A flexible all-gel zinc-air battery and its preparation method

Abstract

The present invention discloses a flexible all-gel zinc-air battery and a preparation method thereof, belonging to the technical field of zinc-air batteries. The preparation method includes: adding water to an acrylamide matrix and stirring, then adding a conductive active substance or a conductive polymer, a pore-forming agent, and a binder and stirring evenly, and then adding a cross-linking agent, an initiator, and a catalyst to obtain a mixed solution, and then drying to obtain a conductive gel; adding water to an acrylamide matrix and stirring, then adding a cross-linking agent, an initiator, and a catalyst and stirring and mixing evenly, and then drying to obtain a gel; soaking the gel in a zinc salt alkaline electrolyte to obtain an alkaline gel electrolyte; drying the conductive gel and dropping a platinum-carbon catalyst as the positive electrode, and then performing dry cross-linking at the interface with the alkaline gel electrolyte to obtain an all-gel, and using a zinc foil or a zinc sheet as the negative electrode; wrapping the positive electrode, the all-gel, and the negative electrode with a soft-pack outer package to form a flexible all-gel zinc-air battery.

Description

Technical Field

[0001] The present invention belongs to the technical field of zinc-air batteries, and particularly relates to a flexible all-gel zinc-air battery and a preparation method thereof. Background Art

[0002] With the development and prosperity of flexible wearable electronic products, it is imperative to produce flexible energy storage devices with high energy density, reliability and safety. The structures of existing traditional batteries can no longer meet the requirements of microelectronic devices, especially the separator film layer inside the existing traditional batteries. Conventional traditional batteries are assembled with a positive electrode, a separator film layer and a negative electrode, but this may cause relative sliding, is not firm, and moreover, affects the product quality. Summary of the Invention

[0003] In order to overcome the above-mentioned disadvantages of the prior art, the purpose of the present invention is to provide a flexible all-gel zinc-air battery and a preparation method thereof. The flexible all-gel zinc-air battery of the present invention uses a dry cross-linking method based on hydrogen bond adsorption to bond the conductive gel loaded with active substances on the outer surface of the gel electrolyte, effectively avoiding the interfacial contact impedance between battery components, and greatly improving the problem of the load area of the positive electrode, so as to obtain an all-gel zinc-air battery with high areal energy density and high volumetric energy density.

[0004] To achieve the above purpose, the present invention adopts the following technical solutions:

[0005] The present invention discloses a preparation method of a flexible all-gel zinc-air battery, comprising the following steps:

[0006] S1: Add water to the acrylamide matrix and stir, then add a conductive active substance or a conductive polymer, a pore former, a binder and stir evenly, then add a cross-linking agent, an initiator and a catalyst to obtain a mixed solution, and then dry it to obtain a conductive gel;

[0007] S2: Add water to the acrylamide matrix and stir, then add a cross-linking agent, an initiator and a catalyst and stir and mix evenly, then dry it to obtain a gel; soak the gel in a zinc salt alkaline electrolyte to obtain an alkaline gel electrolyte;

[0008] S3: Dry the conductive gel and drop platinum-carbon catalyst as the positive electrode, then perform dry cross-linking at the interface with the alkaline gel electrolyte to obtain an all-gel, and use a zinc foil or a zinc sheet as the negative electrode;

[0009] S4: Wrap the positive electrode, the all-gel and the negative electrode with a soft-pack outer package to form a flexible all-gel zinc-air battery.

[0010] Furthermore, the outer package of the soft package includes: a positive electrode, a positive electrode tab, a negative electrode, a negative electrode tab, a vent hole, and an adhesive layer;

[0011] A positive electrode tab is provided on the positive electrode, a negative electrode tab is provided on the negative electrode, and a vent hole is provided at the central part of the positive electrode; the vent hole corresponds to the position where the platinum-carbon catalyst is dropped; the positive electrode and the negative electrode are adhered through the adhesive layer; the outer package is an aluminum-plastic film.

[0012] Furthermore, the cross-linking agent is N,N'-methylenebisacrylamide; the catalyst is tetramethylethylenediamine; the initiator is one of ammonium persulfate or potassium persulfate.

[0013] Furthermore, in S1, the conductive active material is one of carbon nanotubes, conductive carbon, and graphene; the conductive polymer is one of polyaniline, polypyrrole, and poly(3,4-ethylenedioxythiophene).

[0014] Furthermore, in S1, the pore-forming agent is one of polyethylene glycol-600 or polyethylene glycol-1000; the binder is one of carboxymethyl cellulose or sodium carboxymethyl cellulose.

[0015] Furthermore, in S1, the mass ratio of acrylamide to the conductive active material or conductive polymer, water, pore-forming agent, binder, cross-linking agent, catalyst, and initiator in the conductive gel is 1:(0.02 - 0.03):(2.5 - 3):(0.12 - 0.15):(0.025 - 0.03):(0.00025 - 0.0003):(0.001 - 0.0015):(0.007 - 0.0073).

[0016] Furthermore, in S2, the mass ratio of acrylamide to water, cross-linking agent, catalyst, and initiator in the alkaline gel electrolyte is 1:(2.5 - 3):(0.00025 - 0.0003):(0.001 - 0.0015):(0.007 - 0.0073).

[0017] Furthermore, in S2, the zinc salt alkaline electrolyte is a compound solution composed of potassium hydroxide and zinc acetate; the mass ratio of potassium hydroxide to zinc acetate is (7 - 8:1); the soaking time is 72h - 96h.

[0018] Furthermore, in S3, the platinum-carbon catalyst is a compound solution composed of platinum-carbon, isopropanol, and Nafion solution; the preparation dosage of platinum-carbon is 1 - 1.5mg / cm 2 , and the mass ratio of isopropanol to Nafion solution is (20 - 24):1.

[0019] The present invention discloses a flexible all-gel zinc-air battery prepared by using the preparation method described in any one of the above.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The present invention provides a preparation method for a flexible all-gel zinc-air battery. By using a dry cross-linking method based on hydrogen bond adsorption, a conductive gel loaded with active substances is bonded to the outer surface of the gel electrolyte, effectively avoiding the interfacial contact impedance between battery components and greatly improving the problem of the load area of the positive electrode. Thus, an all-gel zinc-air battery with high areal energy density and high volumetric energy density can be obtained.

[0022] By using the preparation method of the flexible all-gel zinc-air battery described in the present invention, the obtained battery integrates the positive electrode material and the gel electrolyte, does not require a separator needed for traditional battery preparation, avoids the interface between the electrode and the separator, and thus avoids the short-circuit problem caused during repeated deformation of the battery. Moreover, the interfacial contact impedance is reduced, making the main body more firm, reliable, and safe, and more suitable for flexible device applications. Further, due to the network structures of the conductive gel and the gel electrolyte, the battery obtains a larger load area for the positive electrode material, thereby improving the areal energy density and volumetric energy density of the battery. In addition, the use of a soft-pack design ensures safety and stability. Moreover, because of the simple structural design, the manufacturing efficiency of the manufacturer can be greatly improved, and it can be bent repeatedly for many times, having a wide application space in the field of flexible portable electronic devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is a structural diagram of the flexible all-gel zinc-air battery of the present invention;

[0024] Figure 2 is a stress-strain curve diagram of the flexible integrated all-gel of Examples 1, 2, 3, 4, and 5 of the present invention.

[0025] Wherein: 1 - positive electrode; 2 - negative electrode; 3 - positive electrode tab; 4 - negative electrode tab; 5 - vent hole; 6 - adhesive layer. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0026] To enable those skilled in the art to understand the features and effects of the present invention, the following provides a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used herein shall have the ordinary meaning understood by those skilled in the art for the present invention. In case of conflict, the definition in this specification shall prevail.

[0027] The theories or mechanisms described and disclosed herein, whether right or wrong, shall not in any way limit the scope of the present invention, that is, the content of the present invention can be implemented without being restricted by any specific theory or mechanism.

[0028] In this document, all features defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are only for the sake of brevity and convenience. Accordingly, the description of a numerical range or percentage range should be regarded as having covered and specifically disclosed all possible sub-ranges and individual numerical values (including integers and fractions) within the range.

[0029] In this document, unless otherwise specified, terms such as "comprising", "including", "containing", "having", or similar terms cover the meanings of "consisting of" and "consisting essentially of". For example, "A comprises a" covers the meanings of "A comprises a and others" and "A consists only of a".

[0030] In this document, for the sake of concise description, all possible combinations of all technical features in each embodiment or example are not described. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each embodiment or example can be combined arbitrarily, and all possible combinations should be considered to be within the scope described in this specification.

[0031] The present invention provides a flexible all-gel zinc-air battery and a preparation method thereof.

[0032] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0033] Conventional instrument equipment in the art is used in the following embodiments. For the experimental methods without specific conditions noted in the following embodiments, they are generally carried out under conventional conditions or according to the conditions recommended by the manufacturer. Various raw materials are used in the following embodiments. Unless otherwise stated, commercially available products are used, and their specifications are conventional specifications in the art. In the specification of the present invention and the following embodiments, unless otherwise specified, "%" represents weight percentage, "parts" represents weight parts, and the ratio represents weight ratio.

[0034] The present invention provides a preparation method of a flexible all-gel zinc-air battery. The preparation of the flexible all-gel zinc-air battery is to combine a conductive hydrogel and a hydrogel electrolyte through interfacial dry crosslinking to form an all-gel, and then use a soft-packaging technology to wrap it to form a flexible all-gel zinc-air battery, which specifically includes the following steps:

[0035] I. Preparation of the positive electrode: Take acrylamide matrix, conductive active material or conductive polymer, binder, pore former, and mix with water for physical stirring. Then, add crosslinking agent, initiator, and catalyst to the mixed solution in sequence, continue stirring and mixing. Next, put the obtained solution into a constant-temperature oven to obtain a conductive gel.

[0036] As an alternative, the mass ratio of acrylamide to active material in the conductive gel is 1:0.02 - 0.03, the mass ratio of acrylamide to water is 1:2.5 - 3; the mass ratio of acrylamide to crosslinking agent is 1:0.00025 - 0.0003; the mass ratio of acrylamide to catalyst is 1:0.001 - 0.0015; the mass ratio of acrylamide monomer to initiator is 1:0.007 - 0.0073; the mass ratio of acrylamide to pore former is 1:0.12 - 0.15; the mass ratio of acrylamide to binder is 1:0.025 - 0.03.

[0037] The conductive active material is one of carbon nanotubes, conductive carbon, and graphene; the conductive polymer is one of polyaniline, polypyrrole, and poly(3,4 - ethylenedioxythiophene); the pore former is one of polyethylene glycol - 600 or polyethylene glycol - 1000; the binder is one of carboxymethyl cellulose or sodium carboxymethyl cellulose.

[0038] II. Initiation of the gel electrolyte: Add matrix acrylamide, initiator, crosslinking agent, and catalyst to water for physical stirring, and then put it into a constant-temperature oven at 50 - 60 °C for reaction to obtain a gel. Immerse the gel in an alkaline zinc salt electrolyte to obtain an alkaline gel electrolyte.

[0039] As an alternative, the mass ratio of acrylamide to water in the alkaline gel electrolyte is 1:2.5 - 3, the mass ratio of acrylamide monomer to crosslinking agent is 1:0.00025 - 0.0003, the mass ratio of acrylamide monomer to catalyst is 1:0.001 - 0.0015, and the mass ratio of acrylamide monomer to initiator is 1:0.007 - 0.0073.

[0040] The alkaline zinc salt electrolyte is a compound solution composed of 6M / L potassium hydroxide and 0.2M / L zinc acetate; the dosage of the alkaline zinc salt electrolyte is 250 ml; the mass ratio of potassium hydroxide to zinc acetate is (7 - 8:1); the soaking time is 72h - 96h.

[0041] III. Crosslinking of the conductive gel and the gel electrolyte: The conductive gel prepared in step I is dried in an oven and platinum carbon catalyst is added dropwise, and then it is crosslinked with the alkaline electrolyte in step II through interfacial dry crosslinking to obtain a full gel.

[0042] The platinum-carbon catalyst is a compound solution composed of platinum-carbon (catalyst), isopropyl alcohol (dispersant), and Nafion solution (ionic polymer); the dosage of platinum-carbon is 1 - 1.5 mg / cm 2 The mass ratio of isopropyl alcohol to the 5 wt% Nafion solution is (20 - 24):1.

[0043] IV. Assembling and synthesizing a flexible all-gel zinc-air battery: Dry the conductive gel and drop the platinum-carbon catalyst as the positive electrode 1, and then conduct dry interfacial cross-linking with the alkaline gel electrolyte to obtain an all-gel. Use a zinc foil or zinc sheet as the negative electrode 2; Wrap the positive electrode 1, all-gel, and negative electrode 2 with a soft-pack outer package to form a flexible all-gel zinc-air battery.

[0044] As an alternative, the matrix is acrylamide; the cross-linking agent is N,N'-methylenebisacrylamide; the catalyst is tetramethylethylenediamine; the initiator is one of ammonium persulfate or potassium persulfate.

[0045] The soft-pack outer package includes: positive electrode 1, positive electrode tab 3, negative electrode 2, negative electrode tab 4, vent hole 5, adhesive layer 6;

[0046] A positive electrode tab 3 is provided on the positive electrode 1, a negative electrode tab 4 is provided on the negative electrode 2, and a vent hole 5 is provided at the central part of the positive electrode 1; the vent hole 5 corresponds to the position where the platinum-carbon catalyst is dropped; the positive electrode 1 and the negative electrode 2 are adhered through the adhesive layer 6; the outer package is an aluminum-plastic film.

[0047] As Figure 1 shown, the flexible all-gel zinc-air battery includes a conductive gel and the platinum-carbon catalyst dropped thereon as the positive electrode 1, a positive electrode tab 3 provided on the positive electrode 1, a gel electrolyte, a negative electrode 2, and a negative electrode tab 4 provided on the negative electrode 2;

[0048] Among them, the conductive gel and the platinum-carbon catalyst dropped on its surface as the positive electrode and the all-gel obtained by dry interfacial cross-linking of the conductive gel and the gel electrolyte, and the zinc foil or zinc sheet as the negative electrode 2 are wrapped inside by a soft-pack outer package.

[0049] Furthermore, the edges of the positive electrode 1 and the negative electrode ② are sealed: the positive electrode 1 is connected to the positive electrode tab 3, the negative electrode 2 is connected to the negative electrode tab 4, and both the positive electrode tab 3 and the negative electrode tab 4 are exposed on the outside. The positive electrode includes a positive electrode conductive gel and the dropped positive electrode catalyst (platinum-carbon catalyst), and an integral all-gel, and the negative electrode composed of a zinc foil or zinc sheet is wrapped inside by a soft-pack outer package. The positive electrode catalyst (platinum-carbon catalyst) is dropped on one side of the positive electrode conductive gel and faces the vent hole 5.

[0050] The positive electrode tab 3 is connected to the positive electrode 1 carrier, and the negative electrode tab 4 is connected to the negative electrode 2 carrier.

[0051] The positive electrode 1 and the negative electrode 2 are laminated, the adhesive layer 6 is folded over the back of the positive electrode 1 and bonded to seal the edges of the positive electrode 1 and the negative electrode 2; the positive electrode 1 and the positive electrode tab 3 are connected, and the negative electrode 2 and the negative electrode tab 4 are connected, and the positive electrode tab 3 and the negative electrode tab 4 are both exposed on the outside.

[0052] Specifically, the positive electrode 1 includes a full gel formed by interfacial dry crosslinking of the positive conductive gel and the gel electrolyte and a positive electrode catalyst layer (platinum-carbon catalyst), and the negative electrode 2 includes zinc foil or zinc sheet. One side of the positive electrode catalyst layer faces the vent 5.

[0053] Example 1

[0054] A method for preparing a flexible all-gel zinc-air battery of the present invention comprises the following steps:

[0055] (1) 1.75 g of acrylamide was added to 5 g of ultrapure water and stirred thoroughly. Then, 0.05 g of graphene, 0.25 g of polyethylene glycol-1000, and 0.05 g of sodium carboxymethyl cellulose were slowly added dropwise while stirring at room temperature, and stirred at room temperature for 20 min.

[0056] (2) 0.0025 g of tetramethylethylenediamine, 0.0005 g of N,N'-methylenebisacrylamide and 0.0125 g of potassium persulfate were added to the above solution in sequence, stirred for 30 min to obtain a mixed solution, the mixed solution was injected into a mold, placed in a 60°C oven for reaction and drying for 20 min, and a platinum-carbon catalyst was added dropwise to obtain a conductive gel.

[0057] (3) 3.5 g of acrylamide was added to 10 g of ultrapure water and stirred thoroughly. Then, 0.005 g of tetramethylethylenediamine, 0.001 g of N,N'-methylenebisacrylamide, and 0.025 g of potassium persulfate were slowly added dropwise while stirring at room temperature. After stirring for 30 min, a mixed solution was obtained. The mixed solution was injected into a mold and placed in an oven at 60°C for reaction for 20 min to obtain a gel polymer.

[0058] (4) The prepared gel polymer was immersed in 20 mL of a strong alkaline electrolyte for 72 h to obtain a polymer gel electrolyte (alkaline gel electrolyte) with high ionic conductivity.

[0059] The conductive gel is then bonded to the alkaline gel electrolyte through interfacial dry cross-linking to obtain a full gel.

[0060] (5) Combine the aforementioned flexible all-gel zinc-air battery with specific practices in reality and make corresponding elaborations as follows: A flexible all-gel zinc-air battery includes a positive electrode 1, a positive electrode tab 3, a positive electrode ventilation hole 5, a negative electrode 2, and a negative electrode tab 4. The positive electrode and the negative electrode are adhered to each other. The adhesive layer 6 is folded and adhered to the back of the positive electrode 1, and the edges of the positive electrode 1 and the negative electrode 2 are sealed. The positive electrode 1 is connected to the positive electrode tab 3, and the negative electrode 2 is connected to the negative electrode tab 4. Both the positive electrode tab and the negative electrode tab are exposed on the outside.

[0061] Specifically, the positive electrode 1 includes an all-gel formed by interfacial dry cross-linking of a positive electrode conductive gel and a gel electrolyte, and a positive electrode catalytic layer. The negative electrode 2 includes a zinc foil or a zinc sheet. One side of the positive electrode catalytic layer faces the ventilation hole 5 exactly.

[0062] Example 2

[0063] A method for preparing an integrated cathode and electrolyte all-gel zinc-air battery of the present invention includes the following steps:

[0064] (1) Add 3.5 g of acrylamide to 10 g of ultrapure water and stir well. Then, slowly add 0.1 g of carbon nanotubes, 0.5 g of polyethylene glycol-1000, and 0.1 g of carboxymethyl cellulose during stirring at room temperature, and stir at room temperature for 20 min.

[0065] (2) Add 0.005 g of tetramethylethylenediamine, 0.001 g of N,N'-methylenebisacrylamide, and 0.025 g of ammonium persulfate to the above solution in sequence. After stirring for 30 min, a mixed solution is obtained. Inject this mixed solution into a mold, place it in an oven at 60 °C for reaction and drying for 20 min, and then dropwise add a platinum-carbon catalyst to obtain a conductive gel.

[0066] (3) Add 7 g of acrylamide to 20 g of ultrapure water and stir well. Then, slowly add 0.01 g of tetramethylethylenediamine, 0.002 g of N,N'-methylenebisacrylamide, and 0.05 g of ammonium persulfate during stirring at room temperature, and stir for 30 min to obtain a mixed solution. Inject this mixed solution into a mold and place it in an oven at 60 °C for reaction for 20 min to obtain a gel polymer.

[0067] (4) Immerse the prepared gel polymer in 20 mL of a strong base electrolyte for 72 h to obtain a polymer gel electrolyte with high ionic conductivity. Bond the conductive gel and the alkaline gel electrolyte through interfacial dry cross-linking to obtain an all-gel.

[0068] (5) The aforementioned flexible all-gel zinc-air battery is combined with a specific practice in reality and explained accordingly, as follows: A flexible all-gel zinc-air battery includes a positive electrode 1, a positive electrode tab 3, a positive electrode vent 5, a negative electrode 2, and a negative electrode tab 4. The positive electrode 1 and the negative electrode 2 are bonded together, and the adhesive layer 6 is folded over the back of the positive electrode 1 and bonded to seal the edges of the positive electrode 1 and the negative electrode 2; the positive electrode 1 and the positive electrode tab 3 are connected, and the negative electrode 2 and the negative electrode tab 4 are connected, and the positive electrode tab 3 and the negative electrode tab 4 are both exposed on the outside.

[0069] Specifically, the positive electrode 1 includes a full gel formed by interfacial dry crosslinking of the positive conductive gel and the gel electrolyte and a positive electrode catalyst layer (platinum-carbon catalyst), and the negative electrode 2 includes zinc foil or zinc sheet. One side of the positive electrode catalyst layer faces the vent 5.

[0070] Example 3

[0071] The preparation method of a fully gelled zinc-air battery with an integrated cathode and electrolyte of the present invention comprises the following steps:

[0072] (1) 7 g of acrylamide was added to 20 g of ultrapure water and stirred thoroughly. Then, 0.2 g of polyaniline, 1 g of polyethylene glycol-1000, and 0.2 g of sodium carboxymethyl cellulose were slowly added dropwise while stirring at room temperature. The mixture was stirred at room temperature for 20 min.

[0073] (2) 0.01 g of tetramethylethylenediamine, 0.002 g of N,N'-methylenebisacrylamide and 0.05 g of ammonium persulfate were added to the above solution in sequence, stirred for 30 min to obtain a mixed solution, the mixed solution was injected into a mold, placed in a 60 ° C oven for reaction and drying for 25 min, and a platinum carbon catalyst was added dropwise to obtain a conductive gel.

[0074] (3) 14 g of acrylamide was added to 40 g of ultrapure water and stirred thoroughly. Then, 0.02 g of tetramethylethylenediamine, 0.004 g of N,N'-methylenebisacrylamide, and 0.1 g of ammonium persulfate were slowly added dropwise while stirring at room temperature. After stirring for 30 min, a mixed solution was obtained. The mixed solution was injected into a mold and placed in an oven at 60°C for reaction for 25 min to obtain a gel polymer.

[0075] (4) The prepared gel polymer was immersed in 20 mL of a strong alkaline electrolyte for 84 h to obtain a polymer gel electrolyte with high ionic conductivity. The conductive gel and the alkaline gel electrolyte were bonded by interfacial dry crosslinking to obtain a full gel.

[0076] (5) The aforementioned flexible all-gel zinc-air battery is combined with a specific practice in reality and explained accordingly, as follows: A flexible all-gel zinc-air battery includes a positive electrode 1, a positive electrode tab 3, a positive electrode vent 5, a negative electrode 2, and a negative electrode tab 4. The positive electrode 1 and the negative electrode 2 are bonded together, and the adhesive layer 6 is folded over the back of the positive electrode 1 and bonded to seal the edges of the positive electrode 1 and the negative electrode 2; the positive electrode 1 and the positive electrode tab 3 are connected, and the negative electrode 2 and the negative electrode tab 4 are connected, and the positive electrode tab 3 and the negative electrode tab 4 are both exposed on the outside.

[0077] Specifically, the positive electrode 1 includes a full gel formed by interfacial dry crosslinking of the positive conductive gel and the gel electrolyte and a positive electrode catalyst layer (platinum-carbon catalyst), and the negative electrode 2 includes zinc foil or zinc sheet. One side of the positive electrode catalyst layer faces the vent 5.

[0078] Example 4

[0079] The preparation method of a fully gelled zinc-air battery with an integrated cathode and electrolyte of the present invention comprises the following steps:

[0080] (1) 8.75 g of acrylamide was added to 25 g of ultrapure water and stirred thoroughly. Then, 0.25 g of polypyrrole, 1.25 g of polyethylene glycol-1000, and 0.25 g of sodium carboxymethyl cellulose were slowly added dropwise while stirring at room temperature, and stirred at room temperature for 20 min.

[0081] (2) 0.0125 g of tetramethylethylenediamine, 0.0025 g of N,N'-methylenebisacrylamide and 0.0625 g of ammonium persulfate were added to the above solution in sequence, stirred for 30 min to obtain a mixed solution, the mixed solution was injected into a mold, placed in a 60 ° C oven for reaction and drying for 25 min, and a platinum carbon catalyst was added dropwise to obtain a conductive gel.

[0082] (3) 17.5 g of acrylamide was added to 50 g of ultrapure water and stirred thoroughly. Then, 0.025 g of tetramethylethylenediamine, 0.005 g of N,N'-methylenebisacrylamide, and 0.125 g of ammonium persulfate were slowly added dropwise while stirring at room temperature. After stirring for 30 min, a mixed solution was obtained. The mixed solution was injected into a mold and placed in an oven at 60°C for reaction for 25 min to obtain a gel polymer.

[0083] (4) The prepared gel polymer was immersed in 20 mL of a strong alkaline electrolyte for 84 h to obtain a polymer gel electrolyte with high ionic conductivity. The conductive gel and the alkaline gel electrolyte were bonded by interfacial dry crosslinking to obtain a full gel.

[0084] (5) Incorporate the aforementioned flexible all-gel zinc-air battery into specific real-world practices and provide corresponding elaborations as follows: A flexible all-gel zinc-air battery includes a positive electrode 1, a positive electrode tab 3, a positive electrode vent hole 5, a negative electrode 2, and a negative electrode tab 4. The positive electrode 1 and the negative electrode 2 are adhered together, the adhesive layer 6 is folded over the back of the positive electrode 1 and adhered, and the edges of the positive electrode 1 and the negative electrode 2 are sealed. The positive electrode 1 is connected to the positive electrode tab 3, and the negative electrode 2 is connected to the negative electrode tab 4. Both the positive electrode tab 3 and the negative electrode tab 4 are exposed on the outside.

[0085] Specifically, the positive electrode 1 includes an all-gel formed by interfacial dry cross-linking of a positive electrode conductive gel and a gel electrolyte, and a positive electrode catalytic layer (platinum-carbon catalyst). The negative electrode 2 includes a zinc foil or a zinc sheet. One side of the positive electrode catalytic layer faces the vent hole 5 exactly.

[0086] Example 5

[0087] A preparation method for an integrated cathode and electrolyte all-gel zinc-air battery of the present invention includes the following steps:

[0088] (1) Add 10.5 g of acrylamide to 30 g of ultrapure water and stir well. Then, slowly add 0.33 g of poly(3,4-ethylenedioxythiophene), 1.5 g of polyethylene glycol-1000, and 0.3 g of sodium carboxymethylcellulose while stirring at room temperature, and stir at room temperature for 20 min.

[0089] (2) Add 0.015 g of tetramethylethylenediamine, 0.003 g of N,N'-methylenebisacrylamide, and 0.075 g of ammonium persulfate to the above solution in sequence. After stirring for 30 min, a mixed solution is obtained. Inject this mixed solution into a mold, place it in an oven at 60 °C for reaction and drying for 30 min, and then dropwise add a platinum-carbon catalyst to obtain a conductive gel.

[0090] (3) Add 21 g of acrylamide to 60 g of ultrapure water and stir well. Then, slowly add 0.03 g of tetramethylethylenediamine, 0.003 g of N,N'-methylenebisacrylamide, and 0.15 g of ammonium persulfate while stirring at room temperature, and stir for 30 min to obtain a mixed solution. Inject this mixed solution into a mold and place it in an oven at 60 °C for reaction for 30 min to obtain a gel polymer.

[0091] (4) Immerse the obtained gel polymer in 20 mL of a strong base electrolyte for 96 h to obtain a polymer gel electrolyte with high ionic conductivity. Bond the conductive gel and the alkaline gel electrolyte through interfacial dry cross-linking to obtain an all-gel.

[0092] (5) The above-mentioned flexible all-gel zinc-air battery is combined with specific practices in reality and corresponding elaborations are made as follows: A flexible all-gel zinc-air battery includes a positive electrode 1, a positive electrode tab 3, a positive electrode vent hole 5, a negative electrode 2, and a negative electrode tab 4. The positive electrode 1 and the negative electrode 2 are adhered, the adhesive layer 6 is folded and adhered to the back of the positive electrode 1, and the edges of the positive electrode 1 and the negative electrode 2 are sealed; the positive electrode 1 is connected to the positive electrode tab 3, the negative electrode 2 is connected to the negative electrode tab 4, and both the positive electrode tab 3 and the negative electrode tab 4 are exposed on the outside.

[0093] Specifically, the positive electrode 1 includes an all-gel formed by interfacial dry cross-linking of a positive electrode conductive gel and a gel electrolyte and a positive electrode catalytic layer (platinum-carbon catalyst), and the negative electrode 2 includes a zinc foil or a zinc sheet. One side of the positive electrode catalytic layer exactly faces the vent hole 5.

[0094] Figure 2 It is the stress-strain curve graph of the flexible integrated all-gel of Embodiments 1, 2, 3, 4, and 5 of the present invention. As Figure 2 shown, as the sample is extended, that is, as the strain increases, while maintaining a constant speed of extension, its stress also gradually increases, and finally, due to the rupture of the sample, the stress plummets. And the strength is related to Figure 2 the highest point of the curve plateau shown. The higher it is, the greater the strength. As can be seen from Figure 2 this, the all-gel of Embodiment 2 has the greatest strength, which can reach 150 Pa and has the best effect.

[0095] For the flexible all-gel zinc-air battery of the present invention, due to the network structure of the conductive gel and the gel electrolyte, the battery obtains a larger load area of the positive electrode material, thereby improving the area specific energy and volume specific energy of the battery. In addition, the use of a soft-pack design ensures safety and stability. Moreover, because the structural design is simple, it can greatly improve the manufacturing efficiency of manufacturers, and can be bent repeatedly for many times, having a wide application space in the field of flexible portable electronic devices.

[0096] The above content is only to illustrate the technical idea of the present invention and cannot be used to limit the protection scope of the present invention. Any changes made on the basis of the technical solution according to the technical idea proposed by the present invention shall fall within the protection scope of the claims of the present invention.

Claims

1. A preparation method of a flexible all-gel zinc-air battery, characterized in that, It includes the following steps: S1: After adding water to the acrylamide matrix and stirring, add a conductive active substance or a conductive polymer, a pore-forming agent, a binder and stir evenly. Then add a cross-linking agent, an initiator and a catalyst to obtain a mixed solution, and then dry it to obtain a conductive gel; S2: After adding water to the acrylamide matrix and stirring, add a cross-linking agent, an initiator and a catalyst and stir and mix evenly. Then dry it to obtain a gel; Immerse the gel in a zinc salt alkaline electrolyte to obtain an alkaline gel electrolyte; S3: Dry the conductive gel and drop platinum-carbon catalyst as the positive electrode (1). Then perform dry cross-linking at the interface with the alkaline gel electrolyte to obtain a full gel, and use a zinc foil or a zinc sheet as the negative electrode (2); S4: Wrap the positive electrode (1), the full gel and the negative electrode (2) with a soft-pack outer package to form a flexible full gel zinc-air battery; In S2, the zinc salt alkaline electrolyte is a compound solution composed of potassium hydroxide and zinc acetate; The mass ratio of potassium hydroxide to zinc acetate is (7-8:1); The soaking time is 72h-96h; The soft-pack outer package includes: a positive electrode (1), a positive electrode tab (3), a negative electrode (2), a negative electrode tab (4), a vent hole (5), and an adhesive layer (6); A positive electrode tab (3) is provided on the positive electrode (a positive electrode (1)), a negative electrode tab (4) is provided on the negative electrode (2), and a vent hole (5) is provided at the central part of the positive electrode (1); The vent hole (5) corresponds to the position where the platinum-carbon catalyst is dropped; The positive electrode (1) and the negative electrode (2) are bonded through an adhesive layer (6); The outer package is an aluminum-plastic film.

2. The preparation method of the flexible all-gel zinc-air battery according to claim 1, characterized in that, The cross-linking agent is N,N'-methylenebisacrylamide; The catalyst is tetramethylethylenediamine; The initiator is one of ammonium persulfate or potassium persulfate.

3. The preparation method of the flexible all-gel zinc-air battery according to claim 1, wherein, In S1, the conductive active substance is one of carbon nanotubes, conductive carbon, and graphene; The conductive polymer is one of polyaniline, polypyrrole, and poly(3,4-ethylenedioxythiophene).

4. The preparation method of the flexible all-gel zinc-air battery according to claim 1, characterized in that, In S1, the pore-forming agent is one of polyethylene glycol-600 or polyethylene glycol-1000; The binder is one of carboxymethyl cellulose or sodium carboxymethyl cellulose.

5. The preparation method of the flexible all-gel zinc-air battery according to claim 1, characterized in that, In S1, the mass ratio of acrylamide to the conductive active substance or conductive polymer, water, pore-forming agent, binder, cross-linking agent, catalyst and initiator in the conductive gel is 1:(0.02~0.03):(2.5-3):(0.12-0.15):(0.025-0.03):(0.00025-0.0003):(0.001-0.0015):(0.007-0.0073).

6. The preparation method of the flexible all-gel zinc-air battery according to claim 1, characterized in that, In S2, the mass ratio of acrylamide to water, cross-linking agent, catalyst and initiator in the alkaline gel electrolyte is 1:(2.5-3):(0.00025-0.0003):(0.001-0.0015):(0.007-0.0073).

7. The preparation method of the flexible all-gel zinc-air battery according to claim 1, wherein In S3, the platinum-carbon catalyst is a compound solution composed of platinum-carbon, isopropanol, and Nafion solution; the dosage of the prepared platinum-carbon is 1-1.5 mg / cm 2 , and the mass ratio of the isopropanol to the Nafion solution is (20-24):

1.

8. A flexible full gel zinc-air battery prepared by the preparation method according to any one of claims 1 to 7.

Images