CN115036518A - 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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CN115036518A
CN115036518A CN202210747661.5A CN202210747661A CN115036518A CN 115036518 A CN115036518 A CN 115036518A CN 202210747661 A CN202210747661 A CN 202210747661A CN 115036518 A CN115036518 A CN 115036518A
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zinc
electrode
air
ink
agent
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CN115036518B (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

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 sequentially printing an air electrode, a zinc electrode and injecting gel electrolyte on the planar substrate by the 3D printing ink through the 3D printer parameters, performing first solidification after printing each layer of the air electrode, performing second solidification after printing each layer of the zinc electrode, 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 the 3D printing manufacture of the zinc-air battery becomes possible; the printed electrodes are designed in an interdigital counter electrode structure, so that the micro-patterning preparation is facilitated, the rapid reciprocating of ions in electrolyte between the positive electrode and the negative electrode is facilitated, and the printed electrodes 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 lightweight, miniaturized, and compact energy devices is becoming stronger. In recent years, miniature energy storage devices have been developed, mainly focusing on supercapacitors and lithium ion batteries. However, due to the limitation of energy storage mechanism, the energy density (300Wh/kg) of lithium ion batteries still cannot meet the requirement of long endurance time of electronic products. The metal-air battery, which uses metal as a negative electrode and uses a matched salt or alkali solution as an electrolyte, has a unique semi-open battery structure, can use air in the surrounding environment as a positive electrode active material, does not occupy the volume and mass of a battery body, and therefore has an energy density (1353Wh/kg) 4.5 times that of a lithium ion battery, and is considered to be one of the best candidates of a next-generation high-specific-energy device. Among them, zinc-air batteries are receiving more and more research attention due to the high abundance and low toxicity of the metal zinc of the negative electrode. However, the miniaturization of the zinc-air battery is challenging to prepare, which mainly shows that the unique solid-liquid-gas three-phase structure of the air electrode is difficult to micro-machine and realize, the strong base corrosive electrolyte is difficult to package, and the package requirement of hydrophobic and breathable is required. Therefore, the miniaturization 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, a gel electrolyte technology is developed, and the gel electrolyte does not flow, so that the compact preparation of an energy device is favorably realized. Therefore, the all-solid-state zinc-air battery has two main types, namely a sandwich structure and a fiber structure, wherein the sandwich structure is formed by respectively attaching a flaky air electrode and a zinc cathode to two sides of a gel electrolyte, and the fiber structure is formed by sequentially wrapping the gel electrolyte and the air electrode by taking the fibrous zinc cathode as a center. The sandwich type zinc-air battery is simple in structure, and the fiber type zinc-air battery is fine and soft. However, the two device forms are difficult to realize miniaturization of the device, and it is difficult to continuously increase the energy density per unit area of the device.
The design of the interdigital counter electrode is beneficial to the rapid transfer of ions in electrolyte between two counter electrodes with short distance, and the three-dimensional design for longitudinally increasing the thickness of the electrode is beneficial to increasing the content of active substances in unit area. In the aspect of preparation methods, the traditional methods such as screen printing based on ink, etching micro-processing based on a mask plate, micro-fluid injection based on a micro-channel and the like can realize the patterning preparation of the interdigital microelectrode in a plane. However, they cannot build up ultra-high thickness micro electrodes, which greatly limits further improvements in energy density of micro energy devices. In recent years, 3D direct-write printing technology has emerged as a revolutionary manufacturing method, which can print and write complex micro patterns directly on a planar substrate with viscous ink based on design drawing input and digital programming, and has geometric controllability and process flexibility, and most importantly, can realize layer-by-layer printing and stacking to prepare ultra-thick micro electrodes. However, no one has succeeded in realizing 3D printed micro zinc-air battery at present, and the challenge difficulty lies in the development of ink rich in nano-scale catalyst particles, zinc powder particles and strong alkaline electrolyte and the printing and molding with high spatial resolution.
Disclosure of Invention
In view of the above, the present invention is directed to a micro all-solid-state zinc-air battery and a method for manufacturing the same, so as to solve the above-mentioned problems in the background art.
In order to achieve the 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 arranged side by side in the same plane and are in opposite interdigital structures, and the zinc-air battery is manufactured by using a 3D printing technology.
The invention also provides a preparation method of the miniature all-solid-state zinc-air battery, which comprises the steps of
Preparing 3D printing ink;
respectively enabling the 3D printing ink to pass through a 3D printer at a speed of 1-5 mm s and a Kpa of 100-400 Kpa -1 The air electrode and the zinc electrode are subjected to freeze drying treatment, the 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 18-45 wt% of a catalyst, 5-8 wt% of a conductive agent, 40-57 wt% of a solvent, 7-11 wt% of a binder, 1-2 wt% of a rheological agent, 1-2 wt% of a stabilizer and 1-2 wt% of a sacrificial agent;
the catalyst is cobaltosic oxide particles and RuO 2 、Pt/C、Pt/C-RuO 2 Or Pt/C-IrO 2 The conductive agent is at least one of graphene, conductive carbon black, acetylene black, carbon nanotubes or 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, 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.
Further, the zinc electrode ink comprises 31-58 wt% of zinc powder, 4-6 wt% of a conductive agent, 30-50 wt% of a solvent, 3-5 wt% of a binder, 1-1.5 wt% of a rheological agent, 1-1.5 wt% of a stabilizer and 3-5 wt% of a forming 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 a 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 rheological agent is fumed silica, the stabilizer is fatty acid zinc, and the forming reinforcing agent is thermoplastic polyurethane.
Further, 8 wt% of alkali, 5 wt% of polymer, 51 wt% of deionized water, 34 wt% of water-retaining agent and 2 wt% of corrosion inhibitor are added into the gel electrolyte ink;
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 and 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 after printing each layer 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) putting the binder and the solvent into a beaker, and then 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 using a high-speed homogenizer, then adding a sacrificial agent, a rheological agent and a stabilizing agent, and continuously mixing for 30 minutes at 8000rpm until uniform and viscous air electrode ink is obtained;
(2) putting the binder, the forming reinforcing agent and the solvent into a beaker, and then magnetically stirring for 2 hours at 85-95 ℃ until the binder, the forming reinforcing agent and the solvent are completely dissolved; then adding zinc powder and a conductive agent into the prepared solution in sequence, intensively mixing for 30 minutes at 3000rpm by using a high-speed homogenizer, then adding a rheological agent and a stabilizing agent, and continuing mixing for 30 minutes at 8000rpm at a high speed until uniform and viscous zinc electrode ink is obtained;
(3) putting deionized water, polyvinyl alcohol, tetraethylammonium hydroxide and MXene aqueous solution into a beaker, magnetically stirring for 1 hour at 85-95 ℃ until the solution is completely dissolved, adding a corrosion inhibitor and alkali, and continuously stirring for 30 minutes until the solution is completely dissolved to obtain gel electrolyte ink;
(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 and the zinc electrode with a designed interdigital pattern on a PET film after plasma cleaning one by using a flexible electronic printer under an automatic mode controlled by a computer, wherein the air electrode sprays water spray to perform precuring, the zinc electrode is heated and precured, then the next layer is continuously printed, and finally, placing the printed interdigital electrode in a freeze dryer, and freeze-drying for 40 minutes at the temperature of between 40 ℃ below zero and 70 ℃ below zero;
(5) putting the freeze-dried interdigital electrode back into a printer, printing a square silicon rubber frame around an effective interdigital electrode area, standing the printed silicon rubber frame at room temperature overnight, printing gel electrolyte ink to fill gaps among the 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, and forming the solid zinc air micro-battery with the porous three-dimensional interdigital structure after sodium chloride obtained in the air electrode is completely dissolved.
Compared with the prior art, the miniature all-solid-state zinc-air battery and the preparation method thereof have the following advantages:
(1) the printable ink of the air electrode, the zinc electrode and the electrolyte is developed, so that the 3D printing manufacturing of the zinc-air battery is possible, and the printed air electrode has a porous structure and is beneficial to the generation of solid-liquid-gas three-phase reaction;
(2) the printed electrodes are designed into an interdigital counter electrode structure, so that the micro-patterning preparation is facilitated, ions in electrolyte can reciprocate rapidly between the positive electrode and the negative electrode, the printed electrodes can be stacked layer by layer as required, the content of active electrode substances in unit area is improved, and therefore the unit area energy of the battery is improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic view of a process for preparing an ink according to the present invention;
fig. 2 is a schematic diagram of a printing process of the zinc-air battery of 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 diagram of batch fabrication and partial characterization of a zinc-air cell of the present invention;
FIG. 5 is a schematic view of the present invention showing the printing and fabrication of ultra thick cells with different numbers of layers of interdigitated microelectrode;
FIG. 6 is a schematic view showing the micro-morphology of the positive and negative electrodes of the zinc-air battery of the present invention;
FIG. 7 is a schematic of the performance of a zinc-air cell of the present invention;
fig. 8 is a schematic view of the integration and application of the zinc-air battery of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in the orientations and positional relationships indicated in the drawings, which are based on the orientations and positional relationships indicated in the drawings, and are used for convenience in describing the present invention and for simplicity in description, but do not indicate or imply that the device or element so referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus should not be construed as limiting the present invention. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected 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 through specific situations.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
The invention provides a miniature all-solid-state zinc-air battery and a preparation method thereof, wherein the air battery adopts an interdigital design with an air electrode and a zinc cathode opposite to each other, so that ions in electrolyte can go and return in a short distance with the anode and the cathode; printing a polymer fence outside the two electrode areas to surround the gel electrolyte ink; injecting gel electrolyte ink into a circuitous gap between the air electrode and the zinc cathode, completely soaking the two electrodes, and then coating the two electrodes by in-situ curing; the height of the air electrode is higher than that of the gel electrolyte for a certain distance so as to form an air electrode exposed in the air, and oxygen enters from the air electrode and is fully diffused into the whole air electrode along a porous structure formed by stacking two-dimensional graphene sheet layers and dissolving sodium chloride to form a solid-liquid-gas three-phase interface; the polymer fence can be dismantled or reserved according to application requirements after the gel electrolyte is solidified; and (3) integrally packaging by adopting a hydrophobic and breathable film, carrying out positive reaction by using breathable air, and blocking water evaporation to prevent the evaporation of the gel electrolyte.
The invention also provides an ink formula for printing the porous air electrode, the zinc metal electrode and the alkaline gel electrolyte and a preparation process thereof:
air electrode ink: the catalyst comprises 18-45 wt% of a catalyst, 5-8 wt% of a conductive agent, 40-57 wt% of a solvent, 7-11 wt% of a binder, 1-2 wt% of a rheological agent, 1-2 wt% of a stabilizer and 1-2 wt% of a sacrificial agent;
the catalyst is cobaltosic oxide particles and RuO 2 、Pt/C、Pt/C-RuO 2 Or Pt/C-IrO 2 The conductive agent is at least one of graphene, conductive carbon black, acetylene black, carbon nanotubes or 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, 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: the material 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 forming 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 a 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 rheological agent is fumed silica, the stabilizer is fatty acid zinc, and the forming reinforcing agent is thermoplastic polyurethane.
Gel electrolyte ink: comprises 8 wt% of alkali, 5 wt% of polymer, 51 wt% of deionized water, 34 wt% of water-retaining agent and 2 wt% 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 and MXene aqueous solution or at least one of silicon dioxide, glycerol and ethylene glycol, and the corrosion inhibitor is tetrabutylammonium bromide.
The preparation process of the miniature all-solid-state zinc-air battery is shown in the figures 1 and 2.
Example 1:
(1) 9 wt% poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF) particles and 48 wt% dimethylformamide solution were placed in a beaker, respectively, and then magnetically stirred at 85-95 ℃ for 2 hours until completely dissolved. Then, 30 wt% of cobaltosic oxide, 3 wt% of graphene and 4 wt% of conductive carbon black were added to the prepared solution in this order, and intensively mixed with a high-speed homogenizer at 3000rpm for 30 minutes, and then 2 wt% of sodium chloride, 2 wt% of fumed silica and 2 wt% of fatty acid zinc were added, and mixing was continued at high speed 8000rpm for 30 minutes until a uniformly 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) Respectively putting 4 wt% of poly (vinylidene fluoride-co-hexafluoropropylene) particles, 4 wt% of thermoplastic polyurethane particles (TPU) and 38 wt% of dimethylformamide solution into a beaker, and then magnetically stirring for 2 hours at 85-95 ℃ until the poly (vinylidene fluoride-co-hexafluoropropylene) particles are completely dissolved. Then 47 wt% of zinc powder, 3 wt% of graphene and 2 wt% of conductive carbon black were added to the prepared solution in this order, and they were intensively mixed with a high-speed homogenizer at 3000rpm for 30 minutes, and then 1 wt% of fumed silica and 1 wt% of fatty acid zinc were added, and mixing was continued at 8000rpm at a high speed 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) Putting 51 wt% of deionized water, 3 wt% of polyvinyl alcohol, 17 wt% of tetraethylammonium hydroxide and 17 wt% of MXene aqueous solution into a beaker, then magnetically stirring for 1 hour at 85-95 ℃ until the solution is completely dissolved, then adding 2 wt% of tetrabutylammonium bromide and 10 wt% of 9M potassium hydroxide solution, and continuing stirring for 30 minutes until the solution is completely dissolved to obtain the gel electrolyte ink. Wherein the weight ratio of the deionized water to the polyvinyl alcohol to the tetraethylammonium hydroxide to the MXene aqueous solution is about 5:1:5: 1.
(4) Before printing, the air electrode ink, zinc electrode ink, silicone rubber and gel electrolyte ink were each loaded into a 4mL polypropylene syringe with a nozzle (internal diameter between 350 and 750 μm). Next, air electrodes and zinc electrodes with designed interdigitated pattern were printed one after another on the plasma-cleaned PET film using a flexible electronic printer in an automated mode controlled by a computer. Wherein the air electrode sprays water spray to perform precuring, the zinc electrode is heated (30 ℃ for 10 minutes) to perform precuring, then the next layer is continuously printed, and finally the printed interdigital electrode is placed in a freeze dryer and is freeze-dried for 40 minutes at the temperature of minus 40 to minus 70 ℃.
(5) And (4) putting the freeze-dried interdigital electrode back into a printer, and printing a square silicon rubber framework around the effective interdigital electrode area. The printed silicone rubber frame was left at room temperature overnight. And then printing gel electrolyte ink to fill gaps among the 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, and forming the solid zinc air micro battery with the porous three-dimensional interdigital structure after sodium chloride in the air electrode is completely dissolved. Finally, if a compact and compact device is required, the silicone rubber frame can be removed.
Example 2:
(1) separately, 11 wt% poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF) particles and 57 wt% dimethylformamide solution were placed in a beaker and then magnetically stirred at 85-95 ℃ for 2 hours until completely dissolved. Then, 18 wt% of cobaltosic oxide, 4 wt% of graphene and 4 wt% of conductive carbon black were added to the prepared solution in this order, and intensively mixed with a high-speed homogenizer at 3000rpm for 30 minutes, and then 2 wt% of sodium chloride, 2 wt% of fumed silica and 2 wt% of fatty acid zinc were added, and mixing was continued at high-speed 8000rpm for 30 minutes until a uniformly 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 remaining steps were the same as in example 1.
Example 3:
(1) 7 wt% poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF) particles and 40 wt% dimethylformamide solution were placed in a beaker, respectively, and then magnetically stirred at 85-95 ℃ for 2 hours until completely dissolved. Then, 45 wt% of cobaltosic oxide, 3 wt% of graphene and 2 wt% of conductive carbon black were added to the prepared solution in this order, and intensively mixed with a high-speed homogenizer at 3000rpm for 30 minutes, then 1 wt% of sodium chloride, 1 wt% of fumed silica and 1 wt% of fatty acid zinc were added, and mixing was continued at high speed 8000rpm for 30 minutes until a uniformly 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 remaining steps were the same as in example 1.
Example 4:
(1) 9 wt% poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF) particles and 48 wt% dimethylformamide solution were placed in a beaker, respectively, and then magnetically stirred at 85-95 ℃ for 2 hours until completely dissolved. Then, 31 wt% of cobaltosic oxide, 4 wt% of graphene and 4 wt% of conductive carbon black were added to the prepared solution in this order, and intensively mixed with a high-speed homogenizer at 3000rpm for 30 minutes, and then 2 wt% of fumed silica and 2 wt% of fatty acid zinc were added, and mixing was continued at 8000rpm at a high speed 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 was the same as in example 1
Comparative example 1:
in this example, the procedure of step (2) was changed as follows, and the other conditions were the same as in example 1.
(2) 5 wt% poly (vinylidene fluoride-co-hexafluoropropylene) particles, 5 wt% thermoplastic polyurethane particles (TPU), and 50 wt% dimethylformamide solution were placed in a beaker and then magnetically stirred at 85-95 ℃ for 2 hours until completely dissolved. Then, 31 wt% of zinc powder, 3 wt% of graphene and 3 wt% of conductive carbon black were added to the prepared solution in this order, and intensively mixed with a high-speed homogenizer at 3000rpm for 30 minutes, then 1.5 wt% of fumed silica and 1.5 wt% of fatty acid zinc were added, and mixing was continued at 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 of step (2) was changed as follows, and the other conditions were the same as in example 1.
(2) Putting 3 wt% of poly (vinylidene fluoride-co-hexafluoropropylene) particles, 3 wt% of thermoplastic polyurethane particles (TPU) and 30 wt% of dimethylformamide solution into a beaker, and then magnetically stirring for 2 hours at 85-95 ℃ until the poly (vinylidene fluoride-co-hexafluoropropylene) particles are completely dissolved. Then, 58 wt% of zinc powder, 2 wt% of graphene and 2 wt% of conductive carbon black were added to the prepared solution in this order, and intensively mixed with a high-speed homogenizer at 3000rpm for 30 minutes, then 1 wt% of fumed silica and 1 wt% of fatty acid zinc were added, and mixing was continued at 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 3:
in this example, the procedure of step (3) was changed as follows, and the other conditions were the same as in example 1.
(3) Putting 51 wt% of deionized water, 3 wt% of polyvinyl alcohol and 34 wt% of tetraethylammonium hydroxide into a beaker, magnetically stirring for 1 hour at 85-95 ℃ until the deionized water, the polyvinyl alcohol and the tetraethylammonium hydroxide are completely dissolved, adding 2 wt% of tetrabutylammonium bromide and 10 wt% of 9M potassium hydroxide solution, and continuously stirring for 30 minutes until the tetrabutylammonium bromide and the potassium hydroxide are completely dissolved to obtain the gel electrolyte ink.
Impedance, discharge polarization tests and specific energy density calculations were performed using an electrochemical workstation (CORRTEST, CS 2350H).
TABLE 1
Figure BDA0003719917680000131
TABLE 2
Figure BDA0003719917680000132
Figure BDA0003719917680000141
It can be seen by comparing examples 1, 2, 3 and 4 that the zinc-air battery prepared based on 30 wt% catalyst content ink has the optimum electrochemical performance, exhibits good internal resistance and excellent catalytic performance at 20mA/cm 2 Discharge voltage of 0.5V. It can be seen by comparing example 1, comparative example 1, and comparative example 2 that the zinc-air cell prepared based on the ink having a zinc powder content of 47 wt% has the best electrochemical properties and excellent mechanical properties, and the utilization rate of zinc is up to 737 mAh/g. It can be found by comparing example 1 and comparative example 4 that the MXene aqueous solution can improve the ionic conductivity of the gel electrolyte.
Fig. 3 shows the operation principle of the adjacent fingers of the zinc-air battery. During discharging, oxygen is gradually diffused through a reticular porous structure formed by stacking two-dimensional graphene sheets and dissolving and sacrificing sodium chloride in the 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 - Move to the negative electrode to react with Zn and lose electrons to generate Zn (OH) 4 2- . When charged, OH - Oxygen evolution reaction is carried out to generate oxygen, Zn (OH) under the catalysis of catalyst cobaltosic oxide 4 2- Electrons are obtained in the negative electrode to generate Zn.
Fig. 4 is a batch preparation and partial characterization diagram of a zinc-air battery.
Fig. 5 is a schematic diagram of the printing and manufacturing of ultra-thick cells by using different numbers of layers of interdigital micro-electrodes.
Fig. 6 is a schematic diagram of the micro-morphology of the positive and negative electrodes of the zinc-air battery.
In order to fully highlight the excellent performance of the three-dimensional interdigital micro zinc-air battery prepared based on 3D printing, a comparison test is carried out on the three-dimensional interdigital micro zinc-air battery and a micro zinc-air battery with a traditional sandwich structure as shown in figure 7, and the result proves that the three-dimensional interdigital micro zinc-air battery is far superior to the traditional micro zinc-air battery in terms of energy density, cycle 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 a PET film, then prints conductive silver paste, connects the four zinc-air batteries in series and in parallel, supplies power to a vibration motor, and can drive the vibration motor to rotate for 1.2 hours, thereby showing the good integration capability and application potential of the zinc-air battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. A miniature all-solid-state zinc-air battery is characterized in that: the zinc-air battery comprises an air electrode, a zinc electrode and a gel electrolyte, wherein the air electrode and the zinc electrode are arranged side by side in the same plane and are in opposite interdigital structures, and the zinc-air battery is manufactured by using a 3D printing technology.
2. A preparation method of a miniature all-solid-state zinc-air battery is characterized by comprising the following steps: comprises that
Preparing 3D printing ink;
respectively enabling the 3D printing ink to pass through a 3D printer at a speed of 1-5 mm s and a Kpa of 100-400 Kpa -1 The air electrode, the zinc electrode and the injected gel electrolyte are sequentially printed on the planar substrate, the first solidification is carried out after each layer of the air electrode is printed, the second solidification is carried out after each layer of the zinc electrode is printed, and the air electrode and the zinc electrode are frozenAnd (4) drying, freezing and crosslinking the gel, soaking the gel in electrolyte, and finally stacking to prepare the zinc-air battery.
3. The method for preparing a miniature all-solid-state zinc-air battery according to claim 2, wherein the method comprises the following steps: the 3D printing ink includes air electrode ink, zinc electrode ink, and gel electrolyte ink.
4. The method for preparing a miniature all-solid-state zinc-air battery according to claim 3, wherein the method comprises the following steps: the air electrode ink comprises 18-45 wt% of a catalyst, 5-8 wt% of a conductive agent, 40-57 wt% of a solvent, 7-11 wt% of a binder, 1-2 wt% of a rheological agent, 1-2 wt% of a stabilizer and 1-2 wt% of a sacrificial agent;
the catalyst is cobaltosic oxide particles and RuO 2 、Pt/C、Pt/C-RuO 2 Or Pt/C-IrO 2 The conductive agent is at least one of graphene, conductive carbon black, acetylene black, carbon nanotubes or 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, 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.
5. The method for preparing a miniature all-solid-state zinc-air battery according to claim 3, wherein the method comprises the following steps: the zinc electrode ink comprises 31-58 wt% of zinc powder, 4-6 wt% of a conductive agent, 30-50 wt% of a solvent, 3-5 wt% of a binder, 1-1.5 wt% of a rheological agent, 1-1.5 wt% of a stabilizer and 3-5 wt% of a forming reinforcing agent;
the conductive agent is at least one of conductive carbon black, graphene or acetylene black, carbon nanotubes and carbon fibers, the solvent is at least one of a 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 rheological agent is fumed silica, the stabilizer is fatty acid zinc, and the forming reinforcing agent is thermoplastic polyurethane.
6. The method for preparing a miniature all-solid-state zinc-air battery according to claim 3, wherein the method comprises the following steps: the gel electrolyte ink comprises 8 wt% of alkali, 5 wt% of polymer, 51 wt% of deionized water, 34 wt% of water-retaining agent and 2 wt% 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 and MXene aqueous solution or at least one of silicon dioxide, glycerol and ethylene glycol, and the corrosion inhibitor is tetrabutylammonium bromide.
7. The method for preparing a miniature all-solid-state zinc-air battery according to claim 2, wherein the method comprises the following steps: the first curing is to perform pre-curing by spraying water after printing each layer of the air electrode.
8. The method for preparing a miniature all-solid-state zinc-air battery according to claim 2, wherein the method comprises the following steps: the second curing is thermal curing, the time of the second curing is 10 minutes, and the temperature of the second curing is 30 ℃.
9. The method for manufacturing a miniature all-solid-state zinc-air battery according to any one of claims 2 to 8, wherein: the preparation process of the miniature all-solid-state zinc-air battery comprises the following steps:
(1) putting the binder and the solvent into a beaker, and then magnetically stirring for 2 hours at 85-95 ℃ until the binder and the solvent are completely dissolved; then adding a catalyst and a conductive agent into the prepared solution in sequence, intensively mixing for 30 minutes at 3000rpm by using a high-speed homogenizer, then adding a sacrificial agent, a rheological agent and a stabilizing agent, and continuing mixing for 30 minutes at 8000rpm at high speed until uniform and viscous air electrode ink is obtained;
(2) putting the binder, the forming reinforcing agent and the solvent into a beaker, and then magnetically stirring for 2 hours at 85-95 ℃ until the binder, the forming reinforcing agent and the solvent are completely dissolved; then adding zinc powder and a conductive agent into the prepared solution in sequence, intensively mixing for 30 minutes at 3000rpm by using a high-speed homogenizer, then adding a rheological agent and a stabilizing agent, and continuing mixing for 30 minutes at 8000rpm at a high speed until uniform and viscous zinc electrode ink is obtained;
(3) putting deionized water, polyvinyl alcohol, tetraethylammonium hydroxide and MXene aqueous solution into a beaker, magnetically stirring for 1 hour at 85-95 ℃ until the solution is completely dissolved, adding a corrosion inhibitor and alkali, and continuously stirring for 30 minutes until the solution is completely dissolved to obtain gel electrolyte ink;
(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 and the zinc electrode with a designed interdigital pattern on a PET film after plasma cleaning one by using a flexible electronic printer under an automatic mode controlled by a computer, wherein the air electrode sprays water spray to perform precuring, the zinc electrode is heated and precured, then the next layer is continuously printed, and finally, placing the printed interdigital electrode in a freeze dryer, and freeze-drying for 40 minutes at the temperature of between 40 ℃ below zero and 70 ℃ below zero;
(5) putting the freeze-dried interdigital electrode back into a printer, printing a square silicon rubber frame around an effective interdigital electrode area, standing the printed silicon rubber frame at room temperature overnight, printing gel electrolyte ink to fill gaps among the 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, and forming the solid zinc air micro-battery with the porous three-dimensional interdigital structure after sodium chloride obtained in the air electrode is completely dissolved.
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