the ether solvent is selected from at least one of diethyl ether and petroleum ether.

[0016] Optionally, the conductive polymer is 3,4-ethylenedioxythiophene / polystyrene sulfonate (PEDOT:PSS); the ratio of PEDOT to PSS is 1:10 to 10:1.

[0017] Optionally, the solvent in the raw material liquid is water.

[0018] Optionally, the raw material liquid also contains graphene oxide.

[0019] Optionally, the freezing method includes, but is not limited to, liquid nitrogen freezing or refrigerator freezing.

[0020] Optionally, the PEDOT:PSS can be either self-synthesized or can be a commercially available product.

[0021] Optionally, the solvent in the raw material liquid is pure water, and other solvents may be added as needed.

[0022] Optionally, other active substances with good water dispersibility may be added to the raw material liquid, including but not limited to aqueous solutions of graphene oxide.

[0023] The beneficial effects of this invention are as follows: This invention combines a hydrophobic coagulation bath with 3D printing, enabling not only the printing of high-concentration PEDOT:PSS but also the 3D printing of low-concentration PEDOT:PSS aerogels. It eliminates the need for cumbersome 3D printing ink preparation processes such as concentration and redispersion; commercially available PEDOT:PSS aqueous solutions can be used directly for 3D printing. This printing method is particularly suitable for directly preparing conductive aerogels of various shapes from low-concentration PEDOT:PSS aqueous solutions through 3D printing. Attached Figure Description

[0024] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0025] Figure 1 This is an optical magnified image of the three-dimensional PEDOT:PSS mesh printed according to Embodiment 1 of the present invention.

[0026] Figure 2 This is a physical image of a single three-dimensional PEDOT:PSS supercapacitor electrode printed according to Embodiment 2 of the present invention;

[0027] Figure 3 This is a physical image of multiple three-dimensional PEDOT:PSS supercapacitor electrodes connected in parallel, printed according to Embodiment 3 of the present invention.

[0028] Figure 4 This is a physical image of multiple three-dimensional PEDOT:PSS supercapacitor electrodes connected in series, printed according to Embodiment 4 of the present invention.

[0029] Figure 5 The image shown is a three-dimensional PEDOT:PSS base grid scanning electron microscope image printed according to Embodiment 5 of the present invention.

[0030] Figure 6 The image shown is a three-dimensional PEDOT:PSS base grid scanning electron microscope image printed according to Embodiment 6 of the present invention. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0032] In one embodiment, the present invention uses PEDOT:PSS aqueous solution as raw material and uses an extrusion 3D printer to directly extrude the raw material into a suitable coagulation bath. 3D printing is completed by means of coagulation bath assistance. After printing, freeze drying is performed to obtain three-dimensional PEDOT:PSS.

[0033] Example 1

[0034] Using a 10 mg / ml PEDOT:PSS aqueous solution as raw material and a mixed solution of phenyl acetate and diethyl ether (volume ratio 5:1) as a coagulation bath, 50 ml of the above coagulation bath was added to a flat-bottomed glass disc. The probe of an extrusion 3D printer was inserted into the coagulation bath to a suitable depth, and the designed grid pattern was input into the 3D printer for printing. After printing, the sample was frozen at -20 degrees Celsius for 5 hours, and then freeze-dried to obtain the desired product. Figure 1 The sample in.

[0035] from Figure 1 As can be seen, this method successfully printed the three-dimensional PEDOT:PSS grid structure.

[0036] Example 2

[0037] Using a 5 mg / ml PEDOT:PSS aqueous solution as raw material and a mixed solution of methyl benzoate and cyclohexane (volume ratio 4:1) as a coagulation bath, 50 ml of the above coagulation bath was added to a flat-bottomed glass disk with a PET substrate of appropriate size. The probe of an extrusion 3D printer was inserted into the coagulation bath to a suitable depth, and the designed single planar supercapacitor electrode pattern was input into the 3D printer for printing. After printing, the sample was frozen in a freezer at -20 degrees Celsius for 5 hours, and then freeze-dried to obtain the desired product. Figure 2 The sample in.

[0038] from Figure 2 As can be seen, this method successfully printed a single three-dimensional PEDOT:PSS supercapacitor electrode pattern.

[0039] Example 3

[0040] Using a 20 mg / ml PEDOT:PSS aqueous solution as raw material, and a mixed solution of butyl acetate, ethyl acetate, and cyclohexane (volume ratio 4:1:1) as a coagulation bath, 80 ml of the above coagulation bath was added to a flat-bottomed glass disk with a PET substrate of appropriate size. The probe of an extrusion 3D printer was inserted into the coagulation bath to a suitable depth, and the designed parallel electrode pattern of multiple planar supercapacitors was input into the 3D printer for printing. After printing, the mixture was rapidly frozen using liquid nitrogen and then freeze-dried to obtain the desired product. Figure 3 The sample in.

[0041] from Figure 3 As can be seen, this method successfully printed multiple three-dimensional PEDOT:PSS supercapacitor parallel electrode patterns.

[0042] Example 4

[0043] Using a 1 mg / ml PEDOT:PSS aqueous solution as raw material and a 1:1 (volume ratio) mixture of octyl acrylate and ethyl acetate as a coagulation bath, 70 ml of the coagulation bath was added to a flat-bottomed glass disk with a PET substrate of appropriate size. The probe of an extrusion 3D printer was inserted into the coagulation bath to a suitable depth, and the designed series-connected electrode pattern of multiple planar supercapacitors was input into the 3D printer for printing. After printing, the mixture was rapidly frozen using liquid nitrogen and then freeze-dried to obtain the desired product. Figure 4 The sample in.

[0044] from Figure 4 As can be seen, this method successfully printed multiple three-dimensional PEDOT:PSS supercapacitor series electrode patterns.

[0045] Example 5

[0046] A 10 mg / ml PEDOT:PSS aqueous solution was mixed evenly with an equal volume of 1 mg / ml graphene oxide as the raw material. Using pure ethyl acetate as the coagulation bath, 50 ml of the coagulation bath was added to a flat-bottomed glass disk. The probe of an extrusion 3D printer was inserted into the coagulation bath to a suitable depth, and the designed grid pattern was input into the 3D printer for printing. After printing, the sample was frozen at -20 degrees Celsius for 5 hours, and then freeze-dried to obtain a scanning electron microscope image. Figure 5 The sample in.

[0047] from Figure 5 As can be seen, this method yielded a two-layer mesh structure based on three-dimensional PEDOT:PSS.

[0048] Example 6

[0049] A 10 mg / ml PEDOT:PSS aqueous solution was mixed with an equal volume of 2 mg / ml electrochemically exfoliated graphene as the raw material. A coagulation bath of ethyl acetate and petroleum ether (volume ratio 1:1) was used. 60 ml of this coagulation bath was added to a flat-bottomed glass disk. The probe of an extrusion 3D printer was inserted to a suitable depth into the coagulation bath, and the designed grid pattern was input into the 3D printer for printing. After printing, the image was rapidly frozen in liquid nitrogen and then freeze-dried to obtain a scanning electron microscope image. Figure 1 The sample in.

[0050] from Figure 6 As can be seen, this method yielded a three-dimensional PEDOT:PSS-based multilayer mesh structure.

[0051] The embodiments described above are some, but not all, embodiments of the present invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

Claims

1. A method for 3D printing three-dimensional aerogel, characterized in that, The printing method involves placing the extrusion part of the 3D printer in a solidification bath during printing; After the raw material liquid is extruded through the extrusion part of the 3D printer, it enters the coagulation bath for molding and is then freeze-dried to obtain the three-dimensional aerogel. The raw material solution contains 0.5~100 mg / mL of conductive polymer; the conductive polymer is 3,4-ethylenedioxythiophene:polystyrene sulfonate in a ratio of 1:10~10:

1. The solidification bath has a solidification point of <5℃, contains hydrophobic substances, and has a density of 0.80 g / cm³ ≤ <1 g / cm³.

2. The method for 3D printing three-dimensional aerogel according to claim 1, characterized in that, The hydrophobic substance is a hydrophobic lipid; The volume content of hydrophobic substances in the coagulation bath is 50% to 100%. The hydrophobic lipids are selected from at least one of phenyl acetate, methyl benzoate, butyl acetate, and ethyl acetate.

3. The method for 3D printing three-dimensional aerogel according to claim 1, characterized in that, The coagulation bath also contains organic solvents; The volume content of the organic solvent in the coagulation bath is 15% to 50%; The organic solvent is selected from alkane solvents and / or ether solvents; The alkane solvent is cyclohexane; The ether solvent is selected from at least one of diethyl ether and petroleum ether.

4. The method for 3D printing three-dimensional aerogel according to claim 1, characterized in that, The solvent in the raw material liquid is water.

5. The method for 3D printing three-dimensional aerogel according to claim 1, characterized in that, The raw material liquid also contains graphene oxide.

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