Flexible breathable zinc air battery based on polypropylene non-woven fabric and preparation method of flexible breathable zinc air battery

Abstract

The invention relates to a flexible breathable zinc air battery based on a polypropylene non-woven fabric and a preparation method thereof. The preparation method comprises the following steps: carrying out hydrophilic treatment on the polypropylene non-woven fabric; immersing a hydrophilic polypropylene non-woven fabric into the carbon nanotube dispersion liquid, and drying to obtain a carbon nanotube non-woven fabric; the method comprises the following steps: coating a carbon nanotube non-woven fabric with ink containing a copper / cobalt double-atom doped oxygen electrocatalyst, and drying to obtain a breathable air cathode; the carbon nano tube non-woven fabric is electroplated and loaded with zinc, and an air-permeable galvanized anode is obtained; the preparation method comprises the following steps: immersing hydrophilic polypropylene non-woven fabric into a polymer gel solution, taking out the hydrophilic polypropylene non-woven fabric to form non-woven fabric-based polymer gel under ultraviolet irradiation, soaking the non-woven fabric-based polymer gel into a mixed solution of KOH and Zn (Ac) 2, and taking out the non-woven fabric-based polymer gel to obtain a non-woven fabric-based alkaline gel polymer electrolyte; and (3) sequentially laminating and pressing the anode, the polymer electrolyte and the cathode, and then packaging. The flexible, breathable, waterproof and tailorable characteristics of the zinc-air battery are realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of flexible energy storage devices, and particularly relates to a flexible breathable zinc-air battery based on polypropylene non-woven fabric and a preparation method thereof. Background Art

[0002] With the rapid development of portable and wearable flexible electronic devices, the demand for flexible energy storage devices is increasing. Rechargeable zinc-air batteries are considered one of the most promising energy storage and conversion devices due to their high theoretical energy density, cost-effectiveness, and renewability. In recent years, with the successful development of breathable sensors, organic transistors, and displays, breathable skin electronics have become a cutting-edge research direction. However, due to the complex device structure caused by complex electrochemical catalytic reactions, the development of breathable high-energy zinc-air batteries remains a challenge.

[0003] The inherent physical properties of conventional components of current flexible zinc-air batteries (FZABs), including an air cathode made on carbon cloth or carbon fiber, a zinc anode made of zinc foil or zinc wire, and a thin film or sheet-like gel polymer electrolyte, result in thick, inflexible, and airtight batteries. In particular, the lack of breathability of the entire battery device hinders normal gas exchange between the covered skin and the external environment, leading to serious skin health issues such as redness, allergies, and even inflammation. Furthermore, flexible zinc-air battery devices based on fabric substrates still do not achieve the breathability of the overall battery device, and most fabric-based flexible zinc-air batteries suffer from poor electrochemical performance and a short lifespan. Summary of the Invention

[0004] Based on the above-mentioned shortcomings and deficiencies in the prior art, one of the purposes of the present invention is to at least solve one or more of the above-mentioned problems in the prior art. In other words, one of the purposes of the present invention is to provide a flexible, breathable zinc-air battery based on polypropylene non-woven fabric and a preparation method thereof that meet one or more of the above-mentioned needs, solve the problems of no air permeability, poor flexibility stability, and insufficient environmental adaptability in the existing zinc-air battery technology, and realize the compatible integrated energy supply application of wearable devices and smart clothing.

[0005] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions:

[0006] A method for preparing a flexible breathable zinc-air battery based on polypropylene non-woven fabric comprises the following steps:

[0007] (1) Plasma-treating a polypropylene non-woven fabric to obtain a hydrophilic polypropylene non-woven fabric;

[0008] (2) immersing the hydrophilic polypropylene non-woven fabric into the carbon nanotube dispersion, taking it out and drying it to obtain the carbon nanotube non-woven fabric;

[0009] An ink containing copper / cobalt diatomic doped oxygen electrocatalyst is drop-coated on a carbon nanotube nonwoven fabric, and after drying, a breathable air cathode is obtained;

[0010] Electroplating another carbon nanotube nonwoven fabric with zinc to obtain a permeable zinc-plated anode;

[0011] Another hydrophilic polypropylene non-woven fabric is immersed in the polymer gel solution, taken out and irradiated with ultraviolet light to form a non-woven fabric-based polymer gel, and then the non-woven fabric-based polymer gel is immersed in a mixture of KOH and Zn(Ac)2, and taken out to obtain a non-woven fabric-based alkaline gel polymer electrolyte;

[0012] (3) The permeable galvanized anode, the non-woven fabric-based alkaline gel polymer electrolyte and the permeable air cathode are stacked and pressed in sequence, and then packaged.

[0013] As a preferred embodiment, in step (2), the resistivity of the carbon nanotube non-woven fabric is not greater than 1Ω / cm.

[0014] As a preferred embodiment, in step (2), the carbon nanotube dispersion comprises 0.1-0.2 wt% carbon nanotubes, 1-1.5 wt% sodium lauryl sulfate, and the remainder is water.

[0015] As a preferred embodiment, in step (2), the ink includes a copper / cobalt diatomic doped oxygen electrocatalyst, carbon black, a 5% Nafion solution, and anhydrous ethanol, and the solid-liquid ratio of the oxygen electrocatalyst, carbon black, 5% Nafion solution, and anhydrous ethanol is (0.05-0.07) g: (0.025-0.035) g: (250-350) μL: (10-15) mL.

[0016] As a preferred embodiment, the synthesis process of the copper / cobalt diatomic doped oxygen electrocatalyst includes:

[0017] (a) adding fumed silica powder to deionized water and ultrasonically dispersing the powder to obtain a light white silica dispersion; then, sequentially adding glucose, dicyandiamide, copper sulfate trihydrate, cobalt nitrate hexahydrate, and zinc chloride to the silica dispersion and stirring until the powder is fully dissolved to obtain a precursor solution;

[0018] (b) rapidly freezing the precursor solution with liquid nitrogen and freeze-drying to obtain a precursor powder;

[0019] (c) carbonizing the precursor powder at 750-850° C. under a nitrogen atmosphere to obtain a carbide;

[0020] (d) immersing the carbide in a potassium hydroxide solution, then filtering to remove the silica template, and drying to obtain a black powder;

[0021] (e) Carbonizing the black powder at 900-1000° C. under a nitrogen atmosphere to obtain a copper / cobalt diatomic doped oxygen electrocatalyst.

[0022] As a preferred embodiment, the oxygen electrocatalyst loading in the permeable air cathode is 1.5 to 2.5 mg / cm 2 .

[0023] As a preferred solution, the zinc coating amount of the permeable zinc-plated anode is 15 to 20 mg / cm 2 .

[0024] As a preferred embodiment, in step (2), the polymer gel solution includes acrylamide, N,N'-methylenebisacrylamide, ammonium persulfate, a photoinitiator and 1-ethyl-3-methylimidazolium chloride EMCI, carboxymethyl cellulose, and water, and the ratio of acrylamide, N,N'-methylenebisacrylamide, ammonium persulfate, photoinitiator, EMCI, carboxymethyl cellulose, and water is: (2-4) g: (0.003-0.01) g: (0.02-0.03) g: (80-120) μL: (1-3) g: (0.15-0.25) g: (17-23) mL.

[0025] As a preferred embodiment, the step (3) further comprises: connecting the negative electrode tab to the air-permeable galvanized anode via a conductive adhesive, and connecting the positive electrode tab to the air-permeable air cathode via a conductive adhesive;

[0026] The packaging is carried out using a PTFE hydrophobic membrane composited with polypropylene non-woven fabric.

[0027] The present invention also provides a flexible breathable zinc-air battery prepared by the preparation method described in any of the above schemes.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] (1) All-fabric-based integrated process: All battery functional components, including catalyst cathode, zinc anode, gel electrolyte, and packaging, are constructed on polypropylene non-woven fabric (PPNWF) through a combination of plasma etching, dip coating, electroplating, and light curing technologies.

[0030] (2) The first breathable flexible zinc-air battery device: This device achieves a balance between sufficient loading of active electrochemical materials for high battery performance and retention of an excellent fabric network for good air permeability throughout the battery device, resolving the contradiction between the closed structure and air permeability of traditional zinc-air batteries;

[0031] (3) Breakthrough in adaptability to multiple scenarios: The overall battery device has good flexibility and can stably charge and discharge under deformation states such as bending, folding, and curling. The battery as a whole can stably supply energy under extreme conditions such as shearing, penetration, and water immersion, expanding the application boundaries in the field of wearable devices and electronic skin power supply. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a flow chart of the preparation of the flexible breathable zinc-air battery PPNWF-FZABs of the present invention;

[0033] Figure 2 Schematic diagram of the characteristics of the flexible breathable zinc-air battery PPNWF-FZABs of the present invention;

[0034] Figure 3 2. ...

[0035] Figure 4 This is a graph showing the correlation between the anode permeability and the amount of zinc plating according to an embodiment of the present invention;

[0036] Figure 5 1 is a comparison chart of the gel properties of the embodiments of the present invention, showing the water absorption (a), water retention (b), impedance spectrum curve (c), and tensile curve (d) of different gel polymer samples;

[0037] Figure 6 Graph (a) showing the correlation between gel loading and conductivity, graph (b) showing the correlation between gel loading and air permeability, and graph (c) showing the correlation between gel loading and air permeability and conductivity of the electrolyte layer according to an embodiment of the present invention;

[0038] Figure 7 The flexible breathable zinc-air battery PPNWF-FZABs device of the embodiment of the present invention is shown in the following parts: (a) photos showing the positive electrode (i), negative electrode (ii) and hydrophobic encapsulation film (iii, iv) based on PPNWF, (b) photos of the PPNWF-FZABs device and thickness, (c) photos of the PPNWF-FZABs device powering an LED display, and (d) photos demonstrating the air permeability of PPNWF-FZABs.

[0039] Figure 8 Performance test of the flexible breathable zinc-air battery PPNWF-FZABs device according to an embodiment of the present invention: (a) open circuit voltage, (b) peak power density, (c) discharge specific capacity, and (d) charge-discharge cycle curve;

[0040] Figure 9The constant current charge and discharge curves (a) of the flexible breathable zinc-air battery PPNWF-FZABs device under different deformation states and the long-term discharge curve (b) under water immersion state of the embodiment of the present invention;

[0041] Figure 10 These are photos of the flexible breathable zinc-air battery PPNWF-FZABs device of an embodiment of the present invention powering an LED display in the following states: water spray (a), shearing (b), penetration (c), bending into a wristband to power an electronic watch (d), integrated into clothing to power an LED display through parallel modules, and charging a smartphone (e). DETAILED DESCRIPTION

[0042] The following is a detailed description of the preparation method of the flexible breathable zinc-air battery based on polypropylene non-woven fabric of the present invention.

[0043] The design concept of the flexible breathable zinc-air battery of the present invention is:

[0044] 1. Fully non-woven fabric integrated structure: The cathode, anode, electrolyte layer and encapsulation layer of the flexible battery device are all based on polypropylene non-woven fabric PPNWF. The application feasibility of different parts of the battery device is achieved through different non-woven fabric technology modification processes;

[0045] 2. Balanced design for breathability and water retention: Using polypropylene non-woven fabric as a porous fiber framework to support the gel electrolyte, combined with ionic liquid moisture absorption technology, this solves the permeability defects of traditional closed structures. While improving the water retention of the gel electrolyte layer, it also introduces the new concept of breathable and flexible zinc-air batteries, providing new application needs in the field of breathable electronic skin energy supply.

[0046] 3. Applicability to multiple application environments: The fully non-woven fabric-based flexible zinc-air battery device is flexible, deformable, waterproof, breathable, and has safe and stable charging and discharging capabilities, enabling it to be successfully integrated into clothing or used in direct contact with human skin, providing energy for wearable devices without affecting wearing comfort and breathability.

[0047] The overall architecture of the flexible breathable zinc-air battery of the present invention adopts a "sandwich" structure, which is composed of a conductive breathable air cathode, a non-woven fabric-based alkaline gel polymer electrolyte, and a breathable zinc-plated anode stacked together, and is encapsulated by a super-hydrophobic PTFE composite non-woven fabric. Each layer is based on a polypropylene non-woven fabric.

[0048] Specifically, the preparation method of the flexible breathable zinc-air battery based on polypropylene non-woven fabric comprises the following steps:

[0049] (1) Plasma treatment is performed on polypropylene non-woven fabric to obtain hydrophilic polypropylene non-woven fabric.

[0050] Among them, the polypropylene non-woven fabric PPNWF is cut into a suitable size and ultrasonically cleaned in alcohol to remove impurities and oil on the surface; then it is plasma bombarded in an air atmosphere in a plasma bombardment cleaning machine to change the polar groups on the surface of the non-woven fabric, making it a hydrophilic substrate.

[0051] (2) Preparation of a breathable air cathode, a non-woven fabric-based alkaline gel polymer electrolyte, and a breathable galvanized anode, specifically Figure 1 As shown:

[0052] I. Breathable air cathode;

[0053] The hydrophilically modified polypropylene non-woven fabric PPNWF is immersed in a carbon nanotube dispersion SWCNTs, taken out and dried to obtain a carbon nanotube non-woven fabric PPNWF-CNTs; wherein the carbon nanotube dispersion comprises 0.1-0.2 wt% carbon nanotubes, 1-1.5 wt% sodium lauryl sulfate, and the remainder water; the specific proportions can be determined according to actual application requirements;

[0054] An ink containing a copper / cobalt diatomic doped oxygen electrocatalyst catalyst is drop-coated onto a carbon nanotube nonwoven fabric, and after drying, a permeable air cathode PPNWF-CNTs electrode is obtained. The synthesis process of the copper / cobalt diatomic doped oxygen electrocatalyst includes:

[0055] (a) adding fumed silica powder to deionized water and ultrasonically dispersing the powder to obtain a light white silica dispersion; then, sequentially adding glucose, dicyandiamide, copper sulfate trihydrate, cobalt nitrate hexahydrate, and zinc chloride to the silica dispersion and stirring until the powder is fully dissolved to obtain a precursor solution;

[0056] (b) rapidly freezing the precursor solution with liquid nitrogen and freeze-drying to obtain a precursor powder;

[0057] (c) carbonizing the precursor powder at 750-850° C. under a nitrogen atmosphere to obtain a carbide;

[0058] (d) immersing the carbide in a potassium hydroxide solution, then filtering to remove the silica template, and drying to obtain a black powder;

[0059] (e) Carbonizing the black powder at 900-1000° C. under a nitrogen atmosphere to obtain a copper / cobalt diatomic doped oxygen electrocatalyst.

[0060] The ink containing the copper / cobalt diatomic doped oxygen electrocatalyst includes the copper / cobalt diatomic doped oxygen electrocatalyst, carbon black, 5% Nafion solution and anhydrous ethanol. The solid-liquid ratio of the oxygen electrocatalyst, carbon black, 5% Nafion solution and anhydrous ethanol is (0.05-0.07) g: (0.025-0.035) g: (250-350) μL: (10-15) mL. The specific ratio can be determined according to actual application requirements.

[0061] Specifically, the present invention immerses a hydrophilic polypropylene non-woven fabric in a single-walled carbon nanotube dispersion, then dries it. This process is repeated and a resistivity test is performed to ultimately produce a carbon nanotube non-woven fabric (PPNWF-CNTs) with a resistivity of no more than 1 Ω / cm. An ink prepared with the oxygen electrocatalyst is then drop-coated on the surface of the carbon nanotube non-woven fabric (PPNWF-CNTs), and the catalyst loading is controlled by weighing to produce an air cathode.

[0062] The oxygen electrocatalyst loading in the air-permeable cathode is 1.5-2.5 mg / cm 2 .

[0063] II. Permeable galvanized anode;

[0064] The hydrophilically modified polypropylene non-woven fabric PPNWF is immersed in the carbon nanotube dispersion SWCNTs, taken out and dried to obtain the carbon nanotube non-woven fabric PPNWF-CNTs;

[0065] Electroplating zinc on carbon nanotube nonwoven fabric to obtain permeable zinc-plated anode PPNWF-CNTs-Zn electrode;

[0066] The specific electrogalvanizing process is: using PPNWF-CNTs as the substrate, electroplating zinc at constant voltage, controlling the electroplating time to adjust the zinc loading amount, and optimizing the balance between permeability and zinc plating amount through the permeability test results to obtain a permeable zinc-plated anode.

[0067] III. Non-woven fabric-based alkaline gel polymer electrolyte;

[0068] The polymer gel solution of the present invention adopts a PAM-CMC-IL double cross-linked gel system composed of acrylamide AM, carboxymethyl cellulose CMC and an ionic liquid, wherein the ionic liquid is 1-ethyl-3-methylimidazolium chloride EMCI. The amount of hygroscopic ionic liquid added is optimized through gel performance testing to obtain a PAM-CMC-IL gel with optimal performance.

[0069] Breathable frame structure: The hydrophilic polypropylene non-woven fabric is immersed in a polymer gel solution. The optimal process parameters for balancing air permeability and ionic conductivity are obtained through adsorption capacity and final gel layer permeability tests. After UV curing, a gel electrolyte layer with adjustable porosity is formed.

[0070] Specifically, the polymer gel solution includes acrylamide, N,N'-methylenebisacrylamide, ammonium persulfate, a photoinitiator and 1-ethyl-3-methylimidazolium chloride EMCI, carboxymethyl cellulose, and water, and the ratio of acrylamide, N,N'-methylenebisacrylamide, ammonium persulfate, photoinitiator, EMCI, carboxymethyl cellulose, and water is: (2-4) g: (0.003-0.01) g: (0.02-0.03) g: (80-120) μL: (1-3) g: (0.15-0.25) g: (17-23) mL;

[0071] The present invention immerses the hydrophilically modified polypropylene non-woven fabric PPNWF into a polymer gel solution AM / CMC / IL, takes it out and performs photocuring under ultraviolet light UV light to form a non-woven fabric-based polymer gel, then immerses the non-woven fabric-based polymer gel in a mixed aqueous solution of 0.6M KOH and 0.2M Zn(Ac)2, and takes it out to obtain a non-woven fabric-based alkaline gel polymer electrolyte PPNWF-PAM-CMC-IL electrode.

[0072] (3) The permeable galvanized anode, the non-woven fabric-based alkaline gel polymer electrolyte, and the permeable air cathode are sequentially stacked and pressed, and then packaged to achieve integrated integration;

[0073] Specifically, the prepared permeable galvanized anode, non-woven fabric-based alkaline gel polymer electrolyte and permeable air cathode are cut into the required size and shape, and the positive and negative electrode ears are connected to the current collector using silver paste conductive glue, that is, the negative electrode ear is connected to the permeable galvanized anode through the conductive glue, and the positive electrode ear is connected to the permeable air cathode through the conductive glue; then, a sandwich structure is assembled in the following order: a permeable galvanized anode, a non-woven fabric-based alkaline gel polymer electrolyte and a permeable air cathode. After the assembly is completed, moderate pressure is applied to ensure that the anode, cathode and electrolyte layer are fully in contact; then, a PTFE hydrophobic membrane composited with a polypropylene non-woven fabric is used for heat sealing to obtain a zinc-air battery PPNWF-FZABs;

[0074] Among them, the PTFE hydrophobic membrane composited with polypropylene non-woven fabric is a composite of polypropylene non-woven fabric and polytetrafluoroethylene PTFE. Specifically, a layer of PTFE electrospinning membrane is deposited on the polypropylene non-woven fabric. The hydrophobic angle is greater than 150°, and it has super hydrophobic properties, and is both breathable and waterproof.

[0075] The present invention also provides a flexible breathable zinc-air battery prepared by the above preparation method.

[0076] Based on the flexibility, air permeability and high acid and alkali resistance of PPNWF, it can be used as an electrode material for zinc-air batteries after modification. Based on the characteristics of PPNWF, the present invention innovatively proposes a design and preparation strategy for zinc-air batteries PPNWF-FZABs. The hydrophilic-modified PPNWF is repeatedly immersed in and coated with a single-walled carbon nanotube dispersion to obtain a polypropylene carbon nanotube non-woven fabric PPNWF-CNTs with good conductivity. The catalyst loaded on the PPNWF-CNTs substrate is used as an air cathode, and the PPNWF-CNTs loaded with zinc through a constant voltage electroplating process are used as a zinc anode. Under a limited thickness, the zinc loading amount and the permeability after electroplating can be quantitatively controlled. PPNWF is also used as a supporting framework for the gel electrolyte to obtain a breathable polymer electrolyte membrane. By controlling the adsorption amount of the gel solution, the non-woven fabric-based alkaline gel polymer electrolyte formed after photopolymerization has a porous structure and can be used as a breathable electrolyte layer of the zinc-air battery PPNWF-FZABs.

[0077] like Figure 2 As shown, the zinc-air battery PPNWF-FZABs is assembled from the aforementioned electrode and electrolyte layers, all made of non-woven fabric. This wearable battery exhibits excellent flexibility, lightweight properties, and most importantly, fabric-like breathability, enabling it to bend, twist, or fold during charging and discharging. Furthermore, the wearable battery can be easily cut into the desired shape to meet the needs of use under specific conditions, demonstrating its excellent functionality. Based on these characteristics, these unique zinc-air batteries PPNWF-FZABs are more suitable for integration into clothing, enabling wearable devices to be powered without affecting the normal wearability and comfort of clothing.

[0078] The preparation method of the flexible breathable zinc-air battery based on polypropylene non-woven fabric of the present invention is further described below through specific examples.

[0079] The preparation process of the flexible breathable zinc-air battery PPNWF-FZABs device of this embodiment is as follows:

[0080] 1. Non-woven fabric pretreatment process;

[0081] The cut PPNWF was ultrasonically cleaned for 30 minutes to remove oil and impurities. After drying, it was placed in a plasma cleaning equipment for 5 minutes of plasma bombardment with a cleaning power of 30W to obtain clean and hydrophilic non-woven fabric substrates with different densities.

[0082] All PPNWFs used in the experiments were pretreated using the above method.

[0083] 2. Non-woven fabric density selection and conductive modification treatment;

[0084] The pre-treated different densities (30, 40, 50 and 60 g / m 2 ) polypropylene non-woven fabrics were immersed in an aqueous dispersion containing 0.1wt% single-walled carbon nanotubes and 1wt% sodium lauryl sulfate, and the dipping was repeated 8-10 times. After drying at 60°C, carbon nanotube non-woven fabrics PPNWF-CNTs were formed. The resistivity of polypropylene non-woven fabrics with different densities after dipping was tested, such as Figure 3 As shown, the density is 40g / m 2 The resistivity of the carbon nanotube non-woven fabric can be reduced to a minimum of 0.6Ω / cm.

[0085] 3. Preparation of breathable air cathode;

[0086] First, prepare the copper / cobalt double-atom doped oxygen electrocatalyst. The specific process is as follows:

[0087] (a) Preparation of mixed precursor solution;

[0088] 1.5 g of fumed silica powder was added to 120 mL of deionized water, and then ultrasonically dispersed using an ultrasonic microbubble crusher for 10 minutes to obtain a uniform light white silica dispersion. 0.6 g of glucose, 1.2 g of dicyandiamide, 30 mg of copper sulfate trihydrate, 30 mg of cobalt nitrate hexahydrate, and 400 mg of zinc chloride were then added to the silica dispersion in sequence, and the mixture was stirred for 4 hours to fully dissolve all the substances.

[0089] (b) Preparation of precursors;

[0090] The mixed precursor solution was rapidly frozen with liquid nitrogen to prevent the silica template from settling. After continuous freeze drying for 48 hours, a white powder precursor with a loose structure was obtained.

[0091] (c) primary carbonization;

[0092] The precursor powder was carbonized at 800°C under a nitrogen atmosphere, with a heating rate of 5°C per minute and a holding time of 3 hours.

[0093] (d) template removal;

[0094] Since the catalyst is used in an alkaline environment, it was soaked in 3M potassium hydroxide solution for 12 hours to remove the nano-silica template. The silica template was removed by filtration to obtain a black powder, which was then dried in a vacuum drying oven for 8 hours.

[0095] (e) secondary carbonization;

[0096] To reconstruct and adjust the three-dimensional morphology of the catalyst and remove zinc chloride, the dried black powder was subjected to secondary carbonization at 950°C for 1 hour under a nitrogen atmosphere, ultimately obtaining a copper / cobalt diatomic-doped oxygen electrocatalyst.

[0097] Next, 60 mg of oxygen electrocatalyst, 30 mg of carbon black, and 300 μL of 5% Nafion solution were added to 10 mL of anhydrous ethanol and homogenized by ultrasonication to obtain catalyst ink.

[0098] Finally, the catalyst ink was evenly dropped onto the cut carbon nanotube non-woven fabric, dried at 60 ° C and weighed, and the final catalyst loading was 2 mg / cm 2 Breathable air cathode.

[0099] 4. Preparation of permeable galvanized anode;

[0100] Prepare an electrogalvanizing aqueous solution with the following composition: 250g / L ZnSO4+5g / L Al2(SO4)3+30g / LNa2SO4, use the carbon nanotube non-woven fabric with the best conductivity as the working electrode, and the zinc plate as the counter electrode, and perform electroplating at a constant voltage of 5V. The electroplating time is 5, 10, 15, 20, 25, 30, 35, and 40 minutes, respectively. After electroplating, the surface is washed several times to remove the residual electroplating solution, and then dried to obtain a breathable zinc-plated anode, such as Figure 4 As shown in the figure, the optimal process parameters obtained by combining the air permeability test are: 5V constant voltage electroplating, galvanizing time 15 minutes, and galvanizing amount 18.3mg / cm 2 , air permeability 1123.6μm Pa –1 s –1 .

[0101] 5. Preparation of polymer gel electrolyte;

[0102] Polymer gel PAM-CMC-IL xPreparation: 3g acrylamide AM, 3mg N,N'-methylenebisacrylamide, 25mg ammonium persulfate, 100μL 2-hydroxy-2-methylpropiophenone (photoinitiator) and different amounts of EMCI (1g, 2g, 3g, corresponding to x=1, 2, 3, respectively) were dissolved in 18g carboxymethyl cellulose CMC solution (the mass fraction of CMC in the CMC solution was 1%), and rapidly stirred for 3 hours to obtain a polymer gel solution; the polymer gel solution was then poured into a suitable mold and irradiated with ultraviolet light for 3 minutes to obtain a polymer gel; the gel was then soaked in an aqueous solution of 6M potassium hydroxide KOH and 0.2M zinc acetate Zn(Ac)2 for 12 hours to obtain the final alkaline gel polymer electrolyte; by changing the amount of ionic liquid IL (i.e., EMCI) added, samples PAM-CMC-IL1, PAM-CMC-IL2 and PAM-CMC-IL3 were obtained.

[0103] In addition, the same preparation process was used to prepare comparative polymer gel electrolytes of PAM and PAM-CMC without adding CMC or IL. Figure 5 As shown in the figure, through the comparison of various performance indicators of the gel, the optimal ratio of the polymer gel was obtained: 3g AM + 3mg N,N'-methylenebisacrylamide + 25mg ammonium persulfate + 100μL photoinitiator + 2g EMCI + 18g 1wt% CMC aqueous solution was mixed and irradiated with UV light at a wavelength of 312nm for 3 minutes.

[0104] 6. Preparation of breathable gel electrolyte layer based on PPNWF;

[0105] The gel solution was prepared according to the polymer gel solution corresponding to PAM-CMC–IL2. The pretreated PPNWF absorbed a sufficient amount of gel solution, and then the excess gel solution on the non-woven fabric was absorbed with dust-free paper. The sample was exposed to UV light for 3 minutes to obtain a non-woven gel composite layer. The sample was then immersed in 6M KOH and 0.2M Zn(Ac)2 solution for 12 hours to obtain a gel electrolyte layer based on PPNWF, that is, a non-woven fabric-based alkaline gel polymer electrolyte. Figure 6 As shown, the adsorption of different amounts of gel solution (5, 10, 15, 20, 25, 30, 35, 40 mg / cm 2 ) of the non-woven gel electrolyte layer, and the balance of the two parameters resulted in the best permeability of the non-woven gel layer, with a gel solution adsorption capacity of 20 mg / cm 2 , ionic conductivity is 100.6mS / cm, air permeability is 828.8μmPa -1 s -1 .

[0106] 7. Assembly of zinc-air battery PPNWF-FZABs;

[0107] The prepared air cathode, gel electrolyte layer and galvanized anode were cut into the required size and shape; the positive and negative electrodes were connected to the current collector using silver paste conductive glue, and then the sandwich structure was assembled in the following order: galvanized anode, electrolyte layer and air cathode; after assembly, moderate pressure was applied to ensure full contact between the anode and cathode and the electrolyte layer; the device was then heat-sealed at 140°C using a non-woven polytetrafluoroethylene (PTFE) membrane. During the sealing process, a certain pre-tightening force was applied to the sealing membrane to finally obtain a zinc-air battery PPNWF-FZABs device.

[0108] like Figure 7 As shown, during battery assembly, conductive silver paste is used to bond the positive and negative tabs to the catalyst-loaded PPNWF-CNTs and PPNWF-CNTs-Zn, respectively, to form the tabs. To integrate the final battery device into clothing, the device requires encapsulation. A nonwoven fabric composited with polytetrafluoroethylene (PTFE) was used as the encapsulation membrane. This membrane exhibits excellent air permeability and superhydrophobicity, with a contact angle greater than 150°. The nonwoven composite PTFE membrane can also be heat-sealed at 140°C. The encapsulated battery device measures 7 cm × 5 cm and is 1.33 mm thick. The PPNWF-FZABs successfully powered an LED display panel. The permeability was also tested in a permeability test device. The battery device was sandwiched between the test devices, water was added, and an airbag was inflated from below. Air flowed smoothly through the device, forming uniform bubbles. Throughout the process, the battery device continuously and stably powered the LED display, demonstrating its excellent air permeability and water resistance.

[0109] like Figure 8 As shown, the open circuit voltage of the battery device can be maintained above 1.4V, and the maximum power density can reach 136mWcm -2 With the increase of discharge current, the discharge capacity of PPNWF-FZABs gradually decreased (806mA hg -1 @2mA cm -2 、774mA hg -1 @5mA cm -2 、711mA hg -1 @10mA cm -2 、631mA hg -1 @20mA cm -2 ); at 2 mA cm -2 When the charge and discharge cycle test was carried out at a current density of , the battery showed stable charge and discharge cycles in nearly 200 hours (the number of charge and discharge cycles was 600 times), showing good cycle stability.

[0110] like Figure 9 As shown, when the battery device transforms from a normal state to a bent, folded, or curled deformation state and then returns to a normal state, its charge and discharge curves remain stable, indicating that the battery device can maintain stable charge and discharge capabilities under different deformation conditions. The good charge and discharge stability under various deformation states enables PPNWF-ZABs to cope with the dynamic deformation process generated during human movement when integrated into wearable devices or clothing. The battery device can continuously discharge for a long time in oxygenated water. The entire discharge process lasted 19 hours, and even after being immersed in water for a long time, it can continue to discharge at a stable voltage, demonstrating its excellent waterproof ability.

[0111] like Figure 10 As shown, PPNWF-FZABs can still stably supply power during dynamic processes such as water spray, shear and penetration. The all-non-woven material enables PPNWF-FZABs to be easily made into wristbands to power portable devices or integrated into smart clothing as an energy device.

[0112] Given the numerous embodiments of the present invention, the raw materials and amounts involved can be selected within a limited range according to actual needs. The experimental data for each embodiment is voluminous and it is not suitable to list and explain them one by one here. However, the content required for verification and the final conclusions obtained in each embodiment are similar. Therefore, the verification content of each embodiment will not be described one by one here.

[0113] The above description is only a detailed description of the preferred embodiments and principles of the present invention. For ordinary technicians in this field, based on the ideas provided by the present invention, there may be changes in the specific implementation methods, and these changes should also be considered as the scope of protection of the present invention.

Claims

1. A method for preparing a flexible breathable zinc-air battery based on polypropylene non-woven fabric, characterized in that: The following steps are involved: (1) Plasma-treating a polypropylene non-woven fabric to obtain a hydrophilic polypropylene non-woven fabric; (2) immersing the hydrophilic polypropylene non-woven fabric into the carbon nanotube dispersion, taking it out and drying it to obtain the carbon nanotube non-woven fabric; An ink containing copper / cobalt diatomic doped oxygen electrocatalyst is drop-coated on a carbon nanotube nonwoven fabric, and after drying, a breathable air cathode is obtained; Electroplating another carbon nanotube nonwoven fabric with zinc to obtain a permeable zinc-plated anode; Another hydrophilic polypropylene non-woven fabric is immersed in the polymer gel solution, taken out and irradiated with ultraviolet light to form a non-woven fabric-based polymer gel, and then the non-woven fabric-based polymer gel is immersed in a mixture of KOH and Zn(Ac)2, and taken out to obtain a non-woven fabric-based alkaline gel polymer electrolyte; (3) The permeable galvanized anode, the non-woven fabric-based alkaline gel polymer electrolyte and the permeable air cathode are stacked and pressed in sequence, and then packaged.

2. The preparation method according to claim 1, characterized in that In the step (2), the resistivity of the carbon nanotube non-woven fabric is not greater than 1Ω / cm.

3. The preparation method according to claim 2, characterized in that In the step (2), the carbon nanotube dispersion comprises 0.1-0.2 wt% carbon nanotubes, 1-1.5 wt% sodium lauryl sulfate, and the remainder is water.

4. The preparation method according to claim 1, characterized in that In step (2), the ink includes a copper / cobalt diatomic doped oxygen electrocatalyst, carbon black, a 5% Nafion solution, and anhydrous ethanol, and the solid-liquid ratio of the oxygen electrocatalyst, carbon black, 5% Nafion solution, and anhydrous ethanol is (0.05-0.07) g: (0.025-0.035) g: (250-350) μL: (10-15) mL.

5. The preparation method according to claim 4, characterized in that The synthesis process of the copper / cobalt diatomic doped oxygen electrocatalyst includes: (a) adding fumed silica powder to deionized water and ultrasonically dispersing the powder to obtain a light white silica dispersion; then, sequentially adding glucose, dicyandiamide, copper sulfate trihydrate, cobalt nitrate hexahydrate, and zinc chloride to the silica dispersion and stirring until the powder is fully dissolved to obtain a precursor solution; (b) rapidly freezing the precursor solution with liquid nitrogen and freeze-drying to obtain a precursor powder; (c) carbonizing the precursor powder at 750-850° C. under a nitrogen atmosphere to obtain a carbide; (d) immersing the carbide in a potassium hydroxide solution, then filtering to remove the silica template, and drying to obtain a black powder; (e) Carbonizing the black powder at 900-1000° C. under a nitrogen atmosphere to obtain a copper / cobalt diatomic doped oxygen electrocatalyst.

6. The preparation method according to claim 4, characterized in that The oxygen electrocatalyst loading in the permeable air cathode is 1.5 to 2.5 mg / cm 2 .

7. The preparation method according to claim 1, characterized in that The zinc coating amount of the permeable zinc-plated anode is 15 to 20 mg / cm 2 .

8. The preparation method according to claim 1, characterized in that In the step (2), the polymer gel solution includes acrylamide, N,N'-methylenebisacrylamide, ammonium persulfate, a photoinitiator and 1-ethyl-3-methylimidazolium chloride EMCI, carboxymethyl cellulose, and water, and the ratio of acrylamide, N,N'-methylenebisacrylamide, ammonium persulfate, photoinitiator, EMCI, carboxymethyl cellulose, and water is: (2-4) g: (0.003-0.01) g: (0.02-0.03) g: (80-120) μL: (1-3) g: (0.15-0.25) g: (17-23) mL.

9. The preparation method according to claim 1, characterized in that The step (3) further comprises: connecting the negative electrode tab to the air-permeable galvanized anode via conductive adhesive, and connecting the positive electrode tab to the air-permeable air cathode via conductive adhesive; The packaging is carried out using a PTFE hydrophobic membrane composited with polypropylene non-woven fabric.

10. A flexible breathable zinc-air battery prepared according to the preparation method according to any one of claims 1 to 9.

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