CN113745711A - Flexible metal-air battery and application thereof - Google Patents
Flexible metal-air battery and application thereof Download PDFInfo
- Publication number
- CN113745711A CN113745711A CN202110807530.7A CN202110807530A CN113745711A CN 113745711 A CN113745711 A CN 113745711A CN 202110807530 A CN202110807530 A CN 202110807530A CN 113745711 A CN113745711 A CN 113745711A
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- Prior art keywords
- metal
- ink
- anode
- cathode
- air
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Images
Classifications
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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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
- B65B25/00—Packaging other articles presenting special problems
- B65B25/001—Packaging other articles presenting special problems of foodstuffs, combined with their conservation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
- B65B31/00—Packaging articles or materials under special atmospheric or gaseous conditions; Adding propellants to aerosol containers
Abstract
The invention relates to a flexible metal-air battery and application thereof, belonging to the technical field of printed electronics and intelligent packaging; including air diffusion layer, the silver mass flow body of negative pole, the silver mass flow body of positive pole, metal anode printing ink, air cathode printing ink and gel electrolyte, follow supreme being in proper order down: the air diffusion layer, the cathode silver current collector and the anode silver current collector are located on the air diffusion layer, the metal anode ink is located on the anode silver current collector, the air cathode ink is located on the cathode silver current collector, the metal anode ink and the air cathode ink are arranged in parallel, and the gel electrolyte wraps the cathode silver current collector and the anode silver current collector. The flexible metal-air battery is low in cost, active interactive, high in sensitivity, flexible, simple in process and wide in application range.
Description
Technical Field
The invention relates to a flexible metal-air battery and application thereof, belonging to the technical field of printed electronics and intelligent packaging.
Background
The intelligent package is a package with functions of 'recognition' and 'judgment' for environmental factors, and can recognize and display important parameters of temperature, humidity, pressure, sealing degree, time and the like of a package space. The appearance of intelligent packaging technology enables commodities and packages thereof to have better affinity for human beings and simpler man-machine interactive communication, and has extremely broad development prospect. Sensors that respond to environmental stimuli are a key basis for smart packaging technology. The oxygen sensor is widely applied to the fields of laboratories, biology, medicine, automobile manufacturing, chemical industry, energy, civil use, military and the like, and is applied to packaging of articles, so that the development of interactive oxygen intelligent packaging with oxygen identification, monitoring and feedback is a hotspot in the academic and industrial fields at present.
At present, the existing technology on the market cannot be really called oxygen intelligent package, and more is an oxygen active indicator package, and oxygen is identified and indicated by changing the color of the oxygen active indicator package through the chemical reaction of oxygen and active substances. Gillanders et al, prepared novel phosphorescent oxygen-sensitive materials of nanostructured high density polyethylene and polypropylene films by solvent cracking, are simple to use, economical and efficient to produce, disposable, and suitable for large-scale applications (Analytical Chemistry, vol.82, No.2, January 15,2010). Lopez-Carballo et al prepared Sensors based on methylene blue, glycerol, titanium dioxide and ethylene-vinyl acetate copolymer, detected oxygen at concentrations as low as 0.5% and enabled commercial printing (Sensors 2019,19, 4684; doi:10.3390/s 19214684). The product has the problems that the content of oxygen cannot be quantitatively detected, the product is a passive oxygen sensor, workers are required to approach the product and judge the product through visual observation, and the subjective influence is large; and its safety for use in food packaging needs to be examined further. Although such as an optical fiber type oxygen sensor, a thermomagnetic type oxygen sensor and a semiconductor type resistance oxygen sensor can effectively perform quantitative detection on the oxygen content, and the detection precision is high, the manufacturing method is complex, the cost is high, the structure is complex, and the method is not suitable for low-cost packaging products. Therefore, it is of great significance to the development of intelligent oxygen packaging to provide a novel oxygen sensor that is low in cost, active interactive, high in sensitivity, and easy to combine with existing packaging.
The metal-air battery takes oxygen in the air as a positive active material and metal (aluminum, magnesium, zinc or the like) as a negative active material, has rich and cheap resources, can be recycled, has no pollution to reactants and products and has excellent environmental compatibility. Theoretically, the output characteristics (voltage and current) of the metal-air battery and the oxygen content participating in the reaction are in a linear relationship within a certain range, and the metal-air battery can be used as an oxygen sensor. Because the metal-air battery is an electrochemical power supply, the oxygen sensor based on the metal-air battery does not need an external power supply, can realize self power supply, meets the requirements of green and energy conservation, and can realize active real-time monitoring by integrating the metal-air battery and the data transmission module. Hooi et al performed a proof of principle in this regard, demonstrating the principle of electrochemical cells as Oxygen sensors by Using commercially available inflexible Zinc-Air cells (Japanese Panasonic PR44 or PR2330) and applied to teaching experiments in schools (Hooi Y.K., Nakano, M., and Koga N. (2014), A Simple Oxygen Detector Using Zinc-Air batteries, J.chem.Educ.,91 (2)), 297-. However, the large-scale application of the metal-air battery in the oxygen intelligent packaging needs to overcome the defects of high cost, complex manufacturing method, difficult integration, conformal attachment and the like of the metal-air battery.
The existing indicative oxygen intelligent package is a passive oxygen sensor, needs workers to approach to a commodity to judge through visual observation, has large subjective influence, cannot carry out quantitative detection on the content of oxygen, and still needs to further investigate the safety when being used for food packaging; the high-sensitivity sensor capable of carrying out quantitative oxygen detection has the advantages of complex manufacturing method, high cost and unsuitability for low-cost packaging products. Printing technology has received wide attention as an additive manufacturing means for flexible electronic products in the last decade, but reports and products related to printing of oxygen smart packages have not been found yet.
Therefore, providing a metal-air battery with low cost, active interaction, high sensitivity, flexibility, simple process and wide application range, and a manufacturing method thereof, and exploring the application of the metal-air battery in oxygen intelligent packaging become technical problems to be overcome in the technical field.
Disclosure of Invention
The invention aims to provide a metal-air battery which is low in cost, active and interactive, high in sensitivity, flexible, simple in process and wide in application range, a manufacturing method of the metal-air battery and application of the metal-air battery in oxygen intelligent packaging.
The above purpose of the invention is realized by the following technical scheme:
scheme 1:
the utility model provides a flexible metal-air battery (coplanar), includes that air diffusion layer, the mass flow body of negative pole silver, the mass flow body of positive pole silver, metal anode printing ink layer, air cathode printing ink layer and gel electrolyte layer are supreme in proper order down: the cathode silver current collector and the anode silver current collector are positioned on the air diffusion layer, the metal anode ink layer is positioned on the anode silver current collector, the air cathode ink layer is positioned on the cathode silver current collector, the metal anode ink layer and the air cathode ink layer are arranged in parallel, and the gel electrolyte layer wraps the air cathode ink layer and the metal anode ink layer; a certain gap is arranged between the cathode silver current collector and the anode silver current collector.
Scheme 2:
the utility model provides a flexible metal-air battery (vertical type), includes flexible substrate, the mass flow body of negative pole silver, the mass flow body of positive pole silver, metal anode printing ink layer, air cathode printing ink layer and gel electrolyte layer, follows supreme being in proper order down: the flexible substrate, an anode silver current collector, a metal anode ink layer, a gel electrolyte layer, an air cathode ink layer and a cathode silver current collector, wherein the gel electrolyte layer is respectively connected with the metal anode ink layer and the air cathode ink layer, and the cathode silver current collector and the anode silver current collector are separated by the air cathode ink layer, the gel electrolyte layer and the metal anode ink layer.
Preferably, the metal is one or an alloy formed by more than two of zinc, aluminum, magnesium, lithium or iron in any proportion.
Preferably, the air cathode ink layer mainly comprises a carbonaceous material, an oxygen reduction catalyst and a binder; the carbonaceous material comprises one or a combination of at least two of carbon black, graphite, graphene, carbon nano tubes, nitrogen-doped carbon black, nitrogen-doped graphite, nitrogen-doped graphene and nitrogen-doped carbon nano tubes in any proportion; the oxygen reduction catalyst comprises one or a combination of at least two of transition metal oxide, conductive polymer, transition metal sulfide, transition metal carbonyl compound, noble metal oxide, metal composite oxide (spinel type, pyrochlore type and perovskite type), organic catalyst and the like in any proportion; the adhesive comprises one or the combination of at least two of polytetrafluoroethylene, carboxymethyl cellulose, styrene-butadiene rubber, polyethylene oxide, styrene-butadiene copolymer, sodium silicate and the like in any proportion.
Preferably, the gel electrolyte layer comprises a gel factor and an electrolyte; the gelator comprises high molecular polymers, such as: one or a combination of at least two of polyvinyl alcohol, polyacrylic acid, polyethylene glycol, gelatin, polyvinylidene fluoride hexa-fluoro phosphate, polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, epoxy derivatives, silicone derivatives and the like in any proportion; and small molecule gelators such as: cholest derivatives, saccharide derivatives, amide derivatives, two-component gelators, metal organic compounds, amino acid compounds, bi- (and) benzene compounds and the like.
Preferably, the electrolyte comprises one of alkali metal hydroxide (such as KOH, NaOH), ionic liquid, inorganic salt or a combination of at least two of the above in any proportion; wherein the ionic liquid is composed of an anion, the cation comprises one of imidazolium variant, pyrrolidinium variant, ammonium variant, pyridinium variant, phosphonium variant and sulfonium variant or a combination of at least two of the imidazolium variant, the pyrrolidinium variant, the ammonium variant, the pyridinium variant, the phosphonium variant and the sulfonium variant in any proportion, and the anion comprises one of chloride, bromide, acetate, tetrafluoroborate, trifluoroacetate, triflate, hexafluorophosphate, bis (trifluoromethanesulfonyl) amide, bis (fluorosulfonyl) imide and the like; the inorganic salt includes one of magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, sodium chloride, lithium chloride, etc.
Another object of the present invention is to provide the above metal-air battery and the manufacturing method.
The above purpose of the invention is realized by the following technical scheme:
preparation of a flexible metal-air cell comprising the steps of:
s1, weighing a certain amount of metal, adhesive and additive, adding the metal, adhesive and additive into a solvent, and stirring all the time to prepare a metal anode ink layer;
s2, weighing a certain amount of carbonaceous material, an oxygen reduction catalyst, a binder and an auxiliary agent, adding the weighed materials into a solvent, and stirring all the time in the process to prepare an air cathode ink layer;
s3, weighing a certain amount of gel factors, and adding the gel factors into an electrolyte aqueous solution to obtain a gel electrolyte layer with water retention property;
s4, respectively manufacturing an anode current collector, a cathode current collector and a battery external circuit on the surface of the porous printing material by adopting different printing, coating, pen drawing or seal modes by using commercially available conductive silver ink, and carrying out post-treatment;
s5, manufacturing a metal electrode on the surface of the anode silver current collector in S4 in a printing, coating, pen drawing or stamp mode by using the metal anode ink layer prepared in S1; after drying and film forming, using the air cathode ink layer prepared in S2 to manufacture an air electrode on the surface of the cathode silver current collector in S4 in a printing, coating, pen drawing or seal mode; and (4) after drying to form a film, using the gel electrolyte layer prepared in the step S3 to manufacture the gel electrolyte layer on the surfaces of the metal electrode and the air electrode by adopting a printing, coating, pen drawing or stamp mode, thus obtaining the flexible metal-air battery.
Preferably, the metal in S1 is an alloy formed by one or two of active metals such as zinc, aluminum, magnesium, lithium or iron in any proportion, and the morphology of the alloy includes zero-dimensional nano-micron particles, two-dimensional nano-micron sheets or formed mixtures; the adhesive comprises one or a mixture of two of polyethylene oxide, polyhydroxy ether, polyurethane, acrylonitrile/vinylidene chloride copolymer, polycarbonate, perfluorinated sulfonic acid resin, polyvinylpyrrolidone, polyvinylidene fluoride hexafluorophosphate, styrene-butadiene copolymer and sodium silicate in any proportion; the solvent comprises one or a combination of at least two of methanol, glycerol, deionized water, toluene, N-ethyl pyrrolidone, tetrahydrofuran, N-methyl pyrrolidone and the like in any proportion; the auxiliary additives include conductive agents such as carbon black and the like, surface tension modifiers such as BYK-024, dimethyl silicone oil, polyalkyl glycols, 2-ethylhexanol and the like, viscosity modifiers such as viscosity-removing agents (8043 viscosity-removing agents, 05-92 viscosity-removing agents, 653 viscosity-removing agents, 903 viscosity-removing agents, 49 viscosity-removing agents and the like) and thickeners (fumed silica, chrysotile and the like), viscosity modifiers such as ethanol, isopropanol, butyl acetate and the like, wetting agents such as dodecenyl glycol polyether, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether and the like, leveling agents such as polydimethylsiloxane, organically modified polysiloxane, acrylic resin, urea resin and the like, pH value modifiers such as ammonia water, triethylamine, triethanolamine and N, N-Dimethylaminoethanol (DMEA), 2-amino-2-methylpropanol (AMP), Diethylethanolamine (DEEA), and the like.
Preferably, the mass fraction of the metal in the metal anode ink layer in S1 is 40% -88.5%; the mass fraction of the adhesive in the metal anode ink layer is 0.5-15%; the mass fraction of the solvent in the metal anode ink layer is 10-50%; the mass fraction of the additive in the metal anode ink layer is 0-30%.
Preferably, the mass fraction of the metal in the metal anode ink layer in S1 is 60-80%; the mass fraction of the adhesive in the metal anode ink layer is 1-5%; the mass fraction of the solvent in the metal anode ink layer is 15-35%; the mass fraction of the additive in the metal anode ink layer is 4-20%.
Preferably, the carbonaceous material in S2 includes one or a combination of at least two of carbon black, graphite, graphene, carbon nanotubes, nitrogen-doped carbon black, nitrogen-doped graphite, nitrogen-doped graphene, and nitrogen-doped carbon nanotubes in any proportion; the oxygen reduction catalyst comprises one or a combination of at least two of transition metal oxide, conductive polymer, transition metal sulfide, transition metal carbonyl compound, noble metal oxide, metal composite oxide (spinel type, pyrochlore type and perovskite type), organic catalyst and the like in any proportion; the adhesive comprises one or the combination of at least two of polytetrafluoroethylene, carboxymethyl cellulose, styrene-butadiene rubber, polyethylene oxide, styrene-butadiene copolymer, sodium silicate and the like in any proportion; the solvent comprises one or the combination of at least two of ethylene glycol, toluene, deionized water, terpineol and the like in any proportion; the auxiliary additives include surface tension modifiers such as BYK-024, dimethyl silicone oil, polyalkyl glycols, 2-ethylhexanol, etc., viscosity modifiers such as viscosity-removing agents (8043 viscosity-removing agents, 05-92 viscosity-removing agents, 653 viscosity-removing agents, 903 viscosity-removing agents, 49 viscosity-removing agents, etc.) and thickeners (fumed silica, chrysotile, etc.), viscosity modifiers such as ethanol, isopropanol, butyl acetate, etc., wetting agents such as dodecenyl glycol polyether, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether, etc., leveling agents such as polydimethylsiloxane, organically modified polysiloxane, acrylic resin, urea-formaldehyde resin, etc., pH modifiers such as ammonia, triethylamine, triethanolamine and N, N-Dimethylaminoethanol (DMEA), 2-amino-2-methylpropanol (AMP), etc, Ink physical property regulators such as Diethylethanolamine (DEEA), and functional additives such as thermal expansion microcapsules such as Japanese pine thermal expansion microspheres F-230D, MXene, titanium carbide (Ti2CTx) MXene multilayer nanosheets XFK 06; the heat expansion microcapsules mainly play a role in adjusting the microstructure of the cathode and increasing the specific surface area of the cathode. MXene acts to enhance cathode conductivity as well as oxygen reduction activity.
Preferably, the mass fraction of the carbonaceous material in the air cathode ink layer in S2 is 10% to 70%; the mass fraction of the oxygen reduction catalyst in the air cathode ink layer is 10-40%; the mass fraction of the adhesive in the air cathode ink layer is 10-45%; the mass fraction of the solvent in the air cathode ink layer is 10-70%; the mass fraction of the additive in the ink layer of the air cathode is 0-30%.
Preferably, the mass fraction of the carbonaceous material in the air cathode ink layer in S2 is 25% to 50%; the mass fraction of the oxygen reduction catalyst in the air cathode ink layer is 15-25%; the mass fraction of the adhesive in the air cathode ink layer is 15-25%; the mass fraction of the solvent in the air cathode ink layer is 15-40%; the mass fraction of the additive in the air cathode ink layer is 5-20%.
Preferably, the gelator in S3 comprises a high molecular polymer, such as: one or a combination of at least two of polyvinyl alcohol, polyacrylic acid, polyethylene glycol, gelatin, polyvinylidene fluoride hexafluorophosphate, polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, epoxy derivatives, silicone derivatives and the like in any proportion; and small molecule gelators such as: cholest derivatives, saccharide derivatives, amide derivatives, two-component gel factors, metal organic compounds, amino acid compounds, bi (o) benzene compounds and the like.
Preferably, the electrolyte in S3 comprises one of alkali metal hydroxide (such as KOH, NaOH), ionic liquid, inorganic salt or a combination of at least two of them in any ratio; wherein the ionic liquid is composed of an anion and the cation comprises one of imidazolium variant, pyrrolidinium variant, ammonium variant, pyridinium variant, phosphonium variant and sulfonium variant or a combination of at least two of the imidazolium variant, the pyrrolidinium variant, the ammonium variant, the pyridinium variant, the phosphonium variant and the sulfonium variant in any proportion, and the anion comprises one of chloride, bromide, acetate, tetrafluoroborate, trifluoroacetate, triflate, hexafluorophosphate, bis (trifluoromethanesulfonyl) amide, bis (fluorosulfonyl) imide and the like; the inorganic salt includes one of magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, sodium chloride, lithium chloride, etc.
Preferably, the mass fraction of the gel factor in the gel electrolyte in S3 is 0.1-25%; the mass fraction of the electrolyte in the gel electrolyte is 8-70%; the mass fraction of the water in the gel electrolyte is 29.5-75%.
Preferably, the mass fraction of the gel factor in the gel electrolyte in S3 is 1-20%; the mass fraction of the electrolyte in the gel electrolyte is 15-60%; the mass fraction of water in the gel electrolyte is 39-65%.
Preferably, the porous substrate material in S4 comprises paper, breathable film or plastic, silicone or fabric; the printing mode includes but is not limited to offset printing, flexo printing, gravure printing, silk screen printing, ink jet printing or pad printing; the post-treatment is heating, the heating temperature is 60-120 ℃, and the heating time is 15-30 minutes.
Preferably, the drying treatment in S5 is heating, the heating temperature is between 60 ℃ and 120 ℃, and the heating time is 15-30 minutes.
It is a further object of the present invention to provide the use of the above flexible metal-air battery in oxygen smart packaging.
The above purpose of the invention is realized by the following technical scheme:
s1, connecting an electronic component for sensing response or data transmission with the flexible metal air battery manufactured in S5 to form a closed-loop circuit, and obtaining the flexible oxygen sensor;
and S2, attaching the printed flexible oxygen sensor manufactured in the S1 to the inner surface or the outer surface of the package to obtain the flexible oxygen intelligent package.
Preferably, the electronic component for sensing response or data transmission in S1 includes RFID, buzzer, LED or electronic color changing film.
Preferably, also included in S1 is an encapsulating material that is a gas-barrier flexible material, including gas-impermeable films, metal foils, polymer laminates with adhesives (adhesive backing), paper/plastic or film composites, and the like.
The electronic component can be prepared by a printing mode or a commercial component is selected.
The flexible metal-air battery can be packaged to be used as a disposable oxygen intelligent package and applied to scenes needing to monitor the oxygen content, such as cellars, underground mine cavities, oxygen impurity detection and the like.
The flexible metal-air battery has the beneficial effects that:
the flexible metal-air battery is low in cost, active interactive, high in sensitivity, flexible, simple in process and wide in application range.
The invention is further illustrated by the following figures and detailed description of the invention, which are not meant to limit the scope of the invention.
Drawings
Fig. 1-1 is a schematic structural view of a coplanar flexible zinc-air battery prepared in example 1 of the present invention.
Fig. 1-2 are schematic structural views of a vertical-type flexible aluminum-air battery prepared in example 2 of the present invention.
FIG. 2 is a graph showing the relationship between the oxygen concentration and the cell potential in application example 1 of the present invention.
Fig. 3 is a schematic structural view of a flexible oxygen sensor in application example 1 of the present invention.
Fig. 4 is a schematic structural view of a flexible oxygen sensor in application example 2 of the present invention.
Fig. 5 is a schematic structural diagram of an experimental device for testing the relationship between the output characteristics of the flexible metal-air battery and the oxygen content participating in the reaction in application example 3 of the present invention.
Name of major component
1 first air diffusion layer 2 first cathode silver current collector
3 first anode silver current collector 4 zinc anode ink layer
5 first air cathode ink layer 6 first gel electrolyte layer
1-1 flexible substrate 2-1 second cathode silver current collector
3-1 second anode silver current collector 4-1 aluminum anode ink layer
5-1 second air cathode ink layer 6-1 second gel electrolyte layer
1-2 second air diffusion layer 2-2 third cathode silver current collector
3-2 third anode silver current collector 4-2 lithium anode ink layer
5-2 third air cathode ink layer 6-2 third gel electrolyte layer
1-3 third air diffusion layer 2-3 fourth anode silver current collector
3-3 fourth cathode silver current collector 4-3 second zinc anode ink layer
5-3 fourth air cathode ink layer 6-3 fourth gel electrolyte layer
7 aluminum-plastic composite film packaging material 8 transparent plastic film
9 RFID tag 10 transparent plastic bag
11 transparent adhesive tape 12 voltmeter
1325 omega resistance 14 flexible metal air battery
15 disposable warmer containing iron powder
Detailed Description
Unless otherwise specified, the raw materials used in the following examples are commercially available raw materials and the methods used are not conventional in the art.
As shown in fig. 1-1, is a schematic structural view of a coplanar flexible zinc-air battery prepared in example 1 of the present invention; as shown in fig. 1-2, is a schematic structural diagram of a vertical flexible aluminum-air battery prepared in example 2 of the present invention; FIG. 2 is a graph showing the relationship between the oxygen concentration and the cell potential in application example 1 of the present invention; fig. 3 is a schematic structural view of a flexible oxygen sensor according to application example 1 of the present invention; fig. 4 is a schematic structural view of a flexible oxygen sensor according to application example 2 of the present invention; fig. 5 is a schematic structural diagram of an experimental apparatus for testing a relationship between output characteristics of a flexible metal-air battery and oxygen content participating in a reaction in application example 3 of the present invention; wherein, 1 is a first air diffusion layer, 2 is a first cathode silver current collector, 3 is a first anode silver current collector, 4 is a zinc anode ink layer, 5 is a first air cathode ink layer, 6 is a first gel electrolyte layer, 1-1 is a flexible substrate, 2-1 is a second cathode silver current collector, 3-1 is a second anode silver current collector, 4-1 is an aluminum anode ink layer, 5-1 is a second air cathode ink layer, 6-1 is a second gel electrolyte layer, 1-2 is a second air diffusion layer, 2-2 is a third cathode silver current collector, 3-2 is a third anode silver current collector, 4-2 is a lithium anode ink layer, 5-2 is a third air cathode ink layer, 6-2 is a third gel electrolyte layer, 1-3 is a third air diffusion layer, 2-3 is a fourth anode silver current collector, 3-3 is a fourth cathode silver current collector, 4-3 is a second zinc anode ink layer, 5-3 is a fourth air cathode ink layer, 6-3 is a fourth gel electrolyte layer, 7 is an aluminum-plastic composite film packaging material, 8 is a transparent plastic film, 9 is an RFID tag, 10 is a transparent plastic bag, 11 is a transparent adhesive tape, 12 is a voltmeter, 13 is a 25 omega resistor, 14 is a flexible metal air battery, and 15 is a disposable warmer containing iron powder.
Example 1 (coplanar type)
Step (1) preparation of zinc anode ink:
3.5g of zinc powder and 0.1g of polyvinylpyrrolidone (average molecular weight of 58000) are weighed and dispersed or dissolved in 0.9g of glycerol and 0.5g of methanol, the stirring speed is kept at 100-500 revolutions per minute in the process, and the zinc anode ink layer is obtained after the system is well dispersed;
step (2) preparation of first air cathode ink:
weighing 2.25g of graphite powder, 0.7g of polytetrafluoroethylene (Sigma Aldrich, less than or equal to 12 mu m), 0.05g of sodium silicate and 0.75g of cerium oxide, and dispersing or dissolving in 0.5g of terpineol and 0.75g of deionized water, wherein the stirring speed is kept at 100-500 revolutions per minute in the process, and the first air cathode ink is obtained after the system is well dispersed;
step (3) preparation of a first gel electrolyte:
weighing 2g of polyvinyl alcohol powder (with the average molecular weight of 146000-186000), dissolving in 10g of deionized water, and continuously stirring in a water bath at the heating temperature of 80-95 ℃ at the stirring speed of 200-500 revolutions per minute until the solution is in a clear state; reducing the stirring speed to 100-200 revolutions per minute, adding 8g of 1-ethyl-3-methylimidazole tetrafluoroborate under soft stirring, uniformly mixing, standing, removing bubbles, sealing, standing and cooling at normal temperature to obtain a first gel electrolyte with a certain water retention property;
step (4) preparation of conducting circuits and current collectors:
printing the surface of a fabric with a polytetrafluoroethylene back plate by using commercially available conductive silver ink in a screen printing mode, heating the fabric at 100 ℃ for 15 minutes, and then respectively manufacturing a first anode current collector, a first cathode current collector and a battery external circuit, wherein the sizes of the first anode current collector and the first cathode current collector are both 2cm multiplied by 2 cm;
and (5) preparing the flexible zinc-air battery:
printing a metal electrode (with the size of 1.8cm multiplied by 1.8 cm) on the upper layer of the anode silver current collector by using the zinc anode ink prepared in the step (1) in a screen printing mode (namely obtaining a zinc anode ink layer); heating for 15 minutes at 60 ℃, and printing an air electrode with the size of 1.8cm multiplied by 1.8cm on the upper layer of the cathode silver current collector by using the first air cathode ink prepared in the step (2) in a screen printing mode (namely obtaining a first air cathode ink layer); after heating for 15 minutes at 60 ℃, printing the gel electrolyte (with the size of 2cm multiplied by 4.3 cm) on the two electrodes by using the gel electrolyte prepared in the step (3) in a screen printing mode to obtain a first gel electrolyte layer, and covering, wrapping and connecting the two electrodes (comprising a metal electrode zinc anode ink layer and an air electrode first air cathode ink layer) of the battery by using the first gel electrolyte layer; installing RFID label or digital display meter with micro-processing chip; the open-circuit voltage of the single flexible zinc-air battery is 1.20V and the energy density is 300Wh/kg through testing and calculation.
The coplanar flexible zinc-air battery prepared in embodiment 1 of the present invention includes a first air diffusion layer 1, a first cathode silver current collector 2, a first anode silver current collector 3, a zinc anode ink layer 4, a first air cathode ink layer 5, and a first gel electrolyte layer 6, and sequentially from bottom to top: the first air diffusion layer 1 is a fabric with a polytetrafluoroethylene back plate, a first cathode silver current collector 2 and a first anode silver current collector 3 (printed conductive silver ink as a lead and the like) are positioned on the first air diffusion layer 1, a zinc anode ink layer 4 is positioned on the first anode silver current collector 3, a first air cathode ink layer 5 is positioned on the first cathode silver current collector 2, the zinc anode ink layer 4 and the first air cathode ink layer 5 are arranged in parallel (printed metal ink and air cathode ink are reserved with a certain distance), and a first gel electrolyte layer 6 (hydrogel of polyvinyl alcohol and 1-ethyl-3-methylimidazolium tetrafluoroborate) wraps and connects the first cathode silver current collector 2, the first air cathode ink layer 5, the first anode silver current collector 3 and the zinc anode ink layer 4 together.
Example 2 (vertical type)
Step (1) preparation of aluminum anode ink:
weighing 3.5g of aluminum powder and 0.1g of polyvinylpyrrolidone (average molecular weight of 58000), dispersing or dissolving in 0.9g of glycerol and 0.5g of methanol, keeping the stirring speed at 100-500 revolutions per minute in the process, and obtaining the aluminum anode ink after the system is well dispersed;
step (2) preparation of second air cathode ink:
weighing 2.25g of graphite powder, 0.7g of polytetrafluoroethylene (Sigma Aldrich, less than or equal to 12 mu m), 0.05g of sodium silicate and 0.75g of cerium oxide, and dispersing or dissolving in 0.5g of terpineol and 0.75g of deionized water, wherein the stirring speed is kept at 100-500 revolutions per minute in the process, and the second air cathode ink is obtained after the system is well dispersed;
step (3) preparation of a second gel electrolyte:
weighing 2g of polyvinyl alcohol powder (with the average molecular weight of 146000-186000), dissolving in 10g of deionized water, and continuously stirring in a water bath at the heating temperature of 80-95 ℃ at the stirring speed of 200-500 revolutions per minute until the solution is in a clear state; reducing the stirring speed to 100-200 revolutions per minute, adding 8g of 1-ethyl-3-methylimidazole tetrafluoroborate under soft stirring, uniformly mixing, standing, removing bubbles, sealing, standing and cooling at normal temperature to obtain a second gel electrolyte with a certain water retention property;
step (4) preparation of conducting circuits and current collectors:
coating the surface of Polyester (PET) by using commercially available conductive silver ink in a coating mode, heating at 100 ℃ for 15 minutes, and then manufacturing a second anode current collector and a battery external circuit, wherein the size of the second anode current collector is 2cm multiplied by 2 cm;
and (5) preparing the flexible aluminum-air battery:
coating a metal electrode with the size of 1.8cm multiplied by 1.8cm on the upper layer of the second anode silver current collector by using the aluminum anode ink prepared in the step (1) (namely obtaining the aluminum anode ink layer); after heating at 60 ℃ for 15 minutes, coating a second gel electrolyte layer with the size of 1.8cm multiplied by 1.8cm on the electrode by using the second gel electrolyte prepared in the step (3) in a coating mode; coating an air electrode with the size of 1.8cm multiplied by 1.8cm on the upper layer of the gel electrolyte layer by using the second air cathode ink prepared in the step (2) (namely obtaining a second air cathode ink layer); after heating for 15 minutes at 60 ℃, coating a second cathode current collector with the size of 2cm multiplied by 2cm by using conductive silver ink in a coating mode; installing RFID label or digital display meter with micro-processing chip; the open-circuit voltage of the single flexible aluminum-air battery is 2.0V and the energy density is 600Wh/kg through testing and calculation.
The vertical flexible aluminum-air battery prepared in embodiment 2 of the invention comprises a flexible substrate 1-1 of Polyester (PET), a second cathode silver current collector 2-1, a second anode silver current collector 3-1, an aluminum anode ink layer 4-1, a second air cathode ink layer 5-1 and a second gel electrolyte layer 6-1, and the following components are sequentially arranged from bottom to top: the flexible substrate 1-1 is Polyester (PET), the second anode silver current collector 3-1, the aluminum anode ink layer 4-1, the second gel electrolyte layer 6-1 (hydrogel of polyvinyl alcohol and 1-ethyl-3-methylimidazolium tetrafluoroborate) is sandwiched between the aluminum anode ink layer 4-1 and the second air cathode ink layer 5-1, the second air cathode ink layer 5-1 and the second cathode silver current collector 2-1; the second anode silver current collector 3-1 is printed on the flexible substrate 1-1 made of Polyester (PET), then the aluminum anode ink layer 4-1 is printed on the second anode silver current collector 3-1, the second gel electrolyte layer 6-1 (hydrogel of polyvinyl alcohol and 1-ethyl-3-methylimidazolium tetrafluoroborate) is printed on the aluminum anode ink layer 4-1, the second air cathode ink layer 5-1 is positioned on the second gel electrolyte layer 6-1 (hydrogel of polyvinyl alcohol and 1-ethyl-3-methylimidazolium tetrafluoroborate), and the second cathode silver current collector 2-1 is positioned on the uppermost layer, namely printed on the second air cathode ink layer 5-1.
Example 3 (coplanar type)
Step (1) preparation of lithium anode ink:
weighing 3.5g of lithium powder and 0.1g of polyvinylpyrrolidone (average molecular weight of 58000), dispersing or dissolving in 0.9g of glycerol and 0.5g of methanol, keeping the stirring speed at 100-500 revolutions per minute in the process, obtaining lithium anode ink after the system is well dispersed, and filling the lithium anode ink into an empty Mark pen for later use;
preparing air cathode ink in step (2):
weighing 2.25g of graphite powder, 0.7g of polytetrafluoroethylene (Sigma Aldrich, less than or equal to 12 mu m), 0.05g of sodium silicate and 0.75g of cerium oxide, and dispersing or dissolving in 0.5g of terpineol and 0.75g of deionized water, wherein the stirring speed is kept at 100-500 revolutions per minute in the process, and after the system is well dispersed, obtaining air cathode ink, and filling the air cathode ink into an empty Mark pen for later use;
preparing a gel electrolyte in the step (3):
weighing 2g of polyvinyl alcohol powder (with the average molecular weight of 146000-186000), dissolving in 10g of deionized water, and continuously stirring in a water bath at the heating temperature of 80-95 ℃ at the stirring speed of 200-500 revolutions per minute until the solution is in a clear state; reducing the stirring speed to 100-200 revolutions per minute, adding 8g of 1-ethyl-3-methylimidazole tetrafluoroborate under soft stirring, uniformly mixing, standing, removing bubbles, cooling for 30 minutes at normal temperature to obtain gel electrolyte, and filling the gel electrolyte into an empty Mark pen for later use;
step (4) preparation of conducting circuits and current collectors:
printing the surface of A4 paper by using a commercial conductive silver ink in a screen printing mode, heating the printed paper at 100 ℃ for 15 minutes, and respectively manufacturing a third anode current collector, a third cathode current collector and a battery external circuit, wherein the sizes of the anode current collector and the cathode current collector are 2cm multiplied by 2 cm;
and (5) preparing the flexible lithium-air battery:
drawing a metal electrode (namely a lithium anode ink layer) with the size of 1.8cm multiplied by 1.8cm on the upper layer of an anode silver current collector by using the lithium anode ink prepared in the step (1) in a direct writing mode, and heating for 20 minutes at the temperature of 60 ℃; drawing an air electrode (namely a third air cathode ink layer) with the size of 1.8cm multiplied by 1.8cm on the upper layer of a cathode silver current collector by using the air cathode ink prepared in the step (2) in a direct writing mode, and heating for 15 minutes at 60 ℃; or drawing an air electrode with the size of 1.8cm multiplied by 1.8cm on the upper layer of the third cathode silver current collector by using an 8B pencil (namely obtaining a third air cathode ink layer);
then, drawing the gel electrolyte with the size of 2cm multiplied by 4.3cm (namely a third gel electrolyte layer) on the two electrodes by using the gel electrolyte prepared in the step (3) in a direct writing mode, and covering, wrapping and connecting the two electrodes of the battery by using the gel electrolyte layer; installing LED color lamps, small music boxes, buzzers and the like; the open-circuit voltage of the single-section flexible lithium-air battery is 2.0V and the energy density is 387Wh/kg through testing and calculation.
The open type flexible metal-air battery manufactured in the direct writing/pen drawing mode can be applied to creative products such as cultural creative electronics, electronic circuit design and personal creative DIY electronics, and scientific knowledge and ideas or activities such as physical teaching are propagated in a form which is easily accepted by the public.
Example 4 (coplanar type)
Step (1) preparation of zinc anode ink:
weighing 3g of zinc powder, 0.25g of polyvinylpyrrolidone (average molecular weight of 58000) and 1g of carbon black, and dispersing or dissolving in 0.5g of glycerol and 0.25g of methanol, wherein the stirring speed is kept at 100-500 revolutions per minute in the process, and the zinc anode ink layer is obtained after the system is well dispersed;
step (2) preparation of first air cathode ink:
weighing 2.5g of graphite powder, 0.7g of polytetrafluoroethylene (Sigma Aldrich, less than or equal to 12 mu m), 0.05g of sodium silicate, 0.75g of cerium oxide and 0.25g of titanium carbide multilayer nanosheet XFK06, dispersing or dissolving in 0.3g of terpineol and 0.45g of deionized water, keeping the stirring speed at 100-500 revolutions per minute in the process, and obtaining the first air cathode ink after the system is well dispersed;
step (3) preparation of a first gel electrolyte:
weighing 0.2g of polyvinyl alcohol powder (with the average molecular weight of 146000-186000), dissolving in 7.8g of deionized water, and continuously stirring in a water bath at the heating temperature of 80-95 ℃ at the stirring speed of 200-500 revolutions per minute until the solution is in a clear state; reducing the stirring speed to 100-200 revolutions per minute, adding 12g of 1-ethyl-3-methylimidazole tetrafluoroborate under soft stirring, uniformly mixing, standing, removing bubbles, sealing, standing and cooling at normal temperature to obtain a first gel electrolyte with a certain water retention property;
step (4) preparation of conducting circuits and current collectors:
printing the surface of a fabric with a polytetrafluoroethylene back plate by using commercially available conductive silver ink in a screen printing mode, heating the fabric at 100 ℃ for 15 minutes, and then respectively manufacturing a first anode current collector, a first cathode current collector and a battery external circuit, wherein the sizes of the first anode current collector and the first cathode current collector are both 2cm multiplied by 2 cm;
and (5) preparing the flexible zinc-air battery:
printing a metal electrode (with the size of 1.8cm multiplied by 1.8 cm) on the upper layer of the anode silver current collector by using the zinc anode ink prepared in the step (1) in a screen printing mode (namely obtaining a zinc anode ink layer); heating for 15 minutes at 60 ℃, and printing an air electrode with the size of 1.8cm multiplied by 1.8cm on the upper layer of the cathode silver current collector by using the first air cathode ink prepared in the step (2) in a screen printing mode (namely obtaining a first air cathode ink layer); after heating for 15 minutes at 60 ℃, printing the gel electrolyte with the size of 2cm multiplied by 4.3cm (namely a first gel electrolyte layer) on the two electrodes by using the gel electrolyte prepared in the step (3) in a screen printing mode, and covering, wrapping and connecting the two electrodes (a metal electrode and an air electrode) of the battery by using the first gel electrolyte layer; installing RFID label or digital display meter with micro-processing chip; the open-circuit voltage of the single flexible zinc-air battery is 1.20V and the energy density is 300Wh/kg through testing and calculation.
The coplanar flexible zinc-air battery prepared in embodiment 1 of the present invention includes a first air diffusion layer 1, a first cathode silver current collector 2, a first anode silver current collector 3, a zinc anode ink layer 4, a first air cathode ink layer 5, and a first gel electrolyte layer 6, and sequentially from bottom to top: the first air diffusion layer 1 is a fabric with a polytetrafluoroethylene back plate, a first cathode silver current collector 2 and a first anode silver current collector 3 (printed conductive silver ink as a lead and the like) are positioned on the first air diffusion layer 1, a zinc anode ink layer 4 is positioned on the first anode silver current collector 3, a first air cathode ink layer 5 is positioned on the first cathode silver current collector 2, the zinc anode ink layer 4 and the first air cathode ink layer 5 are arranged in parallel (printed metal ink and air cathode ink are reserved with a certain distance), and a first gel electrolyte layer 6 (hydrogel of polyvinyl alcohol and 1-ethyl-3-methylimidazolium tetrafluoroborate) wraps and connects the first cathode silver current collector 2, the first air cathode ink layer 5, the first anode silver current collector 3 and the zinc anode ink layer 4 together.
Example 5 (coplanar type)
Step (1) preparation of lithium anode ink:
weighing 2g of lithium powder, 0.75g of polyvinylpyrrolidone (average molecular weight of 58000) and 1.5g of polyalkyl glycol, dispersing or dissolving in 0.5g of glycerol and 0.25g of methanol, keeping the stirring speed at 100-500 revolutions per minute in the process, obtaining lithium anode ink after the system is well dispersed, and filling the lithium anode ink into an empty Mark pen for later use;
preparing air cathode ink in step (2):
weighing 2.5g of graphite powder, 0.47g of polytetrafluoroethylene (Sigma Aldrich, less than or equal to 12 mu m), 0.03g of sodium silicate, 0.5g of cerium oxide and 1g of Japanese pine thermal expansion microspheres F-230D, dispersing or dissolving in 0.2g of terpineol and 0.3g of deionized water, keeping the stirring speed at 100-500 revolutions per minute in the process, obtaining the air cathode ink after the system is well dispersed, and filling the air cathode ink into an empty Mark pen for standby;
preparing a gel electrolyte in the step (3):
weighing 3g of polyvinyl alcohol powder (with the average molecular weight of 146000-186000), dissolving in 12g of deionized water, and continuously stirring in a water bath at the heating temperature of 80-95 ℃ at the stirring speed of 200-500 revolutions per minute until the solution is in a clear state; reducing the stirring speed to 100-200 revolutions per minute, adding 5g of 1-ethyl-3-methylimidazole tetrafluoroborate under soft stirring, uniformly mixing, standing, removing bubbles, cooling for 30 minutes at normal temperature to obtain gel electrolyte, and filling the gel electrolyte into an empty Mark pen for later use;
step (4) preparation of conducting circuits and current collectors:
printing the surface of A4 paper by using a commercial conductive silver ink in a screen printing mode, heating the printed paper at 100 ℃ for 15 minutes, and respectively manufacturing a third anode current collector, a third cathode current collector and a battery external circuit, wherein the sizes of the anode current collector and the cathode current collector are 2cm multiplied by 2 cm;
and (5) preparing the flexible lithium-air battery:
drawing a metal electrode (namely a lithium anode ink layer) with the size of 1.8cm multiplied by 1.8cm on the upper layer of an anode silver current collector by using the lithium anode ink prepared in the step (1) in a direct writing mode, and heating for 20 minutes at the temperature of 60 ℃; drawing an air electrode (namely a third air cathode ink layer) with the size of 1.8cm multiplied by 1.8cm on the upper layer of a cathode silver current collector by using the air cathode ink prepared in the step (2) in a direct writing mode, and heating for 15 minutes at 60 ℃; or drawing an air electrode with the size of 1.8cm multiplied by 1.8cm on the upper layer of the third cathode silver current collector by using an 8B pencil (namely obtaining a third air cathode ink layer);
then, drawing the gel electrolyte with the size of 2cm multiplied by 4.3cm (namely a third gel electrolyte layer) on the two electrodes by using the gel electrolyte prepared in the step (3) in a direct writing mode, and covering, wrapping and connecting the two electrodes of the battery by using the gel electrolyte layer; installing LED color lamps, small music boxes, buzzers and the like; the open-circuit voltage of the single-section flexible lithium-air battery is 2.0V and the energy density is 387Wh/kg through testing and calculation.
The open type flexible metal-air battery manufactured in the direct writing/pen drawing mode can be applied to creative products such as cultural creative electronics, electronic circuit design and personal creative DIY electronics, and scientific knowledge and ideas or activities such as physical teaching are propagated in a form which is easily accepted by the public.
Application example 1: preparation of flexible oxygen sensor
The oxygen concentration required by the human body for normal activities is 19.5% -23.5%, so for human safety, the oxygen concentration cannot be lower than 19.5%, and an alarm must be given when the oxygen-enriched concentration exceeds 23.5%. When the oxygen concentration is reduced to 15% -19%, people feel hard and the working capacity is reduced; when the oxygen concentration is reduced to 12-14%, the person can breathe quickly, the pulse is accelerated, and the coordination ability and the perception judgment ability are reduced; when the oxygen concentration is reduced to 10-12%, the breathing of the human body is weakened, and the lips are bluish purple; when the oxygen concentration is reduced to 8-10%, people can be unconscious, faint, dark-colored, grey-colored, nausea and vomiting; when the oxygen concentration is reduced to 6-8%, death is caused when the oxygen deficiency time exceeds 8 minutes; when the oxygen concentration is reduced to 4-6%, people can be coma, twitch, stop breathing and even die within a few tens of seconds of the hypoxia time.
In order to ensure the physical health and life safety of workers and prevent the occurrence of anoxia; in all places which can cause oxygen deficiency, such as cabins, underground projects, submarines, tunnels and the like, the oxygen concentration of the environment of the ship must be checked regularly. For example, in a mine, the measurement of the oxygen concentration is not only to ensure the life health and safety of miners, but also an important parameter for underground explosion prevention, so that the oxygen concentration in the intake air of a mining working face must be ensured not to be lower than 20%, and the oxygen concentration of the underground working face must be detected at any time. After the flexible metal-air battery prepared by printing or coating method in example 1 or example 2 was packaged, it was used as an oxygen sensor: even if the aluminum-plastic composite film completely covers the back of the air diffusion layer, hot pressing is carried out on the edge of the air diffusion layer, the periphery is sealed to prevent air from entering, and when the air diffusion layer is used, the hot-pressed sealing position at the periphery is opened to introduce air; the flexible co-shaped adhesive has the advantages of high production efficiency, low cost, disposable property, flexibility, co-shaped adhesion, portability, environmental friendliness and the like, and the coal reserves in China are abundant, so that the flexible co-shaped adhesive can be popularized and applied to the scenes, and the prospect is very wide.
The flexible oxygen sensor prepared by the application embodiment 1 comprises a flexible lithium air battery and an aluminum-plastic composite film 7 serving as a packaging material; the flexible lithium-air battery comprises a second air diffusion layer 1-2 nylon (base material, material has air permeability and good printability), a third cathode silver current collector 2-2, a third air cathode ink layer 5-2, a lithium anode ink layer 4-2, a third anode silver current collector 3-2 and a third gel electrolyte layer 6-2; the third gel electrolyte layer 6-2 (hydrogel of polyvinyl alcohol and 1-ethyl-3-methylimidazolium tetrafluoroborate) wraps and connects the third cathode silver current collector 2-2, the third air cathode ink layer 5-2, the third anode silver current collector 3-2 and the lithium anode ink layer 4-2 together, and the packaging material 7 seals the air diffusion layer of the flexible lithium-air battery.
Application example 2
Oxygen is an important factor for normal respiration of plants, and insufficient oxygen inhibits respiration of plants. When fruits and vegetables are stored or transported, the fruits and vegetables are placed in a place with high oxygen concentration, the respiration of the fruits and vegetables is vigorous, a large amount of organic matters are consumed, a large amount of heat is released, and the fruits and vegetables are easy to rot; the oxygen is less, the respiration is weak, the consumption of organic matters can be reduced, and the fresh-keeping of fruits and vegetables is facilitated. Therefore, the oxygen concentration must be constantly detected during the storage or transportation of the fruits and vegetables, and the oxygen concentration is ensured to be between 1 and 10 percent, preferably to be kept at about 5 percent, so as to ensure the quality and the transportation safety of the fruits and vegetables. The flexible metal air battery prepared by printing or coating in the embodiment 1 and the embodiment 2 is integrated in the relatively sealed package to be used as an oxygen sensor and connected with an information and data electronic component, such as a printable electronic component RFID label and the like, and is directly printed and connected with the information and data electronic component, and a non-printable electronic component LED lamp, a buzzer, a digital display meter and the like are bonded by using a conductive copper foil or a conductive adhesive, so that the development trend of IOT is met, and the quality of the product is guaranteed. The data generated in the transportation process can also clarify the claim and payment problems generated by product damage among sellers, transportation companies and consumers, and avoid unnecessary disputes. The flexible oxygen sensor of the present invention can be used for, but is not limited to, detecting whether the food package is air-leaked or not, so as to timely find out the problems of possible spoilage of the food in the package, and the like.
The flexible oxygen sensor prepared in the application embodiment 2 of the invention comprises a flexible zinc-air battery, a transparent plastic film 8 and an RFID label 9; the flexible zinc-air battery comprises a third air diffusion layer 1-3 (which is also part of a vacuum food outer package and only uses a breathable material at a printed or coated cathode for gas diffusion), a fourth anode silver current collector 2-3, a fourth air cathode ink layer 5-3, a second zinc anode ink layer 4-3, a fourth cathode silver current collector 3-3 and a fourth gel electrolyte layer 6-3; and a fourth gel electrolyte layer 6-3 (hydrogel of polyvinyl alcohol and 1-ethyl-3-methylimidazole tetrafluoroborate) wraps and connects a fourth anode silver current collector 2-3, a second zinc anode ink layer 4-3, a fourth cathode silver current collector 3-3 and a fourth air cathode ink layer 5-3 together, an RFID label 9 is connected with the flexible zinc-air battery, and the periphery of the transparent plastic film 8, which is in contact with the outer package, is sealed so as to keep visualization.
Application example 3
The printed metal-air battery is used as a power supply to be connected with an external electronic component or an electrical testing device (such as an ammeter and a voltmeter), active qualitative or quantitative analysis is carried out on the oxygen content in a package through the change of the working state of the external electronic component, and the external connected electronic component comprises a commercial component or a device prepared by using a printing technology, such as: RFID label, LED pilot lamp, bee calling organ, electrochromic film etc..
The flexible metal-air battery prepared in example 1 or example 2 of the present invention, a 25 Ω resistor, a voltmeter, a transparent plastic bag, a transparent adhesive tape, a disposable warmer containing iron powder, and the like were assembled into an apparatus for experiments, in which the warmer and the flexible metal-air battery were put together in a plastic bag, the plastic bag was inflated with air, the plastic bag was sealed, and the opening of the bag around the lead of the voltmeter was sealed with the transparent adhesive tape so as to prevent air from entering or leaking. This is a principle verification example of the use of the flexible metal-air battery as an oxygen sensor such as in application example 1 and application example 2.
Fig. 5 is a schematic structural diagram of an experimental apparatus for testing a relationship between output characteristics of a flexible metal-air battery and oxygen content participating in a reaction in application example 3 of the present invention; the device for verifying that the flexible metal-air battery can be used as a self-powered oxygen sensor comprises a flexible metal-air battery 14 (a flexible zinc-air battery or a flexible aluminum-air battery), a 25 omega resistor 13, a voltmeter 12, a transparent plastic bag 10, a transparent adhesive tape 11 and a disposable warmer 15 containing iron powder; a flexible metal-air battery 14, a disposable warmer containing iron powder 15 and a 25 omega resistor 13 are placed in a transparent plastic bag 10, wherein the flexible metal-air battery 14 and the 25 omega resistor 13 are connected to form a closed loop circuit, a voltmeter 12 is connected in parallel at two ends of the 25 omega resistor 13, the disposable warmer containing iron powder 15 is placed near the flexible metal-air battery 14, a transparent adhesive tape 11 is used for sealing the bag mouth of the transparent plastic bag 10, and especially, the bag mouth around a lead wire of the voltmeter and any other possible air leakage positions need to be strictly sealed.
The flexible metal-air battery has the following advantages:
(1) the current collector, the circuit, the electrode and the electrolyte are all printed to manufacture the flexible metal air battery, besides the printing mode, the flexible metal air battery can also be coated, is suitable for the production of the metal air battery with high efficiency, large area and flexibility, can also creatively present the circuit by using pen drawing, seal design and other modes, and can be applied to products or scenes with creative demands.
(2) The metal-air battery manufactured by the method belongs to a flexible metal-air battery, has the properties of being bendable and foldable and the like, can realize large-scale mass production by printing, coating and the like, and can stably work in the service life proved by experiments; wherein the open-circuit voltage of the flexible zinc-air battery is 1.20V-1.50V, and the energy density is 300 Wh/kg-682 Wh/kg; the open-circuit voltage of the flexible aluminum air battery is 2.0V-2.5V, and the energy density is 600 Wh/kg-2000 Wh/kg; the open circuit voltage of the flexible lithium-air battery is 2.0V-2.9V; the energy density is 300 Wh/kg-2500 Wh/kg.
(3) The results after the design experiment show that: the flexible metal-air battery manufactured in the above way is used as an oxygen sensor for detectionThe accuracy of the oxygen concentration is: less than +/-0.7 percent, and the oxygen content (concentration) in the range of 0-50 percent (volume oxygen) and the logarithm value of the battery potential are in a linear relation, as shown in figure 2 (taking a flexible zinc-air battery as an example), which shows that the voltage or current change caused by the change of the oxygen content in the range can be transmitted to the outside by an electronic device through the known linear relation after being set by related software, so that the purpose of monitoring the oxygen content is achieved; wherein, the flexible zinc-air battery manufactured in the above way is taken as an example, the current density is 2.0mA/cm2～20mA/cm2When discharging, the discharging time of the battery is about 10.5 h-72 h, and the lower the current density, the longer the discharging time; the flexibility of the material is tested by a bending test, and the test shows that: the cells were discharged at the same current density before and after the bending, and the cells exhibited substantially uniform electrical properties in terms of open circuit voltage, discharge time, and the like.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention are equivalent to or changed within the technical scope of the present invention.
Claims (10)
1. A flexible metal-air cell, characterized by: including air diffusion layer, the silver mass flow body of negative pole, the silver mass flow body of positive pole, metal anode printing ink layer, air cathode printing ink layer and gel electrolyte layer, follow supreme being in proper order down: the cathode silver current collector and the anode silver current collector are positioned on the air diffusion layer, the metal anode ink layer is positioned on the anode silver current collector, the air cathode ink layer is positioned on the cathode silver current collector, the metal anode ink layer and the air cathode ink layer are arranged in parallel, and the gel electrolyte layer wraps the air cathode ink layer and the metal anode ink layer; a gap is arranged between the cathode silver current collector and the anode silver current collector.
2. A flexible metal-air cell, characterized by: including flexible substrate, the silver mass flow body of negative pole, the silver mass flow body of positive pole, metal anode printing ink layer, air cathode printing ink layer and gel electrolyte layer, follow supreme being in proper order down: the flexible substrate, an anode silver current collector, a metal anode ink layer, a gel electrolyte layer, an air cathode ink layer and a cathode silver current collector, wherein the gel electrolyte layer is respectively connected with the metal anode ink layer and the air cathode ink layer, and the cathode silver current collector and the anode silver current collector are separated by the air cathode ink layer, the gel electrolyte layer and the metal anode ink layer.
3. The flexible metal-air cell of claim 1 or 2, wherein: the metal in the metal anode ink layer is an alloy formed by one or more than two of zinc, aluminum, magnesium, lithium or iron in any proportion; the air cathode ink layer mainly comprises a carbonaceous material, an oxygen reduction catalyst and a binder; the carbonaceous material comprises one or a combination of at least two of carbon black, graphite, graphene, carbon nano tubes, nitrogen-doped carbon black, nitrogen-doped graphite, nitrogen-doped graphene and nitrogen-doped carbon nano tubes in any proportion; the oxygen reduction catalyst comprises one or a combination of at least two of transition metal oxide, conductive polymer, transition metal sulfide, transition metal carbonyl compound, noble metal oxide, metal composite oxide (spinel type, pyrochlore type and perovskite type), organic catalyst and the like in any proportion; the adhesive comprises one or the combination of at least two of polytetrafluoroethylene, carboxymethyl cellulose, styrene-butadiene rubber, polyethylene oxide, styrene-butadiene copolymer, sodium silicate and the like in any proportion.
4. The flexible metal-air cell of claim 3, wherein: the gel electrolyte layer comprises a gel factor and an electrolyte; the gelator comprises high molecular polymer: one or a combination of at least two of polyvinyl alcohol, polyacrylic acid, polyethylene glycol, gelatin, polyvinylidene fluoride hexafluorophosphate, polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, epoxy derivatives or silicone derivatives in any proportion; or: small molecule gelator: cholesteric derivatives, saccharide derivatives, amide derivatives, bi-component gelators, metal organic compounds, amino acid compounds or bi- (and) benzene compounds; the electrolyte comprises one or a combination of at least two of alkali metal hydroxide, ionic liquid and inorganic salt in any proportion; wherein the ionic liquid is composed of an anion and the cation comprises one of an imidazolium variant, a pyrrolidinium variant, an ammonium variant, a pyridinium variant, a phosphonium variant or a sulfonium variant or a combination of at least two of the imidazolium variant, the pyrrolidinium variant, the ammonium variant, the pyridinium variant, the phosphonium variant or the sulfonium variant in any ratio, and the anion comprises one of chloride, bromide, acetate, tetrafluoroborate, trifluoroacetate, triflate, hexafluorophosphate, bis (trifluoromethanesulfonyl) amide or bis (fluorosulfonyl) imide; the inorganic salt comprises one of magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, sodium chloride or lithium chloride.
5. Preparation of a flexible metal-air cell comprising the steps of:
s1: weighing a certain amount of metal, adhesive and additive, adding the metal, adhesive and additive into a solvent, and stirring all the time in the process to prepare the metal anode ink;
s2: weighing a certain amount of carbonaceous material, an oxygen reduction catalyst, a binder and an auxiliary additive, adding the weighed materials into a solvent, and stirring all the time in the process to prepare the air cathode ink;
s3: weighing a certain amount of gel factors, and adding the gel factors into an electrolyte aqueous solution to obtain gel electrolyte ink with water retention property;
s4: respectively manufacturing an anode current collector, a cathode current collector and a battery external circuit on the surface of the porous printing material by adopting different printing, coating, pen drawing or seal modes by using commercially available conductive silver ink, and performing post-treatment;
s5: manufacturing a metal electrode on the surface of the anode silver current collector in S4 by using the metal anode ink prepared in S1 in a printing, coating, pen drawing or stamp mode; after drying and film forming, using the air cathode ink prepared in S2 to manufacture an air electrode on the surface of the cathode silver current collector in S4 in a printing, coating, pen drawing or seal mode; and (3) after drying to form a film, using the gel electrolyte ink prepared in S3 to prepare a gel electrolyte on the surfaces of the metal electrode and the air electrode in a printing, coating, pen drawing or stamp mode, thus obtaining the flexible metal-air battery.
6. Preparation of a flexible metal-air cell according to claim 5, characterized in that: the metal in S1 is an alloy formed by one or more than two active metals of zinc, aluminum, magnesium, lithium or iron and the like in any proportion, and the shape of the alloy comprises zero-dimensional nano-micron particles, two-dimensional nano-micron sheets or formed mixtures; the adhesive comprises one or a mixture of two of polyethylene oxide, polyhydroxy ether, polyurethane, acrylonitrile/vinylidene chloride copolymer, polycarbonate, perfluorinated sulfonic acid resin, polyvinylpyrrolidone, polyvinylidene fluoride hexafluorophosphate, styrene-butadiene copolymer and sodium silicate in any proportion; the solvent comprises one or the combination of at least two of methanol, glycerol, deionized water, toluene, N-ethyl pyrrolidone, tetrahydrofuran, N-methyl pyrrolidone and the like in any proportion; the auxiliary additive comprises conductive agent such as carbon black, surface tension regulator such as BYK-024, dimethyl silicone oil, polyalkyl glycol and 2-ethyl hexanol, and viscosity regulator is viscosity-removing agent: 8043 adhesive removing agent, 05-92 adhesive removing agent, 653 adhesive removing agent, 903 adhesive removing agent, 49 adhesive removing agent or thickener: fumed silica, chrysotile, viscosity modifiers such as ethanol, isopropanol, butyl acetate and the like, wetting agents such as dodecenyleneglycol polyether, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether and the like, leveling agents such as polydimethylsiloxane, organically modified polysiloxane, acrylic resin, urea resin or pH modifiers such as ammonia, triethylamine, triethanolamine and N, N-dimethylaminoethanol, 2-amino-2-methylpropanol, diethylethanolamine.
7. Preparation of a flexible metal-air cell according to claim 5, characterized in that: the mass fraction of the metal in the S1 in the anode ink is 40-88.5%; the mass fraction of the adhesive in the anode ink is 0.5-15%; the mass fraction of the solvent in the anode ink is 10-50%; the mass fraction of the additive in the anode ink is 0-30%.
8. Preparation of a flexible metal-air cell according to claim 5, characterized in that: the mass fraction of the metal in the anode ink in S1 is 60-80%; the mass fraction of the adhesive in the anode ink is 1-5%; the mass fraction of the solvent in the anode ink is 15-35%; the mass fraction of the additive agent in the anode ink is 4-20%.
9. Preparation of a flexible metal-air cell according to claim 5, characterized in that: the carbonaceous material in the S2 comprises one or a combination of at least two of carbon black, graphite, graphene, carbon nano tubes, nitrogen-doped carbon black, nitrogen-doped graphite, nitrogen-doped graphene and nitrogen-doped carbon nano tubes in any proportion; the oxygen reduction catalyst comprises one or the combination of at least two of transition metal oxide, conductive polymer, transition metal sulfide, transition metal carbonyl compound, noble metal oxide, metal composite oxide and organic catalyst in any proportion; the adhesive comprises one or the combination of at least two of polytetrafluoroethylene, carboxymethyl cellulose, styrene-butadiene rubber, polyethylene oxide, styrene-butadiene copolymer and sodium silicate in any proportion; the solvent comprises one or the combination of at least two of glycol, toluene, deionized water and terpineol in any proportion; the adjuvant additives include surface tension modifiers such as: BYK-024, dimethyl silicone oil, polyalkylglycol, 2-ethylhexanol, viscosity modifiers such as: removing the adhesive: 8043 removing adhesive, 05-92 removing adhesive, 653 removing adhesive, 903 removing adhesive, and 49 removing adhesive; or a thickener: fumed silica, chrysotile, viscosity modifiers such as ethanol, isopropanol, butyl acetate and the like, wetting agents such as dodecene glycol polyether, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether and the like, leveling agents such as polydimethylsiloxane, organic modified polysiloxane, acrylic resin or urea resin, pH modifiers such as ammonia, triethylamine, triethanolamine and N, N-dimethylaminoethanol, 2-amino-2-methylpropanol, diethylethanolamine ink physical property modifiers, and heat-expandable microcapsules such as japanese pine heat-expandable microspheres F-230D, MXene such as titanium carbide MXene nanosheet multilayer XFK06 functional additives; the mass fraction of the carbonaceous material in the cathode ink in S2 is 10-70%; the mass fraction of the oxygen reduction catalyst in the cathode ink is 10-40%; the mass fraction of the adhesive in the cathode ink is 10-45%; the mass fraction of the solvent in the cathode ink is 10-70%; the mass fraction of the additive in the cathode ink is 0-30%; the mass fraction of the carbonaceous material in the cathode ink in S2 is 25-50%; the mass fraction of the oxygen reduction catalyst in the cathode ink is 15-25%; the mass fraction of the adhesive in the cathode ink is 15-25%; the mass fraction of the solvent in the cathode ink is 15-40%; the mass fraction of the additive in the cathode ink is 5-20%; the gelator in S3 comprises high molecular weight polymer: one or a combination of at least two of polyvinyl alcohol, polyacrylic acid, polyethylene glycol, gelatin, polyvinylidene fluoride hexafluorophosphate, polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, epoxy derivatives or silicone derivatives in any proportion; or a small molecule gelator: cholesteric derivatives, saccharide derivatives, amide derivatives, bi-component gelators, metal organic compounds, amino acid compounds or bi- (and) benzene compounds; the electrolyte in S3 comprises one or a combination of at least two of alkali metal hydroxide, ionic liquid and inorganic salt in any proportion; wherein the ionic liquid is composed of an anion and the cation comprises one of an imidazolium variant, a pyrrolidinium variant, an ammonium variant, a pyridinium variant, a phosphonium variant or a sulfonium variant or a combination of at least two of the imidazolium variant, the pyrrolidinium variant, the ammonium variant, the pyridinium variant, the phosphonium variant or the sulfonium variant in any ratio, and the anion comprises one of chloride, bromide, acetate, tetrafluoroborate, trifluoroacetate, triflate, hexafluorophosphate, bis (trifluoromethanesulfonyl) amide or bis (fluorosulfonyl) imide; the inorganic salt comprises one of magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, sodium chloride or lithium chloride; the mass fraction of the gel factors in the gel electrolyte in S3 is 0.1-25%; the mass fraction of the electrolyte in the gel electrolyte is 8-70%; the mass fraction of water in the gel electrolyte is 29.5-75%; or the mass fraction of the gel factor in the gel electrolyte in S3 is 1-20%; the mass fraction of the electrolyte in the gel electrolyte is 15-60%; the mass fraction of water in the gel electrolyte is 39-65%; the porous substrate material in S4 comprises paper, breathable film or plastic or silicone or fabric; the printing mode includes but is not limited to offset printing, flexo printing, gravure printing, silk screen printing, ink jet printing or pad printing; the post-treatment is heating, the heating temperature is 60-120 ℃, and the heating time is 15-30 minutes; the drying treatment in S5 is heating, the heating temperature is 60-120 ℃, and the heating time is 15-30 minutes.
10. The application of the flexible metal-air battery in oxygen intelligent packaging.
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