An integrated cathode and electrolyte all-gel zinc-air battery and preparation method thereof

Abstract

The present invention discloses an integrated cathode and electrolyte 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 acrylamide and stirring, then adding a conductive active substance or a conductive polymer, a pore-forming agent, and a binder and stirring, then adding a cross-linking agent, an initiator, and a catalyst, and then putting it into an oven 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 then putting it into an oven to obtain a gel, soaking the gel in an alkaline zinc salt electrolyte to obtain an alkaline gel electrolyte; drying the conductive gel and dropping a platinum-carbon catalyst, and then performing dry cross-linking at the interface with the alkaline gel electrolyte to obtain an all-gel; sequentially putting the all-gel and a polished zinc sheet into a mold and tightly combining them to obtain a target product. It solves the technical problems of liquid leakage after the traditional zinc-air battery is encapsulated, and there are interfacial contact internal resistances between the positive electrode and the separator and between the negative electrode and the separator.

Description

Technical Field

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

[0002] With the development and prosperity of flexible and wearable electronic products, it is imperative to produce flexible energy storage devices with high energy density, reliability, and safety. Among various energy storage technologies, zinc-air batteries are considered to be one of the new energy storage devices with great development potential due to their low cost, environmental friendliness, and high theoretical energy density (1084 Wh / kg). However, traditional zinc-air batteries have problems such as leakage of alkaline electrolyte after encapsulation, and there is interfacial contact internal resistance between the traditional positive electrode, separator, and negative electrode, which affects the electrochemical performance of the battery. 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 an integrated cathode and electrolyte all-gel zinc-air battery and a preparation method thereof, so as to solve the technical problems of leakage of traditional zinc-air batteries after encapsulation and interfacial contact internal resistance between the positive electrode and the separator and between the negative electrode and the separator.

[0004] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0005] The present invention discloses a preparation method of an integrated cathode and electrolyte all-gel zinc-air battery, comprising the following steps:

[0006] S1: After adding water to the acrylamide matrix and stirring, add a conductive active substance or a conductive polymer, a pore-forming agent, and a binder and stir evenly. Then add a cross-linking agent, an initiator, and a catalyst to obtain a mixed solution, and then put it into a constant-temperature oven for cross-linking reaction to obtain a conductive gel;

[0007] 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 put it into a constant-temperature oven for cross-linking reaction to obtain a gel, and soak the gel in an alkaline zinc salt electrolyte to obtain an alkaline gel electrolyte;

[0008] S3: Dry the conductive gel and drop a platinum-carbon catalyst, and then perform dry cross-linking at the interface with the alkaline gel electrolyte to obtain an integrated cathode and electrolyte all-gel;

[0009] S4: Put the integrated cathode and electrolyte all-gel and the polished zinc sheet into a mold in sequence and tightly combine them to obtain an integrated cathode and electrolyte all-gel zinc-air battery.

[0010] Furthermore, in the present invention, the cross-linking agent is N,N'-methylenebisacrylamide; the catalyst is tetramethylethylenediamine; the initiator is one of ammonium persulfate or potassium persulfate.

[0011] Furthermore, in the present invention, the temperature of the cross-linking reaction is 50°C - 60°C, and the time of the cross-linking reaction is 20 min - 30 min.

[0012] Furthermore, in the present invention, 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).

[0013] Furthermore, in the present invention, 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.

[0014] Furthermore, in the present invention, 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).

[0015] Furthermore, in the present invention, in S2, the mass ratio of polyacrylamide 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).

[0016] Furthermore, in the present invention, in S2, the alkaline zinc salt 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 72 h - 96 h.

[0017] Furthermore, in the present invention, in S3, the platinum-carbon catalyst is a compound solution composed of platinum-carbon, isopropanol, and Nafion solution; the dosage of platinum-carbon is 1 - 1.5 mg / cm 2 , and the mass ratio of isopropanol to Nafion solution is (20 - 24):1.

[0018] The present invention discloses an integrated cathode and electrolyte all-gel zinc-air battery prepared by using the preparation method described in any one of the above.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] A preparation method of an integrated cathode and electrolyte all-gel zinc-air battery disclosed by the present invention. First, a conductive gel loaded with active substances is bonded to the outer surface of a gel electrolyte by an interfacial dry cross-linking method based on hydrogen bond adsorption, effectively avoiding the interfacial contact impedance between battery components and greatly improving the problem of the load area of the positive electrode, so that an integrated cathode and electrolyte all-gel zinc-air battery with high areal energy density and high volumetric energy density can be obtained. Second, 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. Finally, the gel electrolyte is used to replace the separator in the assembly process of a conventional battery, saving the production cost of the separator part; in addition, the gel electrolyte replaces the liquid electrolyte, there is no liquid flow inside the battery, and there is no problem of battery leakage. In addition, in the preparation process, the electrode material only involves two steps of physical blending and chemical polymerization, omitting a series of cumbersome processes in the preparation process of traditional electrode sheets, greatly saving the production cost and production time.

[0021] An integrated cathode and electrolyte all-gel zinc-air battery prepared by the preparation method of the present invention integrates the positive electrode material and the gel electrolyte, does not require a separator required for the preparation of a conventional battery, avoids the interface between the electrode and the separator, and further avoids the problem of short circuit caused by repeated deformation of the battery, and reduces the contact impedance between interfaces. The battery is mainly composed of two gels, so it has very good flexibility and can be bent repeatedly for many times, and has a wide application space in the field of flexible portable electronic devices. And no large and expensive instruments are involved in the preparation process, which is very suitable for the large-scale commercial production of zinc-air batteries. Description of the Drawings

[0022] Figure 1 Figures (a) and (b) in the middle are the scanning electron microscope images of the conductive gel of Example 2 of the present invention and the conductive gel without the addition of a pore-forming agent, respectively;

[0023] Figure 2 are the constant current discharge diagrams of the integrated cathode and electrolyte all-gel zinc-air batteries of Example 2 and Example 5 of the present invention at different current densities;

[0024] Figure 3 are the LSV curves of Example 2 and Example 5 at a rotation speed of 1600 rpm. Detailed Embodiments

[0025] 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 expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used herein shall have the ordinary meanings understood by those skilled in the art with respect to the present invention. In case of conflicts, the definitions in this specification shall prevail.

[0026] The theories or mechanisms described and disclosed herein, whether correct or incorrect, shall not limit the scope of the present invention in any way, that is, the content of the present invention can be implemented without being limited by any specific theory or mechanism.

[0027] In this article, 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 numerical ranges or percentage ranges should be regarded as having covered and specifically disclosed all possible sub-ranges and individual numerical values within the ranges (including integers and fractions).

[0028] In this article, unless otherwise specified, "comprising", "including", "containing", "having" or similar expressions 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".

[0029] In this article, 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 are no contradictions in the combinations of these technical features, the technical features in each embodiment or example can be combined arbitrarily, and all possible combinations should be considered as within the scope described in this specification.

[0030] The present invention provides an integrated cathode and electrolyte all-gel zinc-air battery and a preparation method thereof.

[0031] The following further elaborates the present invention 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.

[0032] Conventional instrument and equipment in the art are used in the following embodiments. For the experimental methods without specific conditions indicated in the following embodiments, they are generally carried out under conventional conditions or according to the conditions recommended by the manufacturers. 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.

[0033] The preparation method of an integrated cathode and electrolyte all-gel zinc-air battery of the present invention is specifically as follows:

[0034] I. Preparation of the positive electrode: Add a certain amount of matrix acrylamide and water into a three-necked flask. After starting stirring, slowly and evenly add a certain amount of conductive active material or conductive polymer, binder, and pore-forming agent into it and stir for 20 min. Then, add the cross-linking agent, initiator, and catalyst into the mixed solution in sequence, continue stirring for 30 min, and then put the obtained solution into a constant-temperature oven at 50 - 60 °C for cross-linking reaction for 20 min - 30 min to obtain a conductive gel.

[0035] As an alternative, the mass ratio of acrylamide to conductive active material or conductive polymer 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 cross-linking 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-forming agent is 1:0.12 - 0.15; the mass ratio of acrylamide to binder is 1:0.025 - 0.03.

[0036] As an alternative, 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-forming agent is one of polyethylene glycol-600 or polyethylene glycol-1000; the binder is one of carboxymethyl cellulose or sodium carboxymethyl cellulose.

[0037] II. Initiation of the gel electrolyte: Add a certain amount of acrylamide matrix and water into a three-necked flask. After starting stirring, add the cross-linking agent, initiator, and catalyst into it in sequence, stir for 30 min, and then put the obtained solution into a constant-temperature oven at 50 - 60 °C for cross-linking reaction for 20 min - 30 min to obtain a gel. Immerse it in an alkaline zinc salt electrolyte composed of potassium hydroxide and zinc acetate for 72 h - 96 h to obtain an alkaline gel electrolyte.

[0038] 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 cross-linking 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.

[0039] The alkaline zinc salt electrolyte is a compound solution composed of 6 M / L potassium hydroxide and 0.2 M / 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.

[0040] III. Crosslinking of the conductive gel and the gel electrolyte: The conductive gel prepared in Step 1 is dried in an oven at 50 - 60 °C and platinum carbon catalyst is added dropwise, and then it is subjected to interfacial dry crosslinking with the alkaline gel electrolyte in Step 2 to obtain an integrated cathode and electrolyte full gel;

[0041] The platinum carbon catalyst is a compound solution composed of platinum carbon (catalyst), isopropyl alcohol (dispersant) and Nafion solution (ionic polymer); the dosage of the platinum carbon catalyst is 1 - 1.5 mg / cm 2 , and the mass ratio of isopropyl alcohol to the Nafion solution with a concentration of 5 wt% is (20 - 24):1.

[0042] IV. Assembling and synthesizing an integrated cathode and electrolyte full gel zinc - air battery: The integrated cathode and electrolyte full gel in Step 3 and the polished zinc sheet are sequentially placed into a mold, and they are closely fitted through the pressure of the mold.

[0043] The mold is a mold of model OMS - T of Cisco brand.

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

[0045] Example 1

[0046] A preparation method of an integrated cathode and electrolyte full gel zinc - air battery of the present invention includes the following steps:

[0047] (1) After adding 1.75 g of acrylamide to 5 g of ultrapure water and stirring well, 0.05 g of graphene, 0.25 g of polyethylene glycol - 1000, and 0.05 g of sodium carboxymethylcellulose are slowly added dropwise during stirring at room temperature, and stirred at room temperature for 20 min.

[0048] (2) 0.0025 g of tetramethylethylenediamine, 0.0005 g of N,N’-methylenebisacrylamide, and 0.0125 g of potassium persulfate are sequentially added to the above solution, stirred for 30 min to obtain a mixed solution, this mixed solution is injected into a mold, placed in an oven at 60 °C for reaction and drying for 20 min, and a catalyst is added dropwise to obtain a conductive gel.

[0049] (3) After adding 3.5 g of acrylamide to 10 g of ultrapure water and stirring well, slowly add 0.005 g of tetramethylethylenediamine, 0.001 g of N,N'-methylenebisacrylamide, and 0.025 g of potassium persulfate dropwise during stirring at room temperature. After stirring for 30 min, a mixed solution is obtained. 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.

[0050] (4) Immerse the prepared gel polymer in 20 mL of strong alkaline electrolyte for 72 h to obtain a polymer gel electrolyte with high ionic conductivity.

[0051] (5) Bond the conductive gel and the alkaline gel electrolyte through interfacial dry crosslinking to obtain an integrated cathode and electrolyte full gel. Then, place the polished zinc sheet, the alkaline gel electrolyte, and the conductive gel in a mold in the order of zinc sheet, alkaline gel electrolyte, and conductive gel, and closely fit them through the pressure of the mold to obtain an integrated cathode and electrolyte full gel zinc-air battery.

[0052] Example 2

[0053] A preparation method of an integrated cathode and electrolyte full gel zinc-air battery of the present invention includes the following steps:

[0054] (1) After adding 3.5 g of acrylamide to 10 g of ultrapure water and stirring well, slowly add 0.1 g of carbon nanotubes, 0.5 g of polyethylene glycol-1000, and 0.1 g of sodium carboxymethylcellulose during stirring at room temperature, and stir at room temperature for 20 min.

[0055] (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 and place it in an oven at 60 °C for reaction and drying for 20 min. After adding a catalyst, a conductive gel is obtained.

[0056] (3) After adding 7 g of acrylamide to 20 g of ultrapure water and stirring well, 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. After stirring for 30 min, a mixed solution is obtained. 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.

[0057] (4) Immerse the prepared gel polymer in 20 mL of strong alkaline electrolyte for 72 h to obtain a polymer gel electrolyte with high ionic conductivity.

[0058] (5) Bond the conductive gel and the alkaline gel electrolyte through interfacial dry cross-linking to obtain an integrated cathode and electrolyte full gel. Then, place the polished zinc sheet, the alkaline gel electrolyte, and the conductive gel in a mold in the order of zinc sheet, alkaline gel electrolyte, and conductive gel, and tightly bond them through the pressure of the mold to obtain an integrated cathode and electrolyte full gel zinc-air battery.

[0059] Example 3

[0060] A method for preparing an integrated cathode and electrolyte full gel zinc-air battery of the present invention includes the following steps:

[0061] (1) Add 7 g of acrylamide to 20 g of ultrapure water and stir well. Then, slowly add 0.2 g of polyaniline, 1 g of polyethylene glycol-1000, and 0.2 g of carboxymethyl cellulose during stirring at room temperature, and stir at room temperature for 20 min.

[0062] (2) Add 0.01 g of tetramethylethylenediamine, 0.002 g of N,N'-methylenebisacrylamide, and 0.05 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 25 min, and a conductive gel is obtained after adding a catalyst.

[0063] (3) Add 14 g of acrylamide to 40 g of ultrapure water and stir well. Then, slowly add 0.02 g of tetramethylethylenediamine, 0.004 g of N,N'-methylenebisacrylamide, and 0.1 g of ammonium persulfate during stirring at room temperature. After stirring for 30 min, a mixed solution is obtained. Inject this mixed solution into a mold, place it in an oven at 50 °C for reaction for 25 min to obtain a gel polymer.

[0064] (4) Immerse the prepared gel polymer in 20 mL of strong base electrolyte for 84 h to obtain a polymer gel electrolyte with high ionic conductivity.

[0065] (5) Bond the conductive gel and the alkaline gel electrolyte through interfacial dry cross-linking to obtain an integrated cathode and electrolyte full gel. Then, place the polished zinc sheet, the alkaline gel electrolyte, and the conductive gel in a mold in the order of zinc sheet, alkaline gel electrolyte, and conductive gel, and tightly bond them through the pressure of the mold to obtain an integrated cathode and electrolyte full gel zinc-air battery.

[0066] Example 4

[0067] A method for preparing an integrated cathode and electrolyte full gel zinc-air battery of the present invention includes the following steps:

[0068] (1) After adding 8.75 g of acrylamide to 25 g of ultrapure water and stirring well, slowly add 0.25 g of polypyrrole, 1.25 g of polyethylene glycol-1000, and 0.25 g of sodium carboxymethylcellulose while stirring at room temperature, and stir at room temperature for 20 min.

[0069] (2) Add 0.0125 g of tetramethylethylenediamine, 0.0025 g of N,N'-methylenebisacrylamide, and 0.0625 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 25 min, and a conductive gel is obtained after adding the catalyst.

[0070] (3) After adding 17.5 g of acrylamide to 50 g of ultrapure water and stirring well, slowly add 0.025 g of tetramethylethylenediamine, 0.005 g of N,N'-methylenebisacrylamide, and 0.125 g of ammonium persulfate while stirring at room temperature. 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 for 25 min to obtain a gel polymer.

[0071] (4) Immerse the prepared gel polymer in 20 mL of strong alkaline electrolyte for 84 h to obtain a polymer gel electrolyte with high ionic conductivity.

[0072] (5) Bond the conductive gel and the alkaline gel electrolyte through interfacial dry cross-linking to obtain an integrated cathode and electrolyte full gel. Then, place the polished zinc sheet, the alkaline gel electrolyte, and the conductive gel in a mold in the order of zinc sheet, alkaline gel electrolyte, and conductive gel, and tightly fit them through the mold pressure to obtain an integrated cathode and electrolyte full gel zinc-air battery.

[0073] Example 5

[0074] A preparation method of an integrated cathode and electrolyte full gel zinc-air battery of the present invention includes the following steps:

[0075] (1) After adding 10.5 g of acrylamide to 30 g of ultrapure water and stirring well, slowly add 0.33 g of poly(3,4-ethylenedioxythiophene), 1.5 g of polyethylene glycol-600, and 0.3 g of sodium carboxymethylcellulose while stirring at room temperature, and stir at room temperature for 20 min.

[0076] (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 a conductive gel is obtained after adding the catalyst.

[0077] (3) After adding 21 g of acrylamide to 60 g of ultrapure water and stirring well, 0.03 g of tetramethylethylenediamine, 0.003 g of N,N'-methylenebisacrylamide, and 0.15 g of ammonium persulfate were slowly added dropwise during stirring at room temperature. After stirring for 30 min, a mixed solution was obtained. This mixed solution was poured into a mold and placed in an oven at 60 °C for reaction for 30 min to obtain a gel polymer.

[0078] (4) The prepared gel polymer was immersed in 20 mL of a strong base electrolyte for 96 h to obtain a polymer gel electrolyte with high ionic conductivity.

[0079] (5) The conductive gel and the alkaline gel electrolyte were bonded by interfacial dry crosslinking to obtain an integrated cathode and electrolyte all-gel. Then, it was placed in a mold together with the polished zinc sheet in the order of zinc sheet, alkaline gel electrolyte, and conductive gel, and they were closely fitted under the pressure of the mold to obtain an integrated cathode and electrolyte all-gel zinc-air battery.

[0080] Figure 1 This is the scanning electron microscope image of the conductive gel of the present invention. Figure 1 In the middle figure (a), it is the scanning electron microscope image of the conductive gel added with the pore-forming agent PEG-1000. Figure 1 In the middle figure (b), it is the scanning electron microscope image of the conductive gel without adding the pore-forming agent PEG. After adding the pore-forming agent, the channel path of the conductive gel is larger, which is beneficial to the entry and reaction of air. It can be clearly seen from the scanning electron microscope image that the pores of the conductive gel after adding the pore-forming agent are obvious.

[0081] Figure 2 It is the constant current discharge diagram of the integrated cathode and electrolyte all-gel zinc-air batteries of Example 2 and Example 5 of the present invention at different current densities. As Figure 2 shown, the battery performances prepared with pore-forming agents of polyethylene glycol with different molecular weights vary greatly. The pore-forming agent added in Example 2 is PEG-1000, and the pore-forming agent added in Example 5 is PEG-600. Compared with Example 5, the voltage of the battery in Example 2 is higher than that of Example 5 at different current densities, and its performance is more excellent than that of the battery in Example 5.

[0082] Figure 3 It is the LSV curves of Example 2 and Example 5 at a rotation speed of 1600 rpm. In this experiment, the overall battery was subjected to LSV testing to obtain the relationship between voltage and current in the battery. The obtained results were quantitatively analyzed and converted into a relationship curve between current density and power density to observe the limiting current density and peak power density under the discharge state. From Figure 3 it can be seen that Example 2 exhibits excellent electrochemical performance (i.e., E 1 / 2 = 0.74 V, and the limiting current at a voltage of 0.2 V is -5.46 mA cm-2 ), has better performance than Example 5 (-5.24 mA cm -2 , 0.67 V).

[0083] The integrated zinc-air battery of the present invention uses an interfacial dry cross-linking method adsorbed by hydrogen bonds to bond the conductive gel loaded with the active substance 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, so that an integrated cathode and electrolyte all-gel zinc-air battery with high areal energy density and high volumetric energy density can be obtained.

[0084] The above content is only to illustrate the technical idea of the present invention, and the protection scope of the present invention cannot be limited thereby. Any modification made on the basis of the technical solution according to the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.

Claims

1. A preparation method of an integrated cathode and electrolyte 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 material or a conductive polymer, a pore-forming agent, a binder and stir evenly. Then add a crosslinking agent, an initiator and a catalyst to obtain a mixed solution. Then put it into a constant-temperature oven for crosslinking reaction to obtain a conductive gel; S2: After adding water to the acrylamide matrix and stirring, add a crosslinking agent, an initiator and a catalyst and stir and mix evenly. Then put it into a constant-temperature oven for crosslinking reaction to obtain a gel. Immerse the gel in an alkaline zinc salt electrolyte to obtain an alkaline gel electrolyte; S3: Dry the conductive gel and drop a platinum-carbon catalyst, and then perform dry crosslinking at the interface with the alkaline gel electrolyte to obtain an integrated cathode and electrolyte all-gel; S4: Put the integrated cathode and electrolyte all-gel and the polished zinc sheet into a mold in sequence and closely combine them to obtain an integrated cathode and electrolyte all-gel zinc-air battery; In S2, the alkaline zinc salt 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.

2. The preparation method according to claim 1, characterized in that The crosslinking agent is N,N'-methylenebisacrylamide; the catalyst is tetramethylethylenediamine; the initiator is one of ammonium persulfate or potassium persulfate.

3. The preparation method according to claim 1, characterized in that The temperature of the crosslinking reaction is 50°C-60°C, and the time of the crosslinking reaction is 20min-30min.

4. The preparation method according to claim 1, characterized in that In S1, the conductive active material is one of carbon nanotubes, conductive carbon, graphene; the conductive polymer is one of polyaniline, polypyrrole, poly(3,4-ethylenedioxythiophene).

5. The preparation method 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.

6. The preparation method according to claim 1, characterized in that In S1, the mass ratio of acrylamide to the conductive active material or conductive polymer, water, pore-forming agent, binder, crosslinking 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).

7. The preparation method according to claim 1, characterized in that In S2, the mass ratio of polyacrylamide to water, crosslinking 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).

8. The preparation method according to claim 1, characterized in that In S3, the platinum-carbon catalyst is a compound solution composed of platinum-carbon, isopropanol, and Nafion solution; the dosage of the platinum-carbon is 1 - 1.5 mg / cm 2 , and the mass ratio of the isopropanol to the Nafion solution is (20 - 24):

1.

9. An integrated cathode and electrolyte all-gel zinc-air battery prepared by using the preparation method according to any one of claims 1 to 8.

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