CN113745711B

CN113745711B - Flexible metal-air battery and application thereof

Info

Publication number: CN113745711B
Application number: CN202110807530.7A
Authority: CN
Inventors: 莫黎昕; 潘雅琴; 李路海; 赵静; 孟祥有
Original assignee: Beijing Institute of Graphic Communication
Current assignee: Beijing Institute of Graphic Communication
Priority date: 2021-07-16
Filing date: 2021-07-16
Publication date: 2024-03-29
Anticipated expiration: 2041-07-16
Also published as: CN113745711A

Abstract

The invention relates to a flexible metal-air battery and application thereof, belonging to the technical field of printed electronics and intelligent packaging; the cathode silver current collector comprises an air diffusion layer, a cathode silver current collector, an anode silver current collector, metal anode ink, air cathode ink and gel electrolyte, which are sequentially from bottom to top: the cathode silver current collector and the anode silver current collector are positioned on the air diffusion layer, the metal anode ink is positioned on the anode silver current collector, the air cathode ink is positioned on the cathode silver current collector, the metal anode ink and the air cathode ink are in parallel, and the gel electrolyte wraps the cathode silver current collector and the anode silver current collector. The flexible metal-air battery has the advantages of low cost, active interaction, high sensitivity, flexibility, simple process and wide application range.

Description

Flexible metal-air battery and application thereof

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 the functions of identifying and judging environmental factors, and can identify and display the temperature, humidity, pressure, sealing degree, time and other important parameters of the package space. The intelligent packaging technology enables the commodity and the package thereof to have more affinity for human beings and more concise man-machine interactive communication, and has extremely wide development prospect. Sensors that are responsive 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 sources, civil use, military use and the like, and is applied to article packaging, so that the development of the interactive oxygen intelligent packaging with oxygen identification, monitoring and feedback is a hot spot in the current academia and industry.

Currently, the existing technology in the market cannot be truly called oxygen intelligent package, more than one kind of oxygen activity indicator package, and the color of the oxygen is changed by the chemical reaction between the oxygen and the active substance, so that the oxygen is identified and indicated. Gillanders et al have prepared novel phosphorescent oxygen sensitive materials of nanostructured high density polyethylene and polypropylene films by solvent cracking treatment, are simple and convenient to use, economical and efficient to produce, disposable, and suitable for large-scale applications (Analytical Chemistry, vol.82, no.2, january 15,2010). Ltsaopez-Carballo et al prepared Sensors based on methylene blue, glycerol, titanium dioxide and ethylene-vinyl acetate copolymers, detected oxygen at concentrations as low as 0.5%, and enabled industrial 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 commodities, judgment is carried out through naked eye observation, and the subjective influence is large; and its safety in food packaging still needs further investigation. Although the optical fiber type oxygen sensor, the thermomagnetic type oxygen sensor and the semiconductor type resistance oxygen sensor can be used for effectively quantitatively detecting 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, the novel oxygen sensor with low cost, active interaction, high sensitivity and convenient combination with the existing package is of great significance for the development of the intelligent oxygen package.

The metal-air battery takes oxygen in air as an anode active material and takes metal (aluminum, magnesium or zinc and the like) as a cathode active material, so that the metal-air battery has the advantages of abundant and low-cost resources, no pollution of reactants and products, and excellent environmental coordination. In theory, the output characteristics (voltage and current) of the metal-air battery and the oxygen content participating in the reaction are in a linear relation in 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 electrochemical power supply does not need an external power supply, can realize self-power supply, meets the requirements of green energy conservation, and can realize active real-time monitoring by integrating the metal air battery with the data transmission module. The principle of electrochemical cells as oxygen sensors was demonstrated by using commercially available inflexible zinc Air cells (PR 44 or PR2330 under japan) and applied to teaching experiments in school (hoo y.k., nakano, m., and Koga n. (2014), A Simple Oxygen Detector Using Zinc-Air Battery, j.chem.duc., 91 (2), 297-299). However, the method is applied to oxygen intelligent packaging on a large scale, and the defects of high cost, complex manufacturing method, difficult integration, conformal adhesion and the like of the metal-air battery are required to be overcome.

The existing indicative oxygen intelligent package is a passive oxygen sensor, a worker needs to judge by naked eye observation when approaching a commodity, the subjective influence is large, the quantitative detection of the oxygen content cannot be carried out, and the safety of the package in food packaging still needs to be further examined; the high-sensitivity sensor capable of quantitatively detecting oxygen is complex in manufacturing method, high in cost and not suitable for low-cost packaging products. Printing technology has received much attention in recent decades as an additive manufacturing means for flexible electronic products, but no reports and products related to intelligent packaging of printed oxygen have been found yet.

Therefore, providing a metal-air battery with low cost, active interaction, high sensitivity, flexibility, simple process and wide application range, a manufacturing method thereof and exploring the application of the metal-air battery in oxygen intelligent packaging become the technical problem to be overcome in the technical field.

Disclosure of Invention

The invention aims to provide a metal-air battery with low cost, active interaction, high sensitivity, flexibility, simple process and wide application range, a manufacturing method thereof and an application of the metal-air battery in oxygen intelligent packaging.

The above object of the present invention is achieved by the following technical solutions:

scheme 1:

a flexible metal-air battery (coplanar type) comprising an air diffusion layer, a cathode silver current collector, an anode silver current collector, a metal anode ink layer, an air cathode ink layer and a gel electrolyte layer, which are sequentially from bottom to top: 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:

a flexible metal-air battery (vertical type) comprises a flexible substrate, a cathode silver current collector, an anode silver current collector, a metal anode ink layer, an air cathode ink layer and a gel electrolyte layer, wherein the flexible substrate, the cathode silver current collector, the anode silver current collector, the metal anode ink layer, the air cathode ink layer and the gel electrolyte layer are sequentially from bottom to top: the flexible substrate, the positive pole silver current collector, metal anode ink layer, gel electrolyte layer, air cathode ink layer, negative pole silver current collector, gel electrolyte layer is connected with metal anode ink layer and air cathode ink layer respectively, and negative pole silver current collector and positive pole silver current collector are separated by air cathode ink layer, gel electrolyte layer and metal anode ink layer.

Preferably, the metal is one or more than two of zinc, aluminum, magnesium, lithium or iron in any proportion.

Preferably, the air cathode ink layer mainly comprises carbonaceous material, oxygen reduction catalyst and binder; the carbonaceous material comprises one or a combination of at least two of carbon black, graphite, graphene, carbon nano tube, nitrogen doped carbon black, nitrogen doped graphite, nitrogen doped graphene and nitrogen doped carbon nano tube 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 a 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 includes a gel factor and an electrolyte; the gel factor includes high molecular polymers 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 derivative, silicone derivative and the like in any proportion; and small molecule gelators such as: cholesteric derivatives, saccharide derivatives, amide derivatives, two-component gelators, metal organic compounds, amino acid compounds, di (acene) benzene compounds, etc.

Preferably, the electrolyte comprises one or a combination of at least two of alkali metal hydroxide (such as KOH and NaOH), ionic liquid and inorganic salt in any proportion; wherein the ionic liquid consists of anions and cations, the cations comprise one or a combination of at least two of imidazolium variant, pyrrolidinium variant, ammonium variant, pyridinium variant, phosphonium variant and sulfonium variant, and the anions comprise one of chloride ion, bromide ion, acetate ion, tetrafluoroborate, trifluoroacetate, trifluoromethane sulfonate, hexafluorophosphate, bis (trifluoromethane sulfonyl) amide, bis (fluorosulfonyl) imide and the like; the inorganic salt comprises one of magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, sodium chloride, lithium chloride, etc.

It is another object of the present invention to provide a metal-air battery and method of manufacture as described above.

a method of making a flexible metal-air battery comprising the steps of:

s1, weighing a certain amount of metal, an adhesive and an additive, adding the metal, the adhesive and the 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, an adhesive and an auxiliary agent additive, and adding the carbonaceous material, the oxygen reduction catalyst, the adhesive and the auxiliary agent additive into a solvent, wherein the process is kept stirring all the time, so as 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 performance;

s4, respectively manufacturing an anode current collector, a cathode current collector and a battery external circuit on the surface of the porous printing material in different printing, coating, painting or stamping modes by using conductive silver ink sold in the market, and performing post-treatment;

s5, using the metal anode ink layer prepared in the step S1, and manufacturing a metal electrode on the surface of the anode silver current collector in the step S4 in a printing, coating, painting or stamping mode; after drying and film forming, using the air cathode ink layer prepared in the step S2, and adopting printing, coating, painting or stamping to manufacture an air electrode on the surface of the cathode silver current collector in the step S4; and (3) after drying and film forming, using the gel electrolyte layer prepared in the step (S3) to prepare the gel electrolyte layer on the surfaces of the metal electrode and the air electrode in a printing, coating, painting or stamping mode, so as to obtain the flexible metal-air battery.

Preferably, the metal in S1 is one or alloy formed by less than two active metals of zinc, aluminum, magnesium, lithium or iron in any proportion, and the morphology of the alloy comprises zero-dimensional nano-micron particles, two-dimensional nano-micron sheets or a formed mixture; the adhesive comprises one or two of polyethylene oxide, polyhydroxy ether, polyurethane, copolymer of acrylonitrile/vinylidene chloride, polycarbonate, perfluorosulfonic acid resin, polyvinylpyrrolidone, polyvinylidene fluoride hexafluorophosphonate, 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 regulators such as BYK-024, dimethicone oil, polyalkyl glycol, 2-ethylhexanol and the like, viscosity regulators such as viscosity regulators (8043 viscosity regulator, 05-92 viscosity regulator, 653 viscosity regulator, 903 viscosity regulator, 49 viscosity regulator and the like) and thickeners (fumed silica, chrysotile and the like), viscosity regulators 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, organomodified polysiloxane, acrylic resin, urea resin and the like, pH regulators such as ammonia, 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 S1 in the metal anode ink layer 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 auxiliary additive in the metal anode ink layer is 0-30%.

Preferably, the mass fraction of the metal in the metal anode ink layer in the 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 auxiliary additive in the metal anode ink layer is 4% -20%.

Preferably, the carbonaceous material in S2 comprises one or a combination of at least two of any proportion of carbon black, graphite, graphene, carbon nanotubes, nitrogen doped carbon black, nitrogen doped graphite, nitrogen doped graphene, nitrogen doped carbon nanotubes; 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 a 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 a combination of at least two of glycol, toluene, deionized water, terpineol and the like in any proportion; the auxiliary additives include surface tension regulators such as BYK-024, dimethyl silicone oil, polyalkyl glycol, 2-ethylhexanol, etc., viscosity regulators such as viscosity regulators (8043 viscosity regulator, 05-92 viscosity regulator, 653 viscosity regulator, 903 viscosity regulator, 49 viscosity regulator, etc.) and thickeners (fumed silica, chrysotile, etc.), viscosity regulators such as ethanol, isopropanol, butyl acetate, etc., wetting agents such as dodecene glycol polyether, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether, etc., leveling agents such as polydimethyl siloxane, organically modified polysiloxane, acrylic resin, urea resin, etc., pH regulators such as ink physical regulators such as ammonia water, triethylamine, triethanolamine and N, N-Dimethylaminoethanol (DMEA), 2-amino-2-methylpropanol (AMP), diethyl ethanolamine (DEEA), etc., and thermally-expandable microcapsules such as japanese thermally-expandable microspheres F-230D, MXene such as titanium carbide (Ti 2 CTx) m 06 nano-multilayer tablet, etc.; the thermal expansion microcapsule mainly plays a role in regulating the microstructure of the cathode and increasing the specific surface area of the cathode. MXene acts to enhance cathode conductivity and oxygen reduction activity.

Preferably, the mass fraction of the carbonaceous material in the S2 in the air cathode ink layer is 10% -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 auxiliary additive in the air cathode ink layer is 0% -30%.

Preferably, the mass fraction of the carbonaceous material in the S2 in the air cathode ink layer is 25% -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 auxiliary additive in the air cathode ink layer is 5% -20%.

Preferably, the gel factor 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 derivative, silicone derivative and the like in any proportion; and small molecule gelators such as: cholesteric derivatives, saccharide derivatives, amide derivatives, two-component gelators, metal organic compounds, amino acid compounds, di (acene) benzene compounds, etc.

Preferably, the electrolyte in S3 comprises one or a combination of at least two of alkali metal hydroxide (such as KOH, naOH), ionic liquid, inorganic salt in any proportion; wherein the ionic liquid consists of anions and cations, the cations comprise one or a combination of at least two of imidazolium variant, pyrrolidinium variant, ammonium variant, pyridinium variant, phosphonium variant and sulfonium variant, and the anions comprise one of chloride ion, bromide ion, acetate ion, tetrafluoroborate, trifluoroacetate, trifluoromethane sulfonate, hexafluorophosphate, bis (trifluoromethane sulfonyl) amide, bis (fluorosulfonyl) imide and the like; the inorganic salt comprises 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 S3 in the gel electrolyte 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%.

Preferably, the mass fraction of the gel factor in the S3 in the gel electrolyte 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 support material in S4 comprises paper, breathable film or plastic, silicone or fabric; printing means including, but not limited to, offset printing, flexography, gravure, screen printing, inkjet printing, or pad printing; the post-treatment is heating, the heating temperature is between 60 ℃ and 120 ℃, and the heating time is between 15 and 30 minutes.

Preferably, the drying treatment in S5 is heating, the heating temperature is between 60 ℃ and 120 ℃, and the heating time is between 15 and 30 minutes.

It is a further object of the present invention to provide the use of the flexible metal-air battery described above in oxygen smart packaging.

s1, connecting an electronic component for sensing response or data transmission with the flexible metal-air battery prepared in the S5 to form a closed-loop circuit, so as to obtain a flexible oxygen sensor;

and S2, attaching the printed flexible oxygen sensor manufactured in the step S1 to the inner surface or the outer surface of the package to obtain the flexible oxygen intelligent package.

Preferably, the electronic components used for sensing response or data transmission in S1 include RFID, buzzer, LED or electrochromic film.

Preferably, S1 further comprises an encapsulation material, which is a flexible material that is gas-impermeable, including a gas-impermeable film, a metal foil, a polymer laminate with an adhesive (adhesive backing), a paper/plastic or film composite, etc.

The electronic components can be prepared in a printing mode or commercial devices can be selected.

The flexible metal-air battery can also be packaged and used as a disposable oxygen intelligent package, and is applied to scenes needing to monitor the oxygen content, such as cellars, underground mine holes, oxygen impurity detection and the like.

The flexible metal-air battery has the beneficial effects that:

the flexible metal-air battery has the advantages of low cost, active interaction, high sensitivity, flexibility, simple process and wide application range.

The invention is further illustrated by the drawings and the detailed description which follow, but 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 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 view showing the structure of a flexible oxygen sensor in application example 1 of the present invention.

Fig. 4 is a schematic view showing the structure of a flexible oxygen sensor in application example 2 of the present invention.

Fig. 5 is a schematic structural view of an experimental apparatus for testing the relationship between the output characteristics of a flexible metal-air battery and the oxygen content involved in the reaction in application example 3 of the present invention.

Main part name

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 aluminium plastic composite film packaging material 8 transparent plastic film

9RFID label 10 transparent plastic bag

11 transparent adhesive tape 12 voltmeter

13 25 ohm resistor 14 flexible metal-air battery

15 disposable baby warmer containing iron powder

Detailed Description

Unless otherwise indicated, the starting materials used in the examples below were all commercially available and the methods used were not conventional in the art.

As shown in fig. 1-1, a schematic structural diagram of a coplanar flexible zinc-air battery prepared in example 1 of the present invention is shown; 1-2, a schematic structural diagram of a vertical flexible aluminum air battery prepared in example 2 of the present invention is shown; 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 view showing the structure of a flexible oxygen sensor according to application example 1 of the present invention; FIG. 4 is a schematic view showing the structure 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 the relationship between the output characteristics of a flexible metal-air battery and the oxygen content involved in the 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 parts of a third air cathode ink layer, 6-2 parts of a third gel electrolyte layer, 1-3 parts of a third air diffusion layer, 2-3 parts of a fourth anode silver current collector, 3-3 parts of a fourth cathode silver current collector, 4-3 parts of a second zinc anode ink layer, 5-3 parts of a fourth air cathode ink layer, 6-3 parts of a fourth gel electrolyte layer, 7 parts of an aluminum plastic composite film packaging material, 8 parts of a transparent plastic film, 9 parts of an RFID label, 10 parts of a transparent plastic bag, 11 parts of a transparent adhesive tape, 12 parts of a voltmeter, 13 parts of a 25 ohm resistor, 14 parts of a flexible metal air battery and 15 parts of a disposable warmer containing iron powder.

Example 1 (coplanar type)

Preparing zinc anode ink in the step (1):

weighing 3.5g of zinc powder and 0.1g of polyvinylpyrrolidone (average molecular weight 58000), dispersing or dissolving the zinc powder and the polyvinylpyrrolidone in 0.9g of glycerol and 0.5g of methanol, keeping the stirring speed at 100-500 revolutions per minute, and obtaining a zinc anode ink layer after the system is well dispersed;

preparing a first air cathode ink in the 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, dispersing or dissolving in 0.5g of terpineol and 0.75g of deionized water, keeping the stirring speed at 100-500 revolutions per minute, and obtaining the first air cathode ink after the system is well dispersed;

step (3) preparation of a first gel electrolyte:

weighing 2g of polyvinyl alcohol powder (average molecular weight 146000 ～ 186000), dissolving in 10g of deionized water, and continuously stirring under the conditions of water bath heating and heating temperature of 80-95 ℃ at the stirring speed of 200-500 rpm until the solution is in a clear state; 8g of 1-ethyl-3-methylimidazole tetrafluoroborate is added under the condition of gentle stirring with the stirring speed reduced to 100-200 revolutions per minute, after uniform mixing, the mixture is stood, bubbles are removed, and the first gel electrolyte with certain water retention performance is obtained after sealing, standing and cooling at normal temperature;

And (4) preparing a conductive circuit and a current collector:

printing on the surface of a fabric with a polytetrafluoroethylene backboard by using conductive silver ink sold in the market in a screen printing mode, heating 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 2cm multiplied by 2cm;

and (5) preparing a flexible zinc-air battery:

printing a metal electrode with the size of 1.8cm multiplied by 1.8cm 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 at 60 ℃ for 15 minutes, 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 at 60 ℃ for 15 minutes, printing gel electrolyte with the size of 2cm multiplied by 4.3cm on two electrodes by adopting a screen printing mode by using the gel electrolyte prepared in the step (3) (namely, obtaining a first gel electrolyte layer), wherein the first gel electrolyte layer covers and wraps the two electrodes of the battery (comprising a metal electrode zinc anode ink layer and an air electrode first air cathode ink layer); installing an RFID tag or a digital display meter with a microprocessor chip and the like; the open circuit voltage of a single flexible zinc-air battery is 1.20V and the energy density is 300Wh/kg.

The coplanar flexible zinc-air battery prepared in the embodiment 1 of the invention comprises 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, which are sequentially from bottom to top: the first air diffusion layer 1 is a fabric with a polytetrafluoroethylene back plate, the first cathode silver current collector 2 and the first anode silver current collector 3 (printing conductive silver ink as a wire and the like) are positioned on the first air diffusion layer 1, the zinc anode ink layer 4 is positioned on the first anode silver current collector 3, the 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 side by side (printing metal ink and air cathode ink with a certain distance left), and the 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)

Preparing aluminum anode ink in the step (1):

3.5g of aluminum powder and 0.1g of polyvinylpyrrolidone (average molecular weight 58000) are weighed and dispersed or dissolved in 0.9g of glycerol and 0.5g of methanol, the stirring speed is kept between 100 and 500 revolutions per minute, and the aluminum anode ink is obtained after the system is well dispersed;

Preparing second air cathode ink in the 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, dispersing or dissolving in 0.5g of terpineol and 0.75g of deionized water, keeping the stirring speed at 100-500 revolutions per minute, and obtaining a second air cathode ink after the system is well dispersed;

step (3) preparation of a second gel electrolyte:

weighing 2g of polyvinyl alcohol powder (average molecular weight 146000 ～ 186000), dissolving in 10g of deionized water, and continuously stirring under the conditions of water bath heating and heating temperature of 80-95 ℃ at the stirring speed of 200-500 rpm until the solution is in a clear state; under the condition of gently stirring at the stirring speed of 100-200 revolutions per minute, adding 8g of 1-ethyl-3-methylimidazole tetrafluoroborate, uniformly mixing, standing, removing bubbles, sealing and standing at normal temperature, and cooling to obtain a second gel electrolyte with certain water retention property;

and (4) preparing a conductive circuit and a current collector:

coating the surface of Polyester (PET) by using conductive silver ink sold in the market 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 2cm;

And (5) preparing a 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) in a coating mode (namely obtaining an aluminum anode ink layer); heating at 60 ℃ for 15 minutes, and 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); 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 at 60 ℃ for 15 minutes, a second cathode current collector with the size of 2cm multiplied by 2cm is coated by using conductive silver ink in a coating mode; installing an RFID tag or a digital display meter with a microprocessor chip and the like; the open circuit voltage of a single flexible aluminum air battery is 2.0V, and the energy density is 600Wh/kg.

The vertical flexible aluminum air battery prepared in the embodiment 2 of the invention comprises a flexible substrate 1-1 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, which are sequentially 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, 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, which is 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, i.e., printed on the second air cathode ink layer 5-1.

Example 3 (coplanar type)

Preparation of lithium anode ink in step (1):

3.5g of lithium powder and 0.1g of polyvinylpyrrolidone (average molecular weight 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, after the system is well dispersed, the lithium anode ink is obtained, and the lithium anode ink is filled into an empty Mark pen for standby;

preparing air cathode ink in the 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, dispersing or dissolving in 0.5g of terpineol and 0.75g of deionized water, keeping the stirring speed at 100-500 revolutions per minute in the process, obtaining air cathode ink after the system is well dispersed, and filling the air cathode ink into an empty Mark pen for later use;

step (3) preparation of gel electrolyte:

weighing 2g of polyvinyl alcohol powder (average molecular weight 146000 ～ 186000), dissolving in 10g of deionized water, and continuously stirring under the conditions of water bath heating and heating temperature of 80-95 ℃ at the stirring speed of 200-500 rpm until the solution is in a clear state; under the condition of gently stirring at the stirring speed of 100-200 revolutions per minute, adding 8g of 1-ethyl-3-methylimidazole tetrafluoroborate, uniformly mixing, standing, removing bubbles, cooling for 30 minutes at normal temperature to obtain gel electrolyte, and filling into an empty Mark pen for later use;

And (4) preparing a conductive circuit and a current collector:

printing on the surface of A4 paper by using conductive silver ink sold in the market in a screen printing mode, heating at 100 ℃ for 15 minutes, and then 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 2cm;

and (5) preparing a 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 the anode silver current collector by adopting a direct writing mode by using the lithium anode ink prepared in the step (1), and heating for 20 minutes at 60 ℃; drawing an air electrode with the size of 1.8cm multiplied by 1.8cm (namely a third air cathode ink layer) on the upper layer of the cathode silver current collector by adopting a direct writing mode by using the air cathode ink prepared in the step (2), and heating the air electrode 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, using the gel electrolyte prepared in the step (3), drawing the gel electrolyte with the size of 2cm multiplied by 4.3cm on the two electrodes in a direct writing mode (namely obtaining a third gel electrolyte layer), and covering and wrapping the gel electrolyte layer and connecting the two poles of the battery; mounting an LED colored lamp, a small music box, a buzzer or the like; the open circuit voltage of a single flexible lithium air battery is 2.0V and the energy density is 387Wh/kg.

The open flexible metal-air battery manufactured by the direct writing/drawing mode adopted in the embodiment can be applied to creative products such as cultural creative electronics, electronic circuit design, personal creative DIY electronics and the like, and scientific knowledge and concepts are transmitted or physical teaching and other activities are conducted through a form which is easy to accept by the public.

Example 4 (coplanar type)

Preparing zinc anode ink in the step (1):

3g of zinc powder, 0.25g of polyvinylpyrrolidone (average molecular weight 58000) and 1g of carbon black are weighed and dispersed or dissolved in 0.5g of glycerol and 0.25g 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;

preparing a first air cathode ink in the step (2):

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 nano-sheet 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, 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 (average molecular weight 146000 ～ 186000), dissolving in 7.8g of deionized water, and continuously stirring under the conditions of water bath heating and heating temperature of 80-95 ℃ until the solution is in a clear state, wherein the stirring speed is 200-500 revolutions per minute; under the condition of gently stirring at the stirring speed of 100-200 revolutions per minute, adding 12g of 1-ethyl-3-methylimidazole tetrafluoroborate, uniformly mixing, standing, removing bubbles, and sealing, standing and cooling at normal temperature to obtain a first gel electrolyte with certain water retention property;

And (4) preparing a conductive circuit and a current collector:

and (5) preparing a flexible zinc-air battery:

printing a metal electrode with the size of 1.8cm multiplied by 1.8cm 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 at 60 ℃ for 15 minutes, 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); heating at 60 ℃ for 15 minutes, printing gel electrolyte with the size of 2cm multiplied by 4.3cm on two electrodes by adopting a screen printing mode by using the gel electrolyte prepared in the step (3) (namely, obtaining a first gel electrolyte layer), and covering and wrapping the first gel electrolyte layer and connecting the two electrodes (a metal electrode and an air electrode) of the battery; installing an RFID tag or a digital display meter with a microprocessor chip and the like; the open circuit voltage of a single flexible zinc-air battery is 1.20V and the energy density is 300Wh/kg.

Example 5 (coplanar type)

Preparation of lithium anode ink in step (1):

weighing 2g of lithium powder, 0.75g of polyvinylpyrrolidone (average molecular weight 58000) and 1.5g of polyalkyl glycol, dispersing or dissolving in 0.5g of glycerol and 0.25g of methanol, keeping stirring speed at 100-500 revolutions per minute, and pouring the lithium anode ink into an empty Mark pen for later use after the system is well dispersed;

Preparing air cathode ink in the step (2):

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 needle thermal expansion microsphere F-230D are weighed and dispersed or dissolved in 0.2g of terpineol and 0.3g of deionized water, the stirring speed is kept between 100 and 500 revolutions per minute, after the system is well dispersed, air cathode ink is obtained, and the air cathode ink is poured into an air Mark pen for standby;

step (3) preparation of gel electrolyte:

weighing 3g of polyvinyl alcohol powder (average molecular weight 146000 ～ 186000), dissolving in 12g of deionized water, and continuously stirring under the conditions of water bath heating and heating temperature of 80-95 ℃ at the stirring speed of 200-500 rpm until the solution is in a clear state; 5g of 1-ethyl-3-methylimidazole tetrafluoroborate is added under the condition of gentle stirring at the stirring speed of 100-200 revolutions per minute, after uniform mixing, the mixture is stood, air bubbles are removed, and gel electrolyte is obtained after cooling for 30 minutes at normal temperature and is filled into an empty Mark pen for standby;

and (4) preparing a conductive circuit and a current collector:

And (5) preparing a flexible lithium air battery:

Application example 1: preparation of flexible oxygen sensor

The oxygen concentration required by the normal activity of the human body is 19.5% -23.5%, so that the oxygen concentration cannot be lower than 19.5% for the safety of the human body, and an alarm must be given when the oxygen concentration exceeds 23.5%. When the oxygen concentration is reduced to 15% -19%, people feel laborious and the working capacity is reduced; when the oxygen concentration is reduced to 12% -14%, the breathing speed and pulse speed of people are increased, and the coordination capacity and the perception judgment are reduced; when the oxygen concentration is reduced to 10% -12%, the respiration of the person is weakened, and the lips are blue and purple; when the oxygen concentration is reduced to 8% -10%, people can become unconscious, faint, complexion, dust, 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%, the people can be coma, convulsion, respiratory arrest and even death in a few tens of seconds.

To ensure the physical health and life safety of the staff, preventing the occurrence of hypoxia; in all places such as cabins, underground engineering, submarines, tunnels and the like which may cause hypoxia, the oxygen concentration of the environment must be checked regularly. For example, in mines, the measurement of the oxygen concentration is not only an important parameter for ensuring the life health and safety of miners, but also for underground explosion prevention, so that the oxygen concentration in the air inlet flow of a mining working face must be ensured to be not 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 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 surface of the air diffusion layer, hot pressing is carried out on the edge of the aluminum-plastic composite film, the periphery is sealed to prevent air from entering, and when the aluminum-plastic composite film is used, the hot-pressing sealing parts around are opened to be filled with air; the method has the advantages of high production efficiency, low cost, disposability, flexibility, conformal adhesion, portability, environmental friendliness and the like, and the coal in China has abundant reserve, can be popularized and applied to the scenes, and has very broad prospects.

The flexible oxygen sensor prepared by the application example 1 comprises a flexible lithium air battery and an encapsulating material aluminum-plastic composite film 7; the flexible lithium air battery comprises a second air diffusion layer 1-2 nylon (base material, material with 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 can inhibit respiration of plants. When fruits and vegetables are stored or transported, the fruits and the vegetables are placed in places with higher oxygen concentration, the respiration of the fruits and the vegetables is vigorous, the consumed organic matters are more, the heat released is more, and the fruits and the 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 fruits and vegetables, and the oxygen concentration is ensured to be 1% -10%, preferably kept around 5%, so as to ensure the quality and transportation safety of the fruits and vegetables. The flexible metal-air battery manufactured in a printing or coating mode as in the embodiment 1 and the embodiment 2 is integrated in the relatively sealed package, is used as an oxygen sensor, is connected with informationized and databased electronic components, such as printable electronic component RFID labels and the like, is directly printed and connected with the flexible metal-air battery, and non-printable electronic component LED lamps, buzzers, digital display tables and the like are bonded by using conductive copper foil or conductive adhesive, so that the flexible metal-air battery accords with the development trend of IOT and ensures the quality of products. The data generated during the transportation process can also clarify the pay-out problem generated by the damage of the products among the seller, the transportation company and the consumer, and avoid unnecessary disputes. The flexible oxygen sensor of the invention can be used for, but is not limited to, detecting whether the food package leaks air or not, so as to find the possible spoilage of the food in the package in time.

The flexible oxygen sensor prepared by the application example 2 of the invention comprises a flexible zinc-air battery, a transparent plastic film 8 and an RFID label 9; the flexible zinc-air cell comprises a third air diffusion layer 1-3 (also part of the vacuum food outer package, only a gas permeable material is used at the 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; the fourth gel electrolyte layer 6-3 (hydrogel of polyvinyl alcohol and 1-ethyl-3-methylimidazole tetrafluoroborate) wraps and connects the fourth anode silver current collector 2-3, the second zinc anode ink layer 4-3, the fourth cathode silver current collector 3-3 and the fourth air cathode ink layer 5-3 together, the RFID tag 9 is connected with a flexible zinc air battery, and the periphery of the transparent plastic film 8, which is in contact with the outer package, is sealed for 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 test device (such as an ammeter and a voltmeter), and the oxygen content in the package is subjected to active qualitative or quantitative analysis through the change of the working state of the external electronic component, wherein the external connected electronic component comprises a device prepared or commercialized by using a printing technology, such as: RFID tags, LED indicators, buzzers, electrochromic films, etc.

The flexible metal-air battery, 25 Ω resistor, voltmeter, transparent plastic bag, transparent adhesive tape, disposable warmer containing iron powder, etc. prepared in example 1 or example 2 of the present invention were assembled into a device for performing experiments, and the warmer and the flexible metal-air battery were put together into a plastic bag, the plastic bag was inflated with air, the plastic bag was sealed, and the opening of the bag around the wire of the voltmeter was sealed with transparent adhesive tape to prevent air from entering or leaking. This is a principle verification example such as that of application example 1 and application example 2 in which the flexible metal-air battery is used as an oxygen sensor.

FIG. 5 is a schematic structural diagram of an experimental apparatus for testing the relationship between the output characteristics of a flexible metal-air battery and the oxygen content involved in the 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; the transparent plastic bag 10 is provided with a flexible metal air battery 14, a disposable baby warmer 15 containing iron powder and a 25 omega resistor 13, wherein the flexible metal air battery 14 and the 25 omega resistor 13 are connected to form a closed loop circuit, the voltmeter 12 is connected in parallel at two ends of the 25 omega resistor 13, the disposable baby warmer 15 containing iron powder is arranged near the flexible metal air battery 14, and the bag opening of the transparent plastic bag 10 is sealed by the transparent adhesive tape 11, and particularly, the bag opening around a wire of the voltmeter and any other positions possibly leaking air are strictly sealed.

The flexible metal-air battery of the invention has the following advantages:

(1) The current collector, the circuit, the electrode and the electrolyte are all manufactured by adopting modes such as printing, the flexible metal-air battery can be manufactured by adopting a coating mode besides the mode of printing, the flexible metal-air battery is suitable for high-efficiency, large-area and flexible metal-air battery production, the circuit can be creatively presented by adopting modes such as painting, stamp design and the like, and the flexible metal-air battery 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 characteristics of being bendable, foldable and the like, can realize large-scale mass production by printing, coating and the like, and experiments prove that the battery can stably work in the service life; 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 mode is used as an oxygen sensor to detect the oxygen concentration with the following precision: the oxygen content (concentration) in the range of 0-50% (volume oxygen) is in linear relation with the logarithmic value of the battery potential, as shown in fig. 2 (in the example of a flexible zinc-air battery), 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 through the known linear relation by utilizing an electronic device after being set by related software, so as to achieve the purpose of monitoring the oxygen content; wherein, the flexible zinc-air battery manufactured in the above way is taken as an example, and the current density is 2.0mA/cm ² ～20mA/cm ² During discharging, the discharging time of the battery is about 10.5-72 h, and the lower the current density is, the longer the discharging time is; the flexibility is tested by a bending test, which shows that: the cells were discharged at the same current density before and after bending, and the cells exhibited substantially uniform electrical properties in terms of open circuit voltage and discharge time.

The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should be covered by the protection scope of the present invention by making equivalents and modifications to the technical solution and the inventive concept thereof.

Claims

1. A flexible oxygen sensor, characterized by: the flexible metal-air battery comprises an air diffusion layer, a cathode silver current collector, an anode silver current collector, a metal anode ink layer, an air cathode ink layer and a gel electrolyte layer, which are sequentially from bottom to top: 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 formed between the cathode silver current collector and the anode silver current collector;

connecting an electronic component for sensing response or data transmission with a flexible metal-air battery to form a closed-loop circuit, so as to obtain a flexible oxygen sensor;

the metal in the metal anode ink layer is one or more than two of zinc, aluminum, magnesium, lithium or iron in any proportion; the mass fraction of the metal in the anode ink is 60% -80%;

the air cathode ink layer comprises a carbonaceous material, an oxygen reduction catalyst and a binder; the carbonaceous material comprises graphite; the oxygen reduction catalyst includes cerium oxide; the adhesive comprises one or a combination of at least two of polytetrafluoroethylene, carboxymethyl cellulose, styrene-butadiene rubber, polyethylene oxide, styrene-butadiene copolymer and sodium silicate in any proportion; the mass fraction of the carbonaceous material in the cathode ink is 25% -50%; the mass fraction of the oxygen reduction catalyst in the cathode ink is 15% -25%; the mass fraction of the binder 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 auxiliary additive in the cathode ink is 5% -20%;

The gel electrolyte layer comprises a gel factor and an electrolyte; the gel factor comprises polyvinyl alcohol; the electrolyte comprises an ionic liquid comprising water, the ionic liquid consisting of anions and cations comprising imidazolium variants, and the anions comprising tetrafluoroborate; the mass fraction of the gel factor in the gel electrolyte 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 preparation method of the flexible oxygen sensor comprises the following steps:

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 metal anode ink;

the metal in S1 is one or more than two of zinc, aluminum, magnesium, lithium or iron active splashing metal in any proportion, and the morphology of the alloy comprises zero-dimensional nano-micron particles, two-dimensional nano-micron sheets or a mixture formed by the two; the adhesive is polyvinylpyrrolidone; the solvent comprises one or a combination of at least two of methanol, glycerol, deionized water, toluene, N-ethyl pyrrolidone, tetrahydrofuran and N-methyl pyrrolidone in any proportion;

The mass fraction of the metal in the anode ink in the 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 auxiliary additive in the anode ink is 4% -20%;

s2: weighing a certain amount of carbonaceous material, an oxygen reduction catalyst, an adhesive and an auxiliary agent additive, and adding the carbonaceous material, the oxygen reduction catalyst, the adhesive and the auxiliary agent additive into a solvent, wherein the process is kept stirring all the time, so as to prepare air cathode ink;

the carbonaceous material in S2 comprises graphite; the oxygen reduction catalyst includes cerium oxide; the adhesive comprises one or a 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 a combination of at least two of glycol, toluene, deionized water and terpineol in any proportion;

the mass fraction of the carbonaceous material in the cathode ink in the S2 is 25% -50%; the mass fraction of the oxygen reduction catalyst in the cathode ink is 15% -25%; the mass fraction of the binder 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 auxiliary additive in the cathode ink is 5% -20%;

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 performance;

the gel factor in S3 comprises polyvinyl alcohol; the electrolyte comprises an ionic liquid comprising water, the ionic liquid consisting of anions and cations comprising imidazolium variants, and the anions comprising tetrafluoroborate;

the mass fraction of the gel factor in the gel electrolyte in the 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%;

s4: respectively manufacturing an anode silver current collector, a cathode silver current collector and a battery external circuit on the surface of a porous printing material by using conductive silver ink sold in the market in a printing, coating, painting or seal mode, and performing post-treatment;

s5: using the metal anode ink prepared in the step S1, and manufacturing a metal electrode on the surface of the anode silver current collector in the step S4 in a printing, coating, painting or stamping mode; after drying and film forming, using the air cathode ink prepared in the step S2, and adopting printing, coating, painting or stamping to manufacture an air electrode on the surface of the cathode silver current collector in the step S4; after drying and film forming, using the gel electrolyte ink prepared in the step S3 to prepare gel electrolyte on the surfaces of the metal electrode and the air electrode in a printing, coating, painting or seal printing mode, so as to obtain the flexible metal air battery;

And (5) connecting the electronic component for sensing response or data transmission with the flexible metal-air battery prepared in the step (S5) to form a closed-loop circuit, so as to obtain the flexible oxygen sensor.

2. A flexible oxygen sensor, characterized by: the flexible metal-air battery comprises a flexible substrate, a cathode silver current collector, an anode silver current collector, a metal anode ink layer, an air cathode ink layer and a gel electrolyte layer, and is characterized in that: the flexible substrate, the anode silver current collector, the metal anode ink layer, the gel electrolyte layer, the air cathode ink layer and the cathode silver current collector are 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. A method of manufacturing a flexible oxygen sensor comprising the steps of:

4. A method of manufacturing a flexible oxygen sensor according to claim 3, wherein: the auxiliary additive in S1 comprises a conductive agent, a surface tension regulator, a viscosity regulator, a wetting agent, a leveling agent or a pH value regulator.

5. The method of manufacturing a flexible oxygen sensor of claim 4, wherein: the conductive agent includes carbon black;

and/or the surface tension modifier comprises BYK-024, dimethyl silicone oil, polyalkyl glycol or 2-ethylhexanol;

And/or the viscosity regulator is an adhesive or a thickener, wherein the adhesive comprises an 8043 adhesive, 05-92 adhesive, 653 adhesive, 903 adhesive or 49 adhesive; the thickening agent comprises smoke silicon or chrysotile;

and/or the viscosity modifier is ethanol, isopropanol or butyl acetate, wetting agent such as ethylene glycol polyether or 2, 4, 7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether;

and/or the leveling agent comprises polydimethylsiloxane, organic modified polysiloxane, acrylic resin and urea resin;

and/or the pH regulator comprises ammonia water, triethylamine, triethanolamine, N-dimethylaminoethanol, 2-amino-2-methylpropanol or diethyl ethanolamine.

6. The method of manufacturing a flexible oxygen sensor of claim 5, wherein: s2, the oxygen reduction catalyst is cerium oxide;

the binder in S2 comprises sodium silicate;

s2, the auxiliary additive comprises a surface tension regulator, a viscosity regulator, a wetting agent, a leveling agent and a pH value regulator;

the electrolyte in S3 is 1-ethyl-3-methylimidazole tetrafluoroborate;

the porous printing material in S4 comprises paper, breathable film or plastic or silicone or fabric; the printing mode comprises offset printing, flexography, gravure, screen printing, inkjet printing or pad printing; the post-treatment is heating, the heating temperature is between 60 ℃ and 120 ℃, and the heating time is between 15 and 30 minutes;

And S5, heating, wherein the heating temperature is between 60 and 120 ℃ and the heating time is between 15 and 30 minutes.

7. The method of manufacturing a flexible oxygen sensor of claim 6, wherein: the surface tension regulator comprises BYK-024, dimethyl silicone oil, polyalkyl glycol or 2-ethylhexanol;

and/or, the viscosity modifier comprises a viscosity-removing agent or a thickener; the adhesive comprises 8043 adhesive, 05-92 adhesive, 653 adhesive, 903 adhesive or 49 adhesive; the thickening agent comprises smoke silicon or chrysotile;

and/or, viscosity modifiers include ethanol, isopropanol, butyl acetate;

and/or the wetting agent comprises dodecene glycol polyether, 2, 4, 7, 9-tetramethyl-5-decyne-4, 7-diol polyoxyethylene ether;

and/or the leveling agent comprises polydimethylsiloxane, organic modified polysiloxane, acrylic resin or urea resin;

and/or the pH value regulator comprises ammonia water, triethylamine, triethanolamine, N-dimethylaminoethanol, 2-amino-2-methylpropanol and diethyl ethanolamine ink physical property regulator.

8. The method of manufacturing a flexible oxygen sensor of claim 6, wherein: and S2, adding thermal expansion microcapsules.

9. The method of manufacturing a flexible oxygen sensor of claim 6, wherein: the thermally-expansive micro-capsule comprises Japanese pine thermally-expansive micro-spheres F-230D or MXene.

10. The method of manufacturing a flexible oxygen sensor of claim 9, wherein: MXene is titanium carbide MXene multi-layer nano-sheet XFK06.

11. Use of a flexible oxygen sensor according to claim 1 or 2, or a flexible oxygen sensor prepared by the method of any one of claims 3 to 10, in oxygen smart packaging.