CN115036518B - Miniature all-solid-state zinc-air battery and preparation method thereof - Google Patents

Miniature all-solid-state zinc-air battery and preparation method thereof Download PDF

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CN115036518B
CN115036518B CN202210747661.5A CN202210747661A CN115036518B CN 115036518 B CN115036518 B CN 115036518B CN 202210747661 A CN202210747661 A CN 202210747661A CN 115036518 B CN115036518 B CN 115036518B
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zinc
electrode
ink
air
printing
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CN115036518A (en
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孟垂舟
刘更升
候占瑞
李国显
禹伟
郭士杰
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Hebei University of Technology
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    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • 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
    • 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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • 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
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0433—Molding
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • 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
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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

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  • Manufacturing & Machinery (AREA)
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Abstract

The invention provides a miniature all-solid-state zinc-air battery and a preparation method thereof, wherein the preparation method comprises the steps of preparing 3D printing ink; and printing the 3D printing ink on a plane substrate through 3D printer parameters to sequentially obtain an air electrode, a zinc electrode and an injected gel electrolyte, printing each layer of the air electrode, performing first curing, printing each layer of the zinc electrode, performing second curing, performing freeze drying treatment on the air electrode and the zinc electrode, performing freeze crosslinking and electrolyte soaking treatment on the gel, and finally stacking to prepare the zinc-air battery. The invention develops printable ink of the air electrode, the zinc electrode and the electrolyte, so that 3D printing and manufacturing of the zinc-air battery are possible; the printed electrode is of an interdigital counter electrode structure design, is beneficial to miniature patterning preparation, is beneficial to quick reciprocation of ions in electrolyte between positive and negative electrodes, and can be stacked layer by layer as required.

Description

Miniature all-solid-state zinc-air battery and preparation method thereof
Technical Field
The invention belongs to the technical field of air batteries, and particularly relates to a miniature all-solid-state zinc-air battery and a preparation method thereof.
Background
With the rapid development of portable and wearable electronic products, the demand for light-weight, miniaturized, and compact energy devices is increasing. In recent years, micro energy storage devices have been developed, focusing mainly on supercapacitors and lithium ion batteries. However, due to the limitation of the energy storage mechanism, the energy density (300 Wh/kg) of the lithium ion battery still cannot meet the requirement of the electronic product on long endurance time. The metal-air battery takes metal as a negative electrode, takes matched salt or alkali solution as electrolyte, has a unique semi-open battery structure, can utilize air in the surrounding environment as positive electrode active material, does not occupy the volume and the mass of a battery body, and therefore has 4.5 times of energy density (1353 Wh/kg) of a lithium ion battery, and is considered as one of the best candidates of next-generation high-specific energy devices. Among them, zinc-air batteries are receiving increasing research attention due to the high abundance and low toxicity of negative metallic zinc. However, the miniaturization preparation of zinc-air batteries has challenges, which are mainly represented in several aspects of difficult realization of micro-processing of a solid-liquid-gas three-phase structure with extremely unique air, difficult encapsulation of strong alkaline corrosive electrolyte, and hydrophobic and breathable encapsulation requirements. Therefore, the miniaturization research and development of the zinc-air battery needs to be comprehensively considered from the aspects of electrode materials, electrode structures, electrolyte forms, device packaging and the like.
In recent years, gel electrolyte technology has been developed, and gel electrolyte does not flow, which is beneficial to realizing compact preparation of energy devices. Therefore, the all-solid-state zinc-air battery has two main structures, namely a sandwich structure and a fiber structure, wherein the air electrode and the zinc cathode are respectively attached to two sides of the gel electrolyte, the fiber-shaped zinc cathode is taken as the center, and the outer layer sequentially wraps the gel electrolyte and the air electrode. The sandwich type zinc-air battery has simple structure, and the fiber type zinc-air battery is slim and flexible. However, the two device forms described above are difficult to achieve miniaturized fabrication of the device and are difficult to continuously increase the energy density per unit area of the device.
In the face of challenges, the following design thought of microelectrodes can be adopted, the design of arranging positive and negative electrodes side by side in the same plane is beneficial to the manufacture of micro devices, the design of interdigital counter electrodes is beneficial to the rapid transfer of ions in electrolyte between two counter electrodes with short intervals, and the three-dimensional design of longitudinally improving the thickness of the electrodes is beneficial to improving the content of active substances in unit area. In terms of the preparation method, the patterning preparation of the in-plane interdigital microelectrode can be realized by the traditional methods of ink-based screen printing, mask-based etching micromachining, micro-fluidic injection based on micro-channels and the like. However, they cannot accumulate ultra-high thickness microelectrodes, which greatly limits further increases in the energy density of the micro-energy device. In recent years, 3D direct-writing printing technology has emerged as a revolutionary manufacturing method, which can print viscous ink directly on a planar substrate to write complex micro patterns based on design drawing input and digital programming programs, and has geometric controllability and process flexibility, and most importantly, can realize layer-by-layer printing stacking to prepare ultra-thick microelectrodes. However, no one has successfully realized 3D printed miniature zinc-air cells at present, and the challenge is the development of inks rich in nano-scale catalyst particles, zinc powder particles and strong alkaline electrolytes and the printing and shaping with high spatial resolution.
Disclosure of Invention
In view of the above, the present invention is directed to a miniature all-solid zinc-air battery and a method for manufacturing the same, which solve the above-mentioned problems in the prior art.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a miniature all-solid-state zinc-air battery comprises an air electrode, a zinc electrode and a gel electrolyte, wherein the air electrode and the zinc electrode are placed side by side in the same plane, the air electrode and the zinc electrode are in opposite interdigital structures, and the zinc-air battery is manufactured by utilizing a 3D printing technology.
The invention also provides a preparation method of the miniature all-solid-state zinc-air battery, which comprises the following steps of
Preparing 3D printing ink;
the 3D printing ink is respectively passed through a 3D printer according to 100-400 Kpa and the speed of 1-5 mm s -1 The parameters of the method are that an air electrode, a zinc electrode and an injected gel electrolyte are printed on a plane substrate in sequence, the air electrode is subjected to first solidification after each layer is printed, the zinc electrode is subjected to second solidification after each layer is printed, the air electrode and the zinc electrode are subjected to freeze drying treatment, gel is subjected to freeze crosslinking and electrolyte soaking treatment, and finally the zinc air battery is prepared by stacking.
Further, the 3D printing ink includes an air electrode ink, a zinc electrode ink, and a gel electrolyte ink.
Further, the air electrode ink comprises 18 to 45 weight percent of catalyst, 5 to 8 weight percent of conductive agent, 40 to 57 weight percent of solvent, 7 to 11 weight percent of binder, 1 to 2 weight percent of rheological agent, 1 to 2 weight percent of stabilizer and 1 to 2 weight percent of sacrificial agent;
the catalyst is cobaltosic oxide particles and RuO 2 、Pt/C、Pt/C-RuO 2 Or Pt/C-IrO 2 At least one of the conductive agent is at least one of graphene, conductive carbon black, acetylene black, carbon nano tube or carbon fiber, the solvent is at least one of dimethylformamide solution, dimethylacetamide, N-methylpyrrolidone, acetone or tetrahydrofuran, and the binder is poly (vinylidene fluoride-co-hexafluoropropylene) or celluloseAt least one of conductive rubber or epoxy resin, wherein the rheologic agent is fumed silica, the stabilizer is fatty acid zinc, and the sacrificial agent is at least one of sodium chloride, sodium carbonate or sodium bicarbonate.
Further, the zinc electrode ink comprises 31 to 58 weight percent of zinc powder, 4 to 6 weight percent of conductive agent, 30 to 50 weight percent of solvent, 3 to 5 weight percent of binder, 1 to 1.5 weight percent of rheological agent, 1 to 1.5 weight percent of stabilizer and 3 to 5 weight percent of molding reinforcing agent;
the conductive agent is at least one of conductive carbon black, graphene or acetylene black, carbon nano tubes and carbon fibers, the solvent is at least one of dimethylformamide solution, dimethylacetamide, N-methylpyrrolidone, acetone or tetrahydrofuran, the binder is at least one of poly (vinylidene fluoride-co-hexafluoropropylene), cellulose or conductive rubber, the rheologic agent is fumed silica, the stabilizer is fatty acid zinc, and the molding enhancer is thermoplastic polyurethane.
Further, the gel electrolyte ink comprises 8wt% of alkali, 5wt% of polymer, 51wt% of deionized water, 34wt% of water retention agent and 2wt% of corrosion inhibitor;
the alkali is at least one of potassium hydroxide or sodium hydroxide, the polymer is at least one of polyvinyl alcohol or polyacrylic acid, the water-retaining agent is tetraethylammonium hydroxide, MXene aqueous solution, or at least one of silicon dioxide, glycerol and ethylene glycol, and the corrosion inhibitor is tetrabutylammonium bromide.
Further, the first curing is pre-curing by spraying water spray after each layer is printed on the air electrode.
Further, the second curing is thermal curing, the time of the second curing is 10 minutes, and the temperature of the second curing is 30 ℃.
Further, the preparation process of the miniature all-solid-state zinc-air battery comprises the following steps:
(1) Placing the binder and the solvent into a beaker, and magnetically stirring for 2 hours at 85-95 ℃ until the binder and the solvent are completely dissolved; sequentially adding a catalyst and a conductive agent into the prepared solution, intensively mixing for 30 minutes at 3000rpm by a high-speed homogenizer, then adding a sacrificial agent, a rheological agent and a stabilizer, and continuously mixing for 30 minutes at 8000rpm at a high speed until uniform and viscous air electrode ink is obtained;
(2) Placing the binder, the molding enhancer and the solvent into a beaker, and magnetically stirring for 2 hours at 85-95 ℃ until the binder, the molding enhancer and the solvent are completely dissolved; sequentially adding zinc powder and a conductive agent into the prepared solution, intensively mixing for 30 minutes at 3000rpm by a high-speed homogenizer, then adding a rheological agent and a stabilizer, and continuously mixing for 30 minutes at 8000rpm at a high speed until uniform and viscous zinc electrode ink is obtained;
(3) Placing deionized water, polyvinyl alcohol, tetraethylammonium hydroxide and MXene aqueous solution into a beaker, magnetically stirring for 1 hour at 85-95 ℃ until the deionized water, the polyvinyl alcohol, the tetraethylammonium hydroxide and the MXene aqueous solution are completely dissolved, adding corrosion inhibitor and alkali, and continuously stirring for 30 minutes until the corrosion inhibitor and the alkali are completely dissolved to obtain gel electrolyte ink;
(4) Before printing, respectively filling air electrode ink, zinc electrode ink, silicone rubber and gel electrolyte ink into a 4mL polypropylene injector with a nozzle, then printing the air electrode with designed interdigital patterns and the zinc electrode on a PET film after plasma cleaning one by using a flexible electronic printer in an automatic mode controlled by a computer, wherein the air electrode is sprayed with water and spray for pre-curing, the zinc electrode is heated and pre-cured, then printing the next layer, and finally placing the printed interdigital electrode in a freeze dryer, and freeze drying for 40 minutes at the temperature of minus 40 ℃ to minus 70 ℃;
(5) Placing the freeze-dried interdigital electrode back into a printer, printing a square silicon rubber frame around the effective interdigital electrode area, standing the printed silicon rubber frame at room temperature overnight, printing gel electrolyte ink to fill gaps between interdigital electrodes in the silicon rubber frame, freezing and crosslinking the printed gel electrolyte at-30 to-40 ℃ for 12 hours, finally soaking the whole device in 1M potassium hydroxide aqueous solution for 30 minutes until sodium chloride is completely dissolved in an air electrode, and forming the solid zinc-air microbattery with the porous three-dimensional interdigital structure.
Compared with the prior art, the miniature all-solid-state zinc-air battery and the preparation method thereof have the following advantages:
(1) The invention develops printable ink of the air electrode, the zinc electrode and the electrolyte, so that 3D printing for manufacturing the zinc-air battery is possible, and the printed air electrode has a porous structure, thereby being beneficial to the occurrence of solid-liquid-gas three-phase reaction;
(2) The printed electrode is of an interdigital counter electrode structure design, so that miniature patterning preparation is facilitated, ions in electrolyte can rapidly reciprocate between positive and negative electrodes, the printed electrodes can be stacked layer by layer as required, the active electrode substance content in unit area is improved, the unit area energy of a battery is improved, the 3D printing technology has the advantages of accurate and controllable and batch preparation, and devices with different shapes and sizes are printed according to the design and are connected for use.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a schematic illustration of a flow chart of ink formulation according to the present invention;
FIG. 2 is a schematic diagram of a printing flow of a zinc-air cell according to the present invention;
FIG. 3 is a schematic diagram of the operation of the zinc-air cell of the present invention;
FIG. 4 is a schematic illustration of the batch production and partial characterization of zinc-air cells of the present invention;
FIG. 5 is a schematic diagram of the printed fabrication of the interdigitated microelectrode of the present invention with different layers to demonstrate an ultra-thick cell;
FIG. 6 is a schematic diagram of the microtopography of the anode and cathode of the zinc-air cell of the present invention;
FIG. 7 is a schematic representation of the performance of a zinc-air cell of the present invention;
fig. 8 is a schematic diagram of the integration and application of the zinc-air cell of the present invention.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first", "a second", etc. may explicitly or implicitly include one or more such feature. In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art in a specific case.
The invention will be described in detail below with reference to the drawings in connection with embodiments.
The invention provides a miniature all-solid-state zinc-air battery and a preparation method thereof, wherein the air battery adopts an interdigital design of an air electrode and a zinc cathode which are opposite, which is beneficial to ions in electrolyte to come and go with the anode and the cathode in a shorter distance; printing a polymer fence outside the two electrode areas to enclose gel electrolyte ink; injecting gel electrolyte ink into the detour gap between the air electrode and the zinc negative electrode, completely infiltrating the two electrodes, and then coating the two electrodes by in-situ solidification; the height of the air electrode is a certain distance higher than that of the gel electrolyte so as to form an air electrode exposed in the air, and oxygen enters the air electrode and fully diffuses into the whole air electrode along a porous structure formed by stacking two-dimensional graphene sheets and dissolving sodium chloride to form a solid-liquid-gas three-phase interface; the macromolecule fence can be removed or reserved according to application requirements after the gel electrolyte is solidified; and the hydrophobic breathable film is adopted for integral encapsulation, breathable air is used for carrying out positive reaction, and moisture evaporation is blocked to prevent gel electrolyte from evaporating.
The invention also provides an ink formula for printing the porous air electrode, the zinc metal electrode and the alkaline gel electrolyte and a blending process thereof:
air electrode ink: comprises 18 to 45 weight percent of catalyst, 5 to 8 weight percent of conductive agent, 40 to 57 weight percent of solvent, 7 to 11 weight percent of binder, 1 to 2 weight percent of rheological agent, 1 to 2 weight percent of stabilizer and 1 to 2 weight percent of sacrificial agent;
the catalyst is cobaltosic oxide particles and RuO 2 、Pt/C、Pt/C-RuO 2 Or Pt/C-IrO 2 At least one of the conductive agent is at least one of graphene, conductive carbon black, acetylene black, carbon nano tube or carbon fiber, the solvent is at least one of dimethylformamide solution, dimethylacetamide, N-methylpyrrolidone, acetone or tetrahydrofuran, the binder is at least one of poly (vinylidene fluoride-co-hexafluoropropylene), cellulose, conductive rubber or epoxy resin, the rheological agent is fumed silica, the stabilizer is fatty acid zinc, and the sacrificial agent is at least one of sodium chloride, sodium carbonate or sodium bicarbonate.
Zinc electrode ink: comprises 31 to 58 weight percent of zinc powder, 4 to 6 weight percent of conductive agent, 30 to 50 weight percent of solvent, 3 to 5 weight percent of binder, 1 to 1.5 weight percent of rheological agent, 1 to 1.5 weight percent of stabilizer and 3 to 5 weight percent of molding reinforcing agent;
the conductive agent is at least one of conductive carbon black, graphene or acetylene black, carbon nano tubes and carbon fibers, the solvent is at least one of dimethylformamide solution, dimethylacetamide, N-methylpyrrolidone, acetone or tetrahydrofuran, the binder is at least one of poly (vinylidene fluoride-co-hexafluoropropylene), cellulose or conductive rubber, the rheologic agent is fumed silica, the stabilizer is fatty acid zinc, and the molding enhancer is thermoplastic polyurethane.
Gel electrolyte ink: comprises 8wt% of alkali, 5wt% of polymer, 51wt% of deionized water, 34wt% of water retention agent and 2wt% of corrosion inhibitor;
the alkali is at least one of potassium hydroxide or sodium hydroxide, the polymer is at least one of polyvinyl alcohol or polyacrylic acid, the water-retaining agent is tetraethylammonium hydroxide, MXene aqueous solution, or at least one of silicon dioxide, glycerol and ethylene glycol, and the corrosion inhibitor is tetrabutylammonium bromide.
The preparation flow of the miniature all-solid-state zinc-air battery is shown in fig. 1 and 2.
Example 1:
(1) 9wt% poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF) particles and 48wt% dimethylformamide solution were placed in a beaker, respectively, and then magnetically stirred at 85-95℃for 2 hours until completely dissolved. Then, 30wt% of tricobalt tetraoxide, 3wt% of graphene and 4wt% of conductive carbon black were sequentially added to the prepared solution, intensively mixed at 3000rpm for 30 minutes with a high-speed homogenizer, then 2wt% of sodium chloride, 2wt% of fumed silica and 2wt% of fatty acid zinc were added, and mixing at 8000rpm was continued for 30 minutes at a high speed until a uniform viscous air electrode ink was obtained. Wherein the weight ratio of poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF) particles to dimethylformamide solution is about 1:5.
(2) 4wt% of poly (vinylidene fluoride-co-hexafluoropropylene) particles, 4wt% of thermoplastic polyurethane particles (TPU) and 38wt% of dimethylformamide solution were placed in a beaker, respectively, and then magnetically stirred at 85 to 95℃for 2 hours until completely dissolved. 47wt% zinc powder, 3wt% graphene and 2wt% conductive carbon black were then added to the prepared solution in this order, and mixed vigorously with a high-speed homogenizer at 3000rpm for 30 minutes, then 1wt% fumed silica and 1wt% fatty acid zinc were added, and mixing was continued at a high speed of 8000rpm for 30 minutes until a uniformly viscous zinc electrode ink was obtained. Wherein the weight ratio of poly (vinylidene fluoride-co-hexafluoropropylene) particles, thermoplastic polyurethane particles (TPU), and dimethylformamide solution is about 1:1:10.
(3) 51wt% deionized water, 3wt% polyvinyl alcohol, 17wt% tetraethylammonium hydroxide, 17wt% MXene aqueous solution were placed in a beaker, then magnetically stirred at 85-95 ℃ for 1 hour until completely dissolved, then 2wt% tetrabutylammonium bromide and 10wt% potassium hydroxide solution with a concentration of 9M were added and stirring was continued for 30 minutes until completely dissolved, to obtain gel electrolyte ink. Wherein, the weight ratio of deionized water, polyvinyl alcohol, tetraethylammonium hydroxide and MXene aqueous solution is about 5:1:5:1.
(4) Before printing, air electrode ink, zinc electrode ink, silicone rubber and gel electrolyte ink were each loaded into a 4mL polypropylene syringe with nozzles (inside diameter between 350 and 750 μm). Next, an air electrode and a zinc electrode having a designed interdigital pattern were printed one by one on the PET film after plasma cleaning using a flexible electronic printer in an automated mode controlled by a computer. The air electrode is sprayed with water for pre-curing, the zinc electrode is heated (30 ℃ for 10 minutes) for pre-curing, then the next layer is continuously printed, and finally the printed interdigital electrode is placed in a freeze dryer and freeze-dried for 40 minutes at the temperature of minus 40 ℃ to minus 70 ℃.
(5) The freeze-dried interdigitated electrodes were returned to the printer and a square silicone rubber frame was printed around the effective interdigitated electrode area. The printed silicone rubber frame was left at room temperature overnight. And then printing gel electrolyte ink to fill gaps between interdigital electrodes in the silicon rubber frame, freezing and crosslinking the printed gel electrolyte at-30 to-40 ℃ for 12 hours, finally soaking the whole device in 1M potassium hydroxide aqueous solution for 30 minutes until sodium chloride in an air electrode is completely dissolved, and forming the solid zinc air micro-battery with the porous three-dimensional interdigital structure. Finally, if a compact device is required, the silicone rubber frame can be removed.
Example 2:
(1) 11wt% poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF) particles and 57wt% dimethylformamide solution were placed in a beaker, respectively, and then magnetically stirred at 85-95℃for 2 hours until completely dissolved. Then 18wt% of tricobalt tetraoxide, 4wt% of graphene and 4wt% of conductive carbon black were added to the prepared solution in this order, and mixed intensively with a high-speed homogenizer at 3000rpm for 30 minutes, then 2wt% of sodium chloride, 2wt% of fumed silica and 2wt% of fatty acid zinc were added, and mixing was continued at high speed 8000rpm for 30 minutes until a uniform viscous air electrode ink was obtained. Wherein the weight ratio of poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF) particles to dimethylformamide solution is about 1:5.
(2) The rest of the procedure is the same as in example 1.
Example 3:
(1) 7wt% poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF) particles and 40wt% dimethylformamide solution were placed in a beaker, respectively, and then magnetically stirred at 85-95℃for 2 hours until completely dissolved. 45wt% of tricobalt tetraoxide, 3wt% of graphene and 2wt% of conductive carbon black are then added to the prepared solution in sequence, and mixed intensively with a high-speed homogenizer at 3000rpm for 30 minutes, then 1wt% of sodium chloride, 1wt% of fumed silica and 1wt% of fatty acid zinc are added, and mixing is continued at high speed 8000rpm for 30 minutes until a uniform viscous air electrode ink is obtained. Wherein the weight ratio of poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF) particles to dimethylformamide solution is about 1:5.
(2) The rest of the procedure is the same as in example 1.
Example 4:
(1) 9wt% poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF) particles and 48wt% dimethylformamide solution were placed in a beaker, respectively, and then magnetically stirred at 85-95℃for 2 hours until completely dissolved. 31wt% of tricobalt tetraoxide, 4wt% of graphene and 4wt% of conductive carbon black are then added to the prepared solution in sequence, intensively mixed for 30 minutes at 3000rpm with a high-speed homogenizer, then 2wt% of fumed silica and 2wt% of fatty acid zinc are added, and mixing is continued for 30 minutes at 8000rpm at a high speed until a uniform viscous air electrode ink is obtained. Wherein the weight ratio of poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF) particles to dimethylformamide solution is about 1:5.
(2) The rest of the procedure is the same as in example 1
Comparative example 1:
in this example, the procedure in step (2) was changed as follows, and the other conditions were the same as in example 1.
(2) 5wt% of poly (vinylidene fluoride-co-hexafluoropropylene) particles, 5wt% of thermoplastic polyurethane particles (TPU) and 50wt% dimethylformamide solution were placed in a beaker and magnetically stirred at 85-95℃for 2 hours until completely dissolved. 31wt% zinc powder, 3wt% graphene and 3wt% conductive carbon black were then added to the prepared solution in this order, vigorously mixed with a high speed homogenizer at 3000rpm for 30 minutes, then 1.5wt% fumed silica and 1.5wt% fatty acid zinc were added, and mixing was continued at a high speed 8000rpm for 30 minutes until a uniformly viscous zinc electrode ink was obtained. Wherein the weight ratio of poly (vinylidene fluoride-co-hexafluoropropylene) particles, thermoplastic polyurethane particles (TPU), and dimethylformamide solution is about 1:1:10.
Comparative example 2:
in this example, the procedure in step (2) was changed as follows, and the other conditions were the same as in example 1.
(2) 3wt% of poly (vinylidene fluoride-co-hexafluoropropylene) particles, 3wt% of thermoplastic polyurethane particles (TPU) and 30wt% dimethylformamide solution were placed in a beaker and magnetically stirred at 85-95℃for 2 hours until completely dissolved. Then 58wt% zinc powder, 2wt% graphene and 2wt% conductive carbon black were added to the prepared solution in this order, and mixed vigorously with a high-speed homogenizer at 3000rpm for 30 minutes, then 1wt% fumed silica and 1wt% fatty acid zinc were added, and mixing was continued at a high speed of 8000rpm for 30 minutes until a uniformly viscous zinc electrode ink was obtained. Wherein the weight ratio of poly (vinylidene fluoride-co-hexafluoropropylene) particles, thermoplastic polyurethane particles (TPU), and dimethylformamide solution is about 1:1:10.
Comparative example 3:
in this example, the procedure in step (3) was changed as follows, and the other conditions were the same as in example 1.
(3) 51wt% of deionized water, 3wt% of polyvinyl alcohol and 34wt% of tetraethylammonium hydroxide are placed in a beaker, then magnetically stirred for 1 hour at 85-95 ℃ until the mixture is completely dissolved, then 2wt% of tetrabutylammonium bromide and 10wt% of 9M potassium hydroxide solution are added, and stirring is continued for 30 minutes until the mixture is completely dissolved, so that gel electrolyte ink is obtained.
Impedance, discharge electrode testing and specific energy density calculations were performed using an electrochemical workstation (CORRTEST, CS 2350H).
TABLE 1
TABLE 2
As can be seen from comparative examples 1, 2, 3, 4, the zinc-air battery prepared based on the ink having a catalyst content of 30wt% has the optimal electrochemical properties, shows good internal resistance and excellent catalytic properties, and is excellent in the range of 20mA/cm 2 The discharge voltage was 0.5V at the current density of (c). It can be found from comparative examples 1, 1 and 2 that the zinc-air battery prepared based on the ink having 47wt% zinc powder content has the optimal electrochemical properties and excellent mechanical properties, and the utilization rate of zinc is 737mAh/g at the highest. As can be seen from comparative examples 1 and 4, the aqueous MXene solution can improve the ionic conductivity of the gel electrolyte.
Fig. 3 shows a schematic diagram of the operation between adjacent fingers of a zinc-air cell. During discharge, oxygen gradually diffuses through a reticular porous structure formed by stacking two-dimensional graphene sheets and dissolving and sacrificing sodium chloride in an air electrode, and oxygen and water undergo an oxygen reduction reaction under the catalysis of a catalyst cobaltosic oxide to obtain electrons to generate OH - ，OH - The electrons are lost to the negative electrode by the reaction with Zn to generate Zn (OH) 4 2- . When charged, OH - In the presence of a catalyst of tricobalt tetraoxideOxygen evolution reaction occurs under catalysis to generate oxygen, zn (OH) 4 2- Electrons are obtained at the negative electrode to generate Zn.
Fig. 4 is a diagram of batch preparation and partial characterization of zinc-air cells.
Fig. 5 is a schematic diagram of the printed fabrication of interdigitated microelectrodes in different layers to demonstrate an ultra-thick cell.
Fig. 6 is a schematic diagram of the microscopic morphology of the positive and negative electrodes of a zinc-air cell.
In order to fully highlight the excellent performance of the three-dimensional interdigital miniature zinc-air battery prepared based on 3D printing, a comparison test is carried out with the miniature zinc-air battery with a traditional sandwich structure, as shown in fig. 7, and the result proves that the three-dimensional interdigital miniature zinc-air battery is far superior to the traditional miniature zinc-air battery in energy density, circulation time and zinc utilization rate.
In the application aspect of the zinc-air battery, as shown in fig. 8, the invention prints four zinc-air batteries on the PET film, then prints conductive silver paste, connects the four zinc-air batteries in series and parallel, supplies power for the vibration motor, can drive the vibration motor to rotate for up to 1.2 hours, and shows good integration capability and application potential of the zinc-air battery.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (3)

1. A preparation method of a miniature all-solid-state zinc-air battery is characterized by comprising the following steps: comprises preparing 3D printing ink, wherein the 3D printing ink comprises air electrode ink, zinc electrode ink and gel electrolyte ink;
the 3D printing ink is respectively passed through a 3D printer according to 100-400 KPa and the speed is 1-5 mm.s -1 Sequentially printing an air electrode, a zinc electrode and injected gel electrolyte on a planar substrate, and printing a macromolecule fence outside the two electrode areas to enclose gel electrolyte ink; gel electrolyte ink is injected into the detour gap between the air electrode and the zinc negative electrode to be completely soakedThe two electrodes are then wrapped by in-situ curing; the height of the air electrode is a certain distance higher than that of the gel electrolyte so as to form an air electrode exposed in the air, and oxygen enters the air electrode and fully diffuses into the whole air electrode along a porous structure formed by stacking two-dimensional graphene sheets and dissolving sodium chloride to form a solid-liquid-gas three-phase interface; the macromolecule fence can be removed or reserved according to application requirements after the gel electrolyte is solidified; adopting a hydrophobic and breathable film to carry out integral encapsulation, carrying out positive reaction by breathable air, blocking moisture evaporation to prevent gel electrolyte from evaporating, carrying out first curing after each layer is printed on an air electrode, carrying out second curing after each layer is printed on a zinc electrode, carrying out freeze drying treatment on the air electrode and the zinc electrode, carrying out freeze crosslinking and electrolyte soaking treatment on gel, and finally stacking to prepare the zinc-air battery;
the specific process comprises the following steps:
(1) Placing the binder and the solvent into a beaker, and magnetically stirring for 2 hours at 85-95 ℃ until the binder and the solvent are completely dissolved; sequentially adding a catalyst and a conductive agent into the prepared solution, intensively mixing for 30 minutes at 3000rpm by a high-speed homogenizer, then adding a sacrificial agent, a rheological agent and a stabilizer, and continuously mixing for 30 minutes at 8000rpm at a high speed until uniform and viscous air electrode ink is obtained;
the air electrode ink comprises 18-45 wt% of catalyst, 5-8 wt% of conductive agent, 40-57 wt% of solvent, 7-11 wt% of binder, 1-2 wt% of rheological agent, 1-2 wt% of stabilizer and 1-2 wt% of sacrificial agent;
the catalyst is cobaltosic oxide particles and RuO 2 、Pt/C、Pt/C-RuO 2 Or Pt/C-IrO 2 At least one of the conductive agent is at least one of graphene, conductive carbon black, acetylene black, carbon nano tube or carbon fiber, the solvent is at least one of dimethylformamide solution, dimethylacetamide, N-methylpyrrolidone, acetone or tetrahydrofuran, the binder is at least one of poly (vinylidene fluoride-co-hexafluoropropylene), cellulose, conductive rubber or epoxy resin, the rheologic agent is fumed silica, the stabilizer is fatty acid zinc, and the sacrificial agent is sodium chloride, sodium carbonate or carbonic acidAt least one of sodium hydrogen
(2) Putting 4wt% of poly (vinylidene fluoride-co-hexafluoropropylene) particles, 4wt% of thermoplastic polyurethane particles (TPU) and 38wt% of dimethylformamide solution into a beaker respectively, magnetically stirring at 85-95 ℃ for 2 hours until complete dissolution, then sequentially adding 47wt% of zinc powder, 3wt% of graphene and 2wt% of conductive carbon black into the prepared solution, intensively mixing for 30 minutes at 3000rpm by a high-speed homogenizer, then adding 1wt% of fumed silica and 1wt% of zinc fatty acid, and continuing mixing for 30 minutes at 8000rpm at a high speed until uniform and viscous zinc electrode ink is obtained;
the zinc electrode ink comprises 31-58 wt% of zinc powder, 4-6 wt% of conductive agent, 30-50 wt% of solvent, 3-5 wt% of binder, 1-1.5 wt% of rheological agent, 1-1.5 wt% of stabilizer and 3-5 wt% of molding reinforcing agent;
the conductive agent is conductive carbon black and graphene, the solvent is dimethylformamide solution, the binder is poly (vinylidene fluoride-co-hexafluoropropylene) particles, the rheologic agent is fumed silica, the stabilizer is fatty acid zinc, and the molding enhancer is thermoplastic polyurethane;
(3) Deionized water, a polymer and a water-retaining agent are placed into a beaker, then magnetically stirred for 1 hour at 85-95 ℃ until the deionized water, the polymer and the water-retaining agent are completely dissolved, then corrosion inhibitor and alkali are added, and stirring is continued for 30 minutes until the deionized water, the polymer and the water-retaining agent are completely dissolved, so that gel electrolyte ink is obtained; the gel electrolyte ink comprises 8wt% of alkali, 5wt% of polymer, 51wt% of deionized water, 34wt% of water-retaining agent and 2wt% of corrosion inhibitor, wherein the alkali is potassium hydroxide or sodium hydroxide, the polymer is polyvinyl alcohol, the water-retaining agent is tetraethylammonium hydroxide and MXene aqueous solution, and the corrosion inhibitor is tetrabutylammonium bromide;
(4) Before printing, respectively filling air electrode ink, zinc electrode ink, silicon rubber and gel electrolyte ink into a 4mL polypropylene injector with a nozzle, then printing the air electrode with designed interdigital patterns and the zinc electrode on a PET film after plasma cleaning one by using a flexible electronic printer in an automatic mode controlled by a computer, wherein the air electrode is sprayed with water and spray for pre-curing, the zinc electrode is heated and pre-cured, then printing the next layer, finally placing the printed interdigital electrode in a freeze dryer, and freeze drying for 40 minutes at the temperature of minus 40 to minus 70 ℃;
(5) Placing the freeze-dried interdigital electrode back into a printer, printing a square silicon rubber frame around the effective interdigital electrode area, standing the printed silicon rubber frame at room temperature overnight, then printing gel electrolyte ink to fill gaps between interdigital electrodes in the silicon rubber frame, then freezing and crosslinking the printed gel electrolyte at-30 to-40 ℃ for 12 hours, finally soaking the whole device in 1M potassium oxide aqueous solution for 30 minutes, waiting until sodium chloride is completely dissolved in an air electrode, and forming the solid zinc-air microbattery with the porous three-dimensional interdigital structure.
2. The method for manufacturing a miniature all-solid-state zinc-air battery according to claim 1, wherein the method comprises the steps of: the first curing is pre-curing by spraying water spray after each layer is printed on the air electrode.
3. The method for manufacturing a miniature all-solid-state zinc-air battery according to claim 1, wherein the method comprises the steps of: the second curing is thermal curing, the time of the second curing is 10 minutes, and the temperature of the second curing is 30 ℃.
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