CN117254039A - Flexible metal-air battery, preparation method thereof and flexible metal-air battery pack - Google Patents
Flexible metal-air battery, preparation method thereof and flexible metal-air battery pack Download PDFInfo
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- CN117254039A CN117254039A CN202311250496.3A CN202311250496A CN117254039A CN 117254039 A CN117254039 A CN 117254039A CN 202311250496 A CN202311250496 A CN 202311250496A CN 117254039 A CN117254039 A CN 117254039A
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- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 141
- 229910052751 metal Inorganic materials 0.000 claims abstract description 70
- 239000002184 metal Substances 0.000 claims abstract description 70
- 239000003792 electrolyte Substances 0.000 claims abstract description 40
- 238000007650 screen-printing Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 27
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 229910052709 silver Inorganic materials 0.000 claims description 21
- 239000004332 silver Substances 0.000 claims description 21
- 239000010410 layer Substances 0.000 claims description 20
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 20
- 239000002356 single layer Substances 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 16
- 239000002482 conductive additive Substances 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 11
- 239000002923 metal particle Substances 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- 238000007731 hot pressing Methods 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- 229920001940 conductive polymer Polymers 0.000 claims description 8
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- 238000002156 mixing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000002174 Styrene-butadiene Substances 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 4
- 239000011115 styrene butadiene Substances 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 210000004027 cell Anatomy 0.000 description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 25
- 238000007639 printing Methods 0.000 description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 230000008901 benefit Effects 0.000 description 13
- 230000001965 increasing effect Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
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- 238000005516 engineering process Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
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- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8673—Electrically conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
Abstract
The invention provides a flexible metal-air battery, a preparation method thereof and a flexible metal-air battery pack, and relates to the technical field of air batteries. The flexible metal-air battery comprises a substrate, a metal electrode and an air electrode, wherein the metal electrode and the air electrode are respectively screen-printed on two sides of the substrate; also included is a solid gel electrolyte or electrolyte solution stored within the substrate for substantially absorbing the electrolyte solution to wet the metal electrode and the air electrode. According to the invention, the metal electrode and the air electrode are respectively printed on the two sides of the substrate by adopting a screen printing method, so that the battery is of an integrated structure, and the structure ensures that the battery has more stable electrode-electrolyte contact when the battery is subjected to frequent deformation, and the discharge stability of the battery is ensured; meanwhile, the battery has a thinner thickness, and high flexibility of the battery is guaranteed.
Description
Technical Field
The invention relates to the technical field of air batteries, in particular to a flexible metal-air battery, a preparation method thereof and a flexible metal-air battery pack.
Background
The new generation of miniature, flexible and wearable electronic products is vigorously developed, the urgent need of people for a miniature energy storage device which is matched with the miniature energy storage device with low cost, high flexibility and light weight is greatly stimulated, the flexible metal-air battery takes oxygen in air as an anode active substance and takes metal as a cathode active substance, for example, a zinc-air battery has the advantages of small volume, large capacity, low cost, meeting the energy supply requirement of the wearable electronic products and the like compared with the traditional lithium-ion battery, and the flexible metal-air battery has very wide application prospect.
The flexible metal-air battery ensures good flexibility to meet wearable application requirements, and the structure of the battery is of paramount importance. The flexible battery structure mainly comprises a one-dimensional cable-shaped structure, a two-dimensional plane structure and a sandwich layered structure which is most used at present. The sandwich laminated structure comprises a metal foil at the bottommost layer, a solid electrolyte at the middle layer and an air electrode at the uppermost layer, and the structure can make each layer very thin so that the battery is thinner and thinner as a whole, and is convenient to curl and fold, but the phenomenon of poor contact between the laminated layers is easily caused when the battery is frequently deformed, thereby influencing the normal use of the battery.
Disclosure of Invention
The invention aims to solve the problem that the performance of the battery is easily affected by contact bad between lamination layers when the flexible metal-air battery with the existing sandwich lamination structure is frequently deformed.
In order to solve the problems, the invention provides a flexible metal-air battery, which comprises a substrate, a metal electrode and an air electrode, wherein the metal electrode and the air electrode are respectively screen-printed on two sides of the substrate; also included is a solid gel electrolyte or electrolyte solution stored within the substrate for substantially absorbing the electrolyte solution to wet the metal electrode and the air electrode.
Preferably, the substrate comprises a single-layer paper substrate or a double-layer paper substrate;
when the substrate is the single-layer paper substrate, the metal electrode and the air electrode are respectively screen-printed on two sides of the single-layer paper substrate;
when the substrate is the double-layer paper substrate, the metal electrode and the air electrode are respectively screen printed on two different paper substrates, and one surfaces of the two paper substrates, on which the metal electrode and the air electrode are not printed, are bonded together.
Preferably, when the substrate is the single-layer paper substrate, the solid gel electrolyte is stored inside the single-layer paper substrate, or the single-layer paper substrate is used to sufficiently absorb the electrolyte solution to wet the metal electrode and the air electrode;
when the substrate is the double-layer paper substrate, the solid gel electrolyte is respectively stored in the two paper substrates, and the two paper substrates are bonded together through the solid gel electrolyte; alternatively, two sheets of the paper substrate are bonded together by an adhesive, and the two sheets of the paper substrate are configured to substantially absorb the electrolyte solution to wet the metal electrode and the air electrode, respectively.
The flexible metal-air battery of the present invention has the advantages over the prior art:
according to the invention, the metal electrode and the air electrode are respectively printed on the two sides of the substrate by adopting a screen printing method, so that the battery is of an integrated structure, and the structure ensures that the battery has more stable electrode-electrolyte contact when the battery is subjected to frequent deformation, and the discharge stability of the battery is ensured; meanwhile, the battery has a thinner thickness, and high flexibility of the battery is guaranteed.
The invention also provides a preparation method of the flexible metal-air battery, which is used for preparing the flexible metal-air battery and comprises the following steps:
respectively manufacturing silver grid current collectors on two sides of a substrate by adopting a screen printing mode to obtain a first substrate;
screen printing a metal electrode on the surface of the silver grid current collector on one side of the first matrix by using metal anode ink, and screen printing an air electrode on the surface of the silver grid current collector on the other side of the first matrix by using air cathode ink to obtain a second matrix;
and carrying out hot pressing treatment on the second substrate to obtain the flexible metal-air battery.
Preferably, after the silver grid current collector, the metal electrode and the air electrode are screen printed, drying treatment is carried out, wherein the drying temperature is 60-70 ℃; the hot pressing treatment is carried out at 90-100deg.C under 1-2MPa for 5-10min.
Preferably, the metal anode ink is obtained by dissolving metal particles, a corrosion inhibitor, a first conductive additive and a first binder in a solvent, and mixing and dispersing the metal particles, wherein the metal particles comprise zinc powder, the corrosion inhibitor comprises one of zinc oxide, bismuth trioxide and sodium silicate, the first conductive additive comprises one of carbon powder, silver powder and a conductive polymer, the first binder comprises one of methylcellulose, sodium polyacrylate, polyethylene oxide, polyvinylidene fluoride and styrene-butadiene, the concentration of the zinc powder in the metal anode ink is 200-800mg/mL, and the concentration of the carbon powder is 60-100mg/mL.
Preferably, the air cathode ink is obtained by dissolving an oxygen reduction catalyst, a second conductive additive and a second binder in a solvent and mixing and dispersing the mixture, wherein the oxygen reduction catalyst comprises manganese dioxide, the second conductive additive comprises one of carbon powder, silver powder and conductive polymer, the second binder comprises perfluorinated sulfonic acid polymer, the concentration of the manganese dioxide in the air cathode ink is 80-160mg/mL, and the concentration of the carbon powder is 20-60mg/mL.
Preferably, the preparation method of the flexible metal-air battery further comprises the following steps: providing an electrolyte solution for absorption by the substrate, wherein the electrolyte solution comprises an alkaline electrolyte and a neutral electrolyte, the concentration of the alkaline electrolyte is 1-4mol/L, and the concentration of the neutral electrolyte is 1-4mol/L.
Compared with the prior art, the preparation method of the flexible metal-air battery has the advantages that:
the electrode ink is integrated on the surface of the substrate by adopting the screen printing technology, so that high-precision, low-cost and low-energy-consumption large-scale battery printing and manufacturing can be realized without battery manufacturing environments such as high temperature, high pressure and the like; the method has the advantages of low raw material price, simple and efficient production mode, environmental friendliness and the like, is very suitable for being applied to novel electronic equipment such as electronic detection test paper, biological sensors, intelligent packaging boxes and the like, and has very broad technical prospect and economic benefit. Other advantages are the same as those of the flexible metal-air battery compared with the prior art, and are not described in detail herein.
The invention also provides a flexible metal-air battery pack, which comprises a plurality of flexible metal-air batteries, wherein the plurality of flexible metal-air batteries are stacked and arranged in series or in parallel;
or the metal electrodes and the air electrodes of the plurality of flexible metal-air batteries are respectively printed on two sides of the same layer of substrate, and the metal electrodes and the air electrodes of two adjacent flexible metal-air batteries are connected with each other.
Preferably, when a plurality of flexible metal-air batteries are stacked, a protrusion is arranged between two adjacent flexible metal batteries, and the protrusion is used for enabling the stacked plurality of flexible metal batteries to be arranged at intervals.
The advantages of the flexible metal-air battery of the present invention over the prior art are the same as those of the flexible metal-air battery over the prior art and are not described in detail herein.
Drawings
FIG. 1 is a block diagram of a flexible metal-air battery in accordance with an embodiment of the present invention;
FIG. 2 is a second block diagram of a flexible metal-air battery in accordance with an embodiment of the present invention;
FIG. 3 is a block diagram III of a flexible metal-air battery in accordance with an embodiment of the present invention;
FIG. 4 is a block diagram of a flexible metal-air battery according to an embodiment of the present invention;
FIG. 5 is a composition of a zinc anode ink and an oxygen reduction cathode ink in an embodiment of the invention;
FIG. 6 is a schematic illustration of a flexible metal-air battery manufacturing process in accordance with an embodiment of the present invention;
FIG. 7 shows the effect of zinc powder concentration in anode ink on cell performance;
FIG. 8 shows the effect of carbon powder concentration in anode ink on cell performance;
FIG. 9 shows MnO in cathode ink 2 Influence of concentration on cell performance;
FIG. 10 shows the effect of carbon powder concentration in a cathode ink on cell performance;
FIG. 11 shows the effect of alkaline electrolytes of different concentrations on cell performance;
FIG. 12 shows the effect of different concentrations of neutral electrolytes on cell performance;
fig. 13 is a schematic view showing the structure of a multi-layered stacked cell stack according to an embodiment of the present invention;
fig. 14 is a schematic view showing the structure of a single-layered arranged cell stack in accordance with an embodiment of the present invention.
Reference numerals illustrate:
1-a substrate; 2-air electrode; 3-metal electrodes; 4-metallic anode ink; 5-air cathode ink; 6-a screen plate; 7-an electrolyte solution; 8-solid gel electrolyte.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
The flexible metal-air battery comprises a substrate 1, a metal electrode 3 and an air electrode 2, wherein the metal electrode 3 and the air electrode 2 are respectively screen-printed on two sides of the substrate 1; also included is a solid gel electrolyte 8 or electrolyte solution 7, the solid gel electrolyte 8 being stored inside the substrate 1, the substrate 1 being adapted to substantially absorb the electrolyte solution 7 to wet the metal electrode 3 and the air electrode 2.
The flexible metal-air battery of this embodiment adopts the screen printing method (may also be referred to as screen printing), and the metal electrode 3 and the air electrode 2 are printed on both sides of the substrate 1, wherein the metal electrode 3 is an anode, and the air electrode 2 is a cathode, and it can be understood that the electrode ink of the cathode and the anode is printed on both sides of the substrate 1 during the screen printing, that is, the metal electrode 3 and the air electrode 2 can be screen printed, and the electrolyte is stored in the substrate 1, so that the contact between the electrode and the electrolyte is stronger, or the cathode and the anode are wetted by the way of absorbing the electrolyte by the substrate 1, thereby realizing the activation of the battery.
The embodiment adopts the integrated battery structure, so that the battery has more stable electrode-electrolyte contact when facing frequent deformation, and the stability of discharging of the battery is ensured; meanwhile, the battery has a thinner thickness, the thickness of the printing electrode is almost negligible, the thickness of the battery is similar to that of the substrate 1, and the high flexibility of the battery is ensured; in addition, the electrode ink is integrated on the surface of the substrate 1 by adopting the screen printing technology, so that high-precision, low-cost and low-energy-consumption large-scale battery printing manufacturing can be realized without battery manufacturing environments such as high temperature, high pressure and the like.
In some embodiments, the substrate 1 comprises a single-layer substrate, and the metal electrode 3 and the air electrode 2 are respectively screen-printed on two sides of the single-layer substrate; the solid gel electrolyte 8 is stored inside the substrate 1 or the substrate 1 is used to fully absorb the electrolyte solution 7 to wet the metal electrode 3 and the air electrode 2.
In this embodiment, the substrate 1 is a single-layer substrate, and the substrate 1 refers to a cellulose paper as the substrate 1, which has a light weight and a certain flexibility, so that the high flexibility of the prepared battery can be ensured; on the other hand, the cellulose paper is porous and has certain hygroscopicity, so the electrolyte of the embodiment can be in a solid gel state or can be in a liquid state, specifically, the solid gel electrolyte 8 can be stored in the internal pores of the substrate 1, once the battery is contacted with air, continuous self-discharge can be caused, the electrolyte solution 7 can also be adopted, and the electrolyte solution 7 can be absorbed by utilizing the hygroscopicity of the paper of the electrolyte solution, so that the metal electrode 3 and the air electrode 2 are wetted, and the activation of the battery is realized; on the other hand, the cellulose paper has no pollution to the environment, and the cellulose paper is adopted as the substrate 1 of the battery, so that the waste battery can be conveniently treated.
Therefore, the embodiment adopts cellulose paper as the substrate 1 material of the whole battery, can simultaneously meet the printing of electrodes, the intake or storage of electrolyte and the flexibility of the battery, and can treat waste batteries in a simple incineration mode, thereby having high environmental protection degree.
Illustratively, as shown in fig. 1, the cell comprises a single layer substrate with cathodes and anodes printed on either side of the substrate 1. The battery has no self-discharge phenomenon and does not need to be stored in a sealed way. In use, electrolyte solution 7 is provided to the bottom of substrate 1 and after substrate 1 has fully absorbed the electrolyte and wetted the printed electrodes, the cell is successfully activated and begins to operate. It should be noted that fig. 1 (a) is an exploded schematic view of the screen printing process, and fig. 1 (b) is a schematic view of the structure of the prepared flexible metal-air battery.
As shown in fig. 2, the battery comprises a single-layer substrate, a cathode and an anode are printed on both sides of the substrate 1, respectively, and a solid gel electrolyte 8 is stored in advance inside the substrate 1. Such batteries, once exposed to air, cause continuous self-discharge and require sealed storage. In the using process, the paper for sealing the cathode is torn, and the battery can start to work. It should be noted that fig. 2 (a) is an exploded schematic view of the screen printing process, and it can be seen that the substrate 1 stores the solid gel electrolyte 8 therein, and fig. 2 (b) is a schematic view of the structure of the prepared flexible metal-air battery.
In some embodiments, the substrate 1 comprises a double-layer substrate, the metal electrode 3 and the air electrode 2 are respectively screen-printed on two different substrates 1, and one surface of the two substrates 1, on which the metal electrode 3 and the air electrode 2 are not printed, is bonded together.
In the present embodiment, the substrate 1 is a double-layered substrate, that is, two substrates 1 are used as the substrates 1 of the battery. The air electrode 2 is printed on one of the substrates 1 by a screen printing method, the metal electrode 3 is printed on the other substrate 1 by a screen printing method, and one surface of the two substrates 1, on which the electrode is not printed, is bonded together, so that the metal electrode 3 and the air electrode 2 correspond back to back.
When a flexible metal-air battery such as a zinc-air battery is used as a secondary battery, zinc in the negative electrode of the electrode forms dendrites during the regeneration process, and is likely to contact the positive electrode, thereby causing a short circuit of the battery. In addition, when the cathode and anode electrodes are printed on the battery substrate 1, the electrode ink used for printing may contact the other electrode through the substrate 1, thereby causing a short circuit. The embodiment adopts the battery structure of the double substrates 1, can effectively avoid internal short circuit of the battery caused by the penetration of electrode ink through the substrates 1, and can accelerate the intake speed of electrolyte through gaps among the substrates 1, thereby improving the activation speed and power output of the battery.
In some embodiments, the solid gel electrolyte 8 is stored in the two substrates 1, and the two substrates 1 are bonded together through the solid gel electrolyte 8; alternatively, both of the substrates 1 sufficiently absorb the electrolyte solution 7 to wet the metal electrode 3 and the air electrode 2, respectively.
For the battery structure of the two substrates 1, when the solid gel electrolyte 8 is employed, the electrolytes can be stored inside the two substrates 1, respectively, and at this time, the two substrates 1 can be bonded by using the viscosity of the gel electrolyte itself. When the electrolyte solution 7 in a liquid state is used, activation of the battery can be achieved by the double-layered substrate from absorbing the electrolyte solution 7 to wetting the cathode and anode electrodes.
Illustratively, as shown in fig. 3, the battery comprises a double-layered substrate, a cathode and an anode are printed on different substrates 1, respectively, and the two substrates 1 are bonded using a hydrophilic adhesive, with the cathode and anode electrodes corresponding back to back. The battery has no self-discharge phenomenon and does not need to be stored in a sealed way. In use, electrolyte solution 7 is provided to the bottom of substrate 1 and after substrate 1 has fully absorbed the electrolyte and wetted the printed electrodes, the cell is successfully activated and begins to operate. It should be noted that fig. 3 (a) is an exploded schematic view of the screen printing process, it can be seen that the battery structure includes two substrates 1, the cathode and anode are correspondingly disposed back to back on the two substrates 1, and fig. 3 (b) is a schematic view of the structure of the prepared flexible metal-air battery.
As shown in fig. 4, the battery comprises a double-layered substrate, a cathode and an anode are printed on different substrates 1, respectively, and a solid gel electrolyte 8 is stored in advance inside the two substrates 1, respectively; finally, the two substrates 1 are bonded by using the self-viscosity of the gel electrolyte, and the cathode and anode electrodes are in back-to-back correspondence. Such batteries, once exposed to air, cause continuous self-discharge and require sealed storage. In the using process, the paper for sealing the cathode is torn, and the battery can start to work. It should be noted that fig. 4 (a) is an exploded schematic view of the screen printing process, it can be seen that the battery structure includes two substrates 1, the cathode and anode are correspondingly disposed back to back on the two substrates 1, the solid gel electrolyte 8 is stored in the two substrates 1, and fig. 4 (b) is a schematic view of the structure of the prepared flexible metal-air battery.
The embodiment of the invention also provides a preparation method of the flexible metal-air battery, which is used for preparing the flexible metal-air battery and comprises the following steps:
respectively manufacturing silver grid current collectors on two sides of a substrate 1 by adopting a screen printing mode to obtain a first matrix;
screen printing a metal electrode 3 on the surface of the silver grid current collector on one side of the first matrix by using metal anode ink 4, and screen printing an air electrode 2 on the surface of the silver grid current collector on the other side of the first matrix by using air cathode ink 5 to obtain a second matrix;
and carrying out hot pressing treatment on the second substrate to obtain the flexible metal-air battery.
In this embodiment, a screen printing method is adopted to print silver grid current collectors on two sides of a substrate 1 respectively, the printing slurry is conductive silver slurry, then a metal anode ink 4 is used to print an anode on the surface of the silver grid current collector on one side, a cathode is printed on the surface of the silver grid current collector on the other side, and finally, a hot pressing treatment is performed on the battery to enhance the mechanical strength of the printed electrode on the surface of the substrate 1, so as to obtain the flexible metal air battery.
The screen printing is a method for applying ink on a printing piece through meshes of the screen printing plate 6 by utilizing a scraper, and can realize mass and low-cost production of flexible film batteries, ensure the processing efficiency and reduce the energy consumption in the processing process; secondly, the screen printing can be used for coating electrode materials with ultra-low thickness with high precision, and the characteristic has great advantages in manufacturing ultra-thin flexible batteries; in addition, screen printing is mainly finished by screen plates and scrapers, high-precision spray nozzle equipment is not needed, and more diversified electrochemical functional ink properties (such as particle size, concentration, corrosiveness and the like) can be tolerated.
The embodiment adopts the screen printing technology to integrate the electrode ink on the surface of the porous substrate 1, does not need high-temperature high-pressure battery manufacturing environments and the like, and can realize high-precision, low-cost and low-energy-consumption large-scale battery printing manufacturing.
In some embodiments, after the silver grid current collector, the metal electrode 3 and the air electrode 2 are screen printed, drying treatment is performed, and the drying temperature is 60-70 ℃.
In this embodiment, the heating and drying treatment is further performed after the cathode and anode electrodes are screen printed, so that on one hand, the uneven thickness of the electrodes caused by the flowing of the electrode ink of printing paste or conductive silver paste is prevented, and on the other hand, the mechanical strength between the electrodes and the substrate 1 can be improved.
In some embodiments, the heat pressing treatment is performed at a temperature of 90-100deg.C and a pressure of 1-2MPa for 5-10min.
In this embodiment, the mechanical strength between the printing electrode and the substrate 1 is enhanced by the heat press treatment under the above conditions.
In some embodiments, the method of making a flexible metal-air battery further comprises: after the battery is subjected to hot pressing treatment, a layer of breathable outer package is added on the surface of the battery, and the electrode is protected so as to avoid direct contact of a user with the electrode.
In some embodiments, the metal anode ink 4 is obtained by dissolving metal particles, a corrosion inhibitor, a first conductive additive and a first binder in a solvent, and mixing and dispersing the metal particles, wherein the metal particles comprise zinc powder, the corrosion inhibitor comprises one of zinc oxide, bismuth trioxide and sodium silicate, the first conductive additive comprises one of carbon powder, silver powder and a conductive polymer, and the first binder comprises one of methylcellulose, sodium polyacrylate, polyethylene oxide, polyvinylidene fluoride and styrene-butadiene.
In this embodiment, the metal particles are used as an electrochemical active material, and the metal anode ink 4 is prepared by mixing the metal particles with a conductive additive, a binder, a corrosion inhibitor and a solvent, and is used as a printing paste for screen printing anodes, wherein the corrosion inhibitor can inhibit the self-corrosion rate of zinc particles in the anode ink, and the storage life of the battery is prolonged; the metal anode ink 4 in this embodiment contains conductive additives such as carbon powder/silver powder/conductive polymer, and binders such as methylcellulose/sodium polyacrylate/polyethylene oxide/polyvinylidene fluoride/styrene-butadiene, and has functions of thickening and viscosity adjustment, and no additional addition of other additives such as a thickening agent and a viscosity regulator is required; meanwhile, the embodiment also uses hot pressing treatment after the electrode is printed, so that the electrode can be ensured to be smooth and flat, and additive auxiliary agents such as leveling agents for enabling the printed electrode to be smooth and flat are omitted.
In some embodiments, the air cathode ink 5 is obtained by dissolving an oxygen reduction catalyst, a second conductive additive and a second binder in a solvent, and mixing and dispersing the mixture, wherein the oxygen reduction catalyst comprises manganese dioxide, the second conductive additive comprises one of carbon powder, silver powder and conductive polymer, and the second binder comprises perfluorinated sulfonic acid polymer.
In the embodiment, the non-noble metal catalyst material such as manganese dioxide is adopted, the price is low, and the battery quality and the cost can be accurately controlled by matching with the low-cost low-energy consumption method such as the screen printing technology.
Illustratively, as shown in fig. 5, the electrode functional ink in the present embodiment mainly includes two kinds of zinc anode ink and air self-breathing cathode ink (or referred to as oxygen reduction cathode ink), wherein the zinc anode ink has the main components: zinc particles, zinc oxide, carbon loading (i.e., carbon powder), binders, and solvents; the main components of the air self-breathing cathode ink are as follows: oxygen reduction catalyst, carbon support, binder, solvent. In consideration of environmental protection, an ethanol aqueous solution is adopted as a solvent of the electrode functional ink, and stirring, ultrasonic and other means are utilized to ensure that all substances in the electrode ink are uniformly dispersed (organic solvents such as dimethyl sulfoxide/toluene and the like can also be adopted).
Illustratively, as shown in fig. 6, the battery screen printing process in the present embodiment is mainly divided into the following steps: (1) Firstly, printing uniformly distributed silver grid current collectors on two sides of a substrate 1 by using commercial conductive silver paste and a corresponding screen printing plate 6, and thoroughly drying at 60 ℃; (2) Printing anodes on the surface of a silver grid on one side by using the zinc anode ink and the corresponding screen printing plate 6, and thoroughly drying at 60 ℃; (3) Printing a cathode on the surface of the silver grid on the other side by using the air self-breathing cathode ink and the corresponding screen printing plate 6, and thoroughly drying at 60 ℃; (4) Carrying out battery hot pressing for 5 minutes at 90 ℃ and 1 megapascal by using a hot press, and enhancing the mechanical strength of the printing electrode on the paper-based surface; 5) Finally, a layer of breathable outer package can be added on the surface of the battery, so that the user is prevented from directly contacting the electrode.
In some embodiments, the concentration of the zinc powder in the metal anode ink 4 is 200-800mg/mL, and the concentration of the carbon powder is 60-100mg/mL.
The concentration of manganese dioxide in the air cathode ink 5 is 80-160mg/mL, and the concentration of carbon powder is 20-60mg/mL.
The electrolyte solution 7 comprises an alkaline electrolyte and a neutral electrolyte, wherein the concentration of the alkaline electrolyte is 1-4mol/L, and the concentration of the neutral electrolyte is 1-4mol/L.
The battery performance is completely dependent on its electrode functional ink and electrolyte, and mainly comprises: zinc powder concentration and carbon powder concentration in the anode ink; mnO in cathode ink 2 Powder concentration, carbon powder concentration; electrolyte composition, concentration, etc. Therefore, the present embodiment finds that optimum battery performance can be obtained by employing parameters within the above-described ranges through experimental study of battery performance. The method specifically comprises the following steps:
(1) Influence of zinc powder concentration in anode ink on cell performance;
three zinc powder concentrations were selected altogether: 200mg/mL, 500mg/mL, 800mg/mL. As shown in fig. 7: when the zinc powder concentration is only 200mg/mL, the performance of the battery is limited, and the maximum power density is only 20mW/cm although the open circuit voltage is kept unchanged at 1.4V 2 The method comprises the steps of carrying out a first treatment on the surface of the When the zinc powder concentration is increased to 500mg/mL, the maximum power density is increased to 32mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The zinc powder concentration was continuously increased to 800mg/mL, and the cell performance was not significantly changed, indicating that a zinc powder concentration of 500mg/mL was sufficient. However, from the energy density point of view, the more zinc powder is contained in the printed anode, the more energy is stored per unit area of the battery, for example, the discharge capacity of a 500mg/mL battery is 1.5mAh/cm 2 While the discharge capacity of the 800mg/mL battery was 2.9mAh/cm 2 . In addition, continued increases in zinc powder concentration can result in excessive viscosity of the anode ink, which is detrimental to screen printing. Therefore, in this embodiment, the concentration of zinc powder in the metallic anode ink 4 is preferably 200 to 800mg/mL, more preferably 500mg/mL.
(2) Influence of carbon powder concentration in the anode ink on battery performance;
three carbon powder concentrations were selected altogether: 60mg/mL, 80mg/mL, 100mg/mL. As shown in fig. 8: when the carbon powder concentration is 60mg/mL, the battery performance is optimal, and the continuous addition of the carbon powder to 80mg/mL and 100mg/mL has negative effects on the battery performance. This is probably because the use of conductive polymers in the anode ink weakens the effect of carbon powder concentration on the conductivity of the electrode, which in turn affects the absorption of electrolyte by zinc powder in the anode. In addition, when the carbon powder concentration reaches 100mg/mL, the viscosity of the anode ink is too high to be beneficial to screen printing. Therefore, in this embodiment, the concentration of carbon powder in the metallic anode ink 4 is preferably 60 to 100mg/mL, more preferably 60mg/mL.
(3) MnO in cathode ink 2 Influence of concentration on cell performance;
three MnO's are selected in total 2 Concentration: 80mg/mL, 120mg/mL, 160mg/mL. As shown in fig. 9: when MnO 2 When the concentration is 80mg/mL, the battery performance reaches the optimum, and MnO is continuously added 2 There was little gain to 120mg/mL, 160mg/mL on battery performance. This is because of 80mg/mL MnO 2 The catalyst is sufficient to support the cathode requirements of the cells of the present invention, continuing to increase MnO 2 Not only increases the manufacturing cost of the battery and the environmental protection pressure, but also causes the viscosity of the cathode ink to be too high, which is unfavorable for screen printing. Thus, in this embodiment, the concentration of manganese dioxide in the air cathode ink 5 is preferably 80-160mg/mL, more preferably 80mg/mL.
(4) Influence of carbon powder concentration in the cathode ink on battery performance;
three carbon powder concentrations were selected altogether: 20mg/mL, 40mg/mL, 60mg/mL. It should be noted that the carbon powder concentration in the cathode ink is much less than that in the anode ink, mainly because the cathode ink already contains high concentration of MnO 2 Further increases in carbon powder concentration can result in too viscous cathode ink, which is detrimental to screen printing. As shown in fig. 10: when the carbon powder concentration is 20mg/mL, the maximum power density of the battery is 20mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Carbon powder is continuously added to 40mg/mL, the battery performance is greatly improved, and the maximum power density is increased to 32.5mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Carbon powder is continuously added to 60mg/mL, and the battery performance is not changed any more. Therefore, in this embodiment, the carbon powder in the air cathode ink 5 is preferably 20 to 60mg/mL, and more preferably 40 mg/mL.
(5) Influence of alkaline electrolytes with different concentrations on battery performance;
KOH is selected as electrolyte solute, and four KOH concentrations are selected: 1M, 2M, 3M, 4M. As shown in fig. 11: when the KOH concentration is 1M, the open-circuit voltage of the battery is only 1.2V, and the power density and the current density are very weak and cannot work normally; when the KOH concentration is increased to 2M, the open-circuit voltage of the battery is increased to 1.4V normal value, the maximumThe power density also reaches 9mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The KOH concentration was increased to 3M and the maximum power density was increased to 18.6mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the When the KOH concentration finally reaches 4M, the maximum power density reaches 32mW/cm 2 . Further increase in the KOH concentration not only causes shrinkage deformation of the battery substrate 1 but also increases the danger of battery use, and therefore, in this embodiment, the concentration of the alkaline electrolyte is preferably 1 to 4M, more preferably 4M KOH as the alkaline electrolyte of the present battery.
(6) Influence of neutral electrolytes with different concentrations on battery performance;
NaCl is selected as electrolyte solute, four NaCl concentrations are selected in total: 1M, 2M, 3M, 4M. As shown in fig. 12: when the NaCl concentration is 1M, the open-circuit voltage of the battery reaches the normal value of 1V, but the maximum power density is only 5.8mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the When the NaCl concentration was increased to 2M, the maximum power density of the cell was increased to 6.5mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Continuously increasing NaCl concentration to 3M, and slightly increasing maximum power density to 6.7mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the When the NaCl concentration finally reaches 4M, the maximum power density is not changed any more and is still 6.7mW/cm 2 . Therefore, in this embodiment, the concentration of the neutral electrolyte is preferably 1 to 4M, more preferably 2 to 3M NaCl as the neutral electrolyte of the present invention. Further, as can be seen from comparing fig. 11 and 12, battery performance far greater than that of the neutral electrolyte can be obtained using the alkaline electrolyte, but higher safety can be obtained using the neutral electrolyte.
In summary, the screen printing flexible metal-air battery has the advantages of low raw material price, simple and efficient production mode, high performance, high flexibility, environmental friendliness and the like, is very suitable for being applied to novel electronic equipment such as electronic detection test paper, biological sensors, intelligent packaging boxes and the like, and has very broad technical prospect and economic benefit.
The invention also provides a flexible metal-air battery pack, which comprises a plurality of flexible metal-air batteries, wherein a plurality of flexible metal-air batteries are stacked and arranged, and the flexible metal-air batteries are connected in series or in parallel.
The present embodiment also provides a stack integration mode corresponding to the screen printed flexible metal-air single cell, for example, the present embodiment adopts a multi-layer stacked stack structure (as shown in fig. 13), the battery is formed by directly stacking a plurality of single cells, and the single cells can be connected in series in a mode of "cathode-anode" or "anode-cathode" or in parallel in a mode of "cathode-cathode" or "anode-anode" so as to obtain higher voltage or current output. The battery pack has the advantages that the battery pack is flexible to assemble, and the area power density and the area energy density increase with the number of single cells; however, since the thickness of the battery pack is increased to continuously impair its flexible characteristics, the number of unit cells is not excessively large, and the present embodiment preferably stacks 3 to 5 unit cells.
In some embodiments, a protrusion is disposed between two adjacent flexible metal batteries, and the protrusion is used to space a plurality of stacked flexible metal batteries.
In this embodiment, a protrusion is disposed between two adjacent flexible metal batteries to separate a plurality of unit cells, for example, a dot protrusion is added on the cathode side of each unit cell, so as to avoid that the cathode of the internal unit cell is completely covered, and air transmission is affected.
The invention also provides a flexible metal-air battery pack, which comprises a plurality of flexible metal-air batteries, wherein the metal electrodes 3 and the air electrodes 2 of the plurality of flexible metal-air batteries are respectively printed on the two sides of the same layer of substrate 1, and the metal electrodes 3 and the air electrodes 2 of two adjacent flexible metal-air batteries are connected with each other.
The present embodiment provides a single-layer arranged cell stack. The battery pack prints a plurality of unit cell electrodes on the same layer of the surface of the substrate 1 (as shown in fig. 14), and a series/parallel mode of the battery pack is predetermined by a connection manner between silver grid current collectors. In the printing process, the silver grid current collectors of different single cells can be connected through printing silver wires according to a galvanic pile design scheme, and the assembly is very convenient as shown by a broken line frame in fig. 14. In addition, the battery pack is more suitably used with the solid gel electrolyte 8 than the liquid electrolyte in consideration of the parasitic current phenomenon between the unit cells. The battery pack has the advantages that the battery pack can be printed and molded at one time without sacrificing the flexibility characteristic of the thin film battery, but the improvement of the area power density and the area energy density is limited.
The invention is further illustrated by the following examples.
Example 1
The formula of the battery anode ink is as follows: 500mg zinc powder, 80mg zinc oxide powder, 1 mg polyethylene dioxythiophene, 60mg carbon powder, dissolved in 1 ml 50% alcohol.
The formula of the cathode ink of the battery is as follows: 80mg of manganese dioxide, 80mg of perfluorosulfonic acid resin and 40mg of carbon powder are dissolved in 1 ml of 50% alcohol.
The anode ink was printed on the surface of one piece of filter paper using a screen printer, the cathode ink was printed on the surface of the other piece of filter paper, and the two pieces were bonded together (cathode and anode were back to back). After natural inhalation by capillary action using 4M sodium chloride solution as electrolyte, the open-circuit voltage of the battery was measured to be 1V, and the maximum power density was measured to be 6.7mW/cm 2 Maximum current density of 16.7mA/cm 2 。
Example 2
The formula of the battery anode ink is as follows: 500mg zinc powder, 80mg zinc oxide powder, 1 mg polyethylene dioxythiophene, 60mg carbon powder, dissolved in 1 ml 50% alcohol.
The formula of the cathode ink of the battery is as follows: 80mg of manganese dioxide, 80mg of perfluorosulfonic acid resin and 40mg of carbon powder are dissolved in 1 ml of 50% alcohol.
The anode ink was printed on the surface of one piece of filter paper using a screen printer, the cathode ink was printed on the surface of the other piece of filter paper, and the two pieces were bonded together (cathode and anode were back to back). After natural inhalation by capillary action using 4M potassium hydroxide solution as electrolyte, the open-circuit voltage of the cell was measured to be 1.4V, and the maximum power density was measured to be 31.9mW/cm 2 Maximum current density of 35.4mA/cm 2 。
Although the invention is disclosed above, the scope of the invention is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications will fall within the scope of the invention.
Claims (10)
1. A flexible metal-air battery, characterized by comprising a substrate (1), a metal electrode (3) and an air electrode (2), wherein the metal electrode (3) and the air electrode (2) are respectively screen-printed on two sides of the substrate (1); also included is a solid gel electrolyte (8) or electrolyte solution (7), the solid gel electrolyte (8) being stored inside the substrate (1), the substrate (1) being adapted to substantially absorb the electrolyte solution (7) to wet the metal electrode (3) and the air electrode (2).
2. A flexible metal-air battery according to claim 1, characterized in that the substrate (1) comprises a single-layer paper substrate or a double-layer paper substrate;
when the substrate (1) is the single-layer paper substrate, the metal electrode (3) and the air electrode (2) are respectively screen-printed on two sides of the single-layer paper substrate;
when the substrate (1) is the double-layer paper substrate, the metal electrode (3) and the air electrode (2) are respectively screen printed on two different paper substrates, and one surfaces of the two paper substrates, on which the metal electrode (3) and the air electrode (2) are not printed, are bonded together.
3. A flexible metal-air battery according to claim 2, characterized in that when the substrate (1) is the single-layer paper substrate, the solid gel electrolyte (8) is stored inside the single-layer paper substrate, or the single-layer paper substrate is used to fully absorb the electrolyte solution (7) to wet the metal electrode (3) and the air electrode (2);
when the substrate (1) is the double-layer paper substrate, the solid gel electrolyte (8) is respectively stored in the two paper substrates, and the two paper substrates are bonded together through the solid gel electrolyte (8); alternatively, two sheets of the paper substrate are bonded together by an adhesive, and the two sheets of the paper substrate are used to sufficiently absorb the electrolyte solution (7) to wet the metal electrode (3) and the air electrode (2), respectively.
4. A method of making a flexible metal-air battery according to any one of claims 1-3, comprising:
respectively manufacturing silver grid current collectors on two sides of a substrate (1) in a screen printing mode to obtain a first matrix;
screen printing a metal electrode (3) on the surface of the silver grid current collector on one side of the first matrix by using metal anode ink (4), and screen printing an air electrode (2) on the surface of the silver grid current collector on the other side of the first matrix by using air cathode ink (5) to obtain a second matrix;
and carrying out hot pressing treatment on the second substrate to obtain the flexible metal-air battery.
5. The method for manufacturing a flexible metal-air battery according to claim 4, wherein after screen printing the silver grid current collector, the metal electrode (3) and the air electrode (2), all are subjected to a drying treatment at a drying temperature of 60-70 ℃; the hot pressing treatment is carried out at 90-100deg.C under 1-2MPa for 5-10min.
6. The method for manufacturing a flexible metal-air battery according to claim 4, wherein the metal anode ink (4) is obtained by dissolving metal particles, a corrosion inhibitor, a first conductive additive and a first binder in a solvent, and mixing and dispersing the metal particles, wherein the metal particles comprise zinc powder, the corrosion inhibitor comprises one of zinc oxide, bismuth trioxide and sodium silicate, the first conductive additive comprises one of carbon powder, silver powder and a conductive polymer, the first binder comprises one of methylcellulose, sodium polyacrylate, polyethylene oxide, polyvinylidene fluoride and styrene-butadiene, the concentration of the zinc powder in the metal anode ink (4) is 200-800mg/mL, and the concentration of the carbon powder is 60-100mg/mL.
7. The method for producing a flexible metal-air battery according to claim 4, wherein the air cathode ink (5) is obtained by dissolving an oxygen reduction catalyst, a second conductive additive and a second binder in a solvent, and mixing and dispersing the mixture, wherein the oxygen reduction catalyst comprises manganese dioxide, the second conductive additive comprises one of carbon powder, silver powder and a conductive polymer, the second binder comprises a perfluorosulfonic acid type polymer, the concentration of manganese dioxide in the air cathode ink (5) is 80-160mg/mL, and the concentration of carbon powder is 20-60mg/mL.
8. The method of manufacturing a flexible metal-air battery of claim 4, further comprising: providing an electrolyte solution (7) for absorption by the substrate (1), the electrolyte solution (7) comprising an alkaline electrolyte having a concentration of 1-4mol/L and a neutral electrolyte having a concentration of 1-4mol/L.
9. A flexible metal-air battery comprising a plurality of flexible metal-air cells according to any one of claims 1-3, a plurality of said flexible metal-air cells being stacked and a plurality of said flexible metal-air cells being connected in series or in parallel;
alternatively, the metal electrodes (3) and the air electrodes (2) of a plurality of the flexible metal-air batteries are respectively printed on two sides of the same layer of substrate (1), and the metal electrodes (3) and the air electrodes (2) of two adjacent flexible metal-air batteries are connected with each other.
10. The flexible metal-air battery of claim 9, wherein when a plurality of the flexible metal-air batteries are stacked, a protrusion is disposed between two adjacent flexible metal batteries, the protrusion being configured to space the stacked plurality of flexible metal batteries.
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