Preparation method of high-safety and bending-resistant flexible fabric battery

Abstract

The invention relates to the technical field of flexible fabric power supplies, and discloses a preparation method of a high-safety and bending-resistant flexible fabric power supply. In order to solve the problems of rapid battery capacity attenuation and insufficient safety caused by the problems of leakage, dendritic crystal growth, positive electrode material dissolution and the like of a traditional energy storage device under mechanical deformation, the method mainly comprises the following steps: performing in-situ polymerization on an interpenetrating network bi-crosslinking gel electrolyte on the surface of a zinc wire to serve as a negative electrode; tight coating, rapid curing, high strength, spontaneous healing and continuous construction of the gel are realized; and spirally winding the fiber cathode on the surface of the fiber anode, and packaging to obtain the fiber battery. And weaving by taking the fiber batteries as wefts and warps or textile yarns as warps to form a safe, folding-resistant and self-healing flexible fabric power supply. The fiber batteries in the fabric are electrically connected through a multi-conductive terminal series / parallel connection technology, the working stability of a fabric power supply is effectively improved, and stable operation can still be kept even if a single battery is accidentally disconnected.

Description

Technical Field

[0001] This invention belongs to the field of flexible wearable power device technology, specifically relating to a method for preparing a highly safe and bend-resistant flexible fabric battery. Background Technology

[0002] In recent years, the rapid development of artificial intelligence and machine learning has endowed flexible and portable wearable electronic devices and smart textiles with advanced intelligent functions, while also placing multiple performance requirements on flexible energy storage devices. Flexible energy storage devices need to possess both high specific capacity and high energy density. Simultaneously, to meet the needs of wearable applications, flexible energy storage devices must exhibit high safety and mechanical stability in various scenarios. Zinc-ion batteries, using water as the electrolyte, are widely recognized as one of the most promising candidates to replace traditional toxic and flammable lithium-ion batteries due to their inherent safety, abundant zinc reserves, and low redox potential. However, traditional two-dimensional planar and sandwich-type zinc-ion battery structures cannot withstand mechanical deformations such as bending, folding, and torsion, making it difficult to meet the high flexibility, breathability, and spinnability requirements of smart textiles. Compared to traditional two-dimensional planar structures, one-dimensional fibrous zinc-ion batteries possess inherent flexibility, smaller volume, and lighter weight, and can withstand repeated mechanical deformations during use and be integrated into functional yarns, thus providing a convenient power supply solution for next-generation wearable electronic devices and smart textiles.

[0003] However, zinc-ion fiber batteries use water as the electrolyte solvent, and its fluid properties present numerous challenges. For example, leakage can occur under mechanical deformation, affecting battery performance. Furthermore, free water in the liquid electrolyte can induce zinc dendrite growth, hydrogen evolution reaction, zinc anode passivation, and cathode material dissolution, leading to rapid capacity decay. Among various solutions, polymer gel electrolytes can effectively limit the free water content in the electrolyte, improving the electrochemical stability of the zinc anode during charge and discharge. Current research has proposed various gel electrolytes, but construction strategies for meter-scale aqueous fiber zinc-ion batteries are still limited. Therefore, there is a need for a method to prepare a gel electrolyte capable of in-situ polymerization in meter-scale long devices and a high-strength, self-healing flexible energy storage fabric power source. Summary of the Invention

[0004] The purpose of this invention is to address the problems of rapid capacity decay and insufficient safety in traditional flexible energy storage devices caused by leakage, interface instability, zinc dendrite growth, and cathode material dissolution under mechanical deformation. This is achieved by providing a method for fabricating a highly safe and bend-resistant flexible fabric battery. This method uses a polymeric interpenetrating network double-crosslinked gel polymer to encapsulate zinc wire as a fiber negative electrode, combined with multi-conductive terminal series / parallel connection technology. This results in a flexible energy storage fabric power supply that not only possesses excellent safety and bend resistance but also effectively improves the battery's cycle stability and voltage output stability.

[0005] To achieve the above objectives, the present invention employs the following technical means:

[0006] A method for preparing a highly safe, bend-resistant flexible fabric battery specifically includes the following steps:

[0007] (1) Preparation of fiber zinc anode based on gel polymer coating

[0008] Before use, the zinc wire is cleaned and then a gel electrolyte is polymerized in situ on its surface to prepare a fibrous negative electrode. This achieves tight encapsulation of the gel on the negative electrode surface, while also enabling the gel to solidify rapidly, achieve high strength and self-healing, thus enabling continuous construction and performance improvement of the fiber battery.

[0009] (2) Preparation of fibrous batteries

[0010] A positive electrode slurry is coated on the surface of a fibrous current collector and dried to obtain a fibrous positive electrode; a separator is uniformly wrapped around the surface of the fibrous positive electrode, and then the fibrous negative electrode obtained in step (1) is spirally wound around its surface to obtain a battery cell; the battery cell is immersed in an aqueous electrolyte and then packaged to obtain an aqueous fiber zinc-ion battery.

[0011] (3) Weaving of flexible energy storage fabric power supply

[0012] The fabric is woven on a loom using weaving or knitting processes; the warp yarns include textile yarns; the weft yarns include water-based fiber zinc-ion batteries, with both ends of the fiber positive and negative electrodes serving as tabs for electrical connection; the fiber battery circuit is connected using multi-conductive terminal series / parallel technology, so that the fabric retains mechanical flexibility while having energy storage capabilities.

[0013] Furthermore:

[0014] In step (1), the polymer gel electrolyte is composed of polymer monomers, crosslinking agents, initiators, emulsifiers and functional additives, and polymerizes a double crosslinked interpenetrating network gel.

[0015] Preferably, the polymer monomer includes one or more of acrylamide, acrylic acid, and vinyl alcohol.

[0016] Preferably, the crosslinking agent includes one or more of N,N-methylenebisacrylamide, N,N′-ethylidenebisacrylamide, N,N′-hexamethylenebisacrylamide, and bisacryloylcysteine.

[0017] Preferably, the initiator includes one or more of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]m-chlorophenylacetone, potassium persulfate, ammonium persulfate, Pluronic F127, and F127 diacrylate.

[0018] Preferably, the emulsifier includes one or more of sodium dodecyl sulfonate, sodium tetradecyl sulfonate, and sodium octyl sulfonate.

[0019] Preferably, the functional additive includes one or more of the following: sodium alginate, 2-methylpropanesulfonic acid-2-acrylamide, octadecyl methacrylate, dopamine, hexafluorobutyl methacrylate, octadecyl methacrylate, dimethylene octadecylacrylamide ammonium bromide, sodium lignin sulfonate, and chitosan.

[0020] In step (1), the specific preparation process for in-situ polymerization of gel electrolytes is as follows:

[0021] S1: Preparation of the gel precursor solution: The gel precursor solution is prepared by ultrasonic dissolution. First, 0.25-1g of emulsifier is added to 5-20mL of deionized water and stirred at room temperature for 30-120min until completely dissolved. Then, 0.15-0.6g of functional additive is added, and the mixture is vigorously stirred at 800-1200rpm using a magnetic stirrer and ultrasonically treated for 30-60min until a stable microemulsion is formed. 0.9-3.6g of polymer monomer and 0.0009-0.09g of crosslinking agent are added to the microemulsion and stirred until the solution is homogeneous. Then, 0.01-0.04g of initiator is added. The mixture is stirred at room temperature in the dark for 12-24h to ensure uniform dispersion of the initiator. Afterward, vacuum degassing is performed for 5 minutes to remove air from the solution.

[0022] S2: In-situ polymerization of gel polymer electrolyte: The high viscosity mixture precursor liquid prepared in step S1 is uniformly coated on the surface of zinc wire, and then placed in an ultraviolet lamp (365nm) irradiation device or heating device for 5-120 minutes to initiate free radical in-situ polymerization and obtain a fiber zinc anode coated with gel polymer.

[0023] S3: Immerse the zinc wire negative electrode obtained in step S2 in an aqueous electrolyte for 6-24 hours to perform secondary ionic cross-linking and achieve ionic equilibrium.

[0024] In step (2), the current collector is one or more of stainless steel wire, copper wire, titanium wire, carbon fiber, and carbon nanotube.

[0025] In step (2), the positive electrode slurry comprises active material, conductive agent, binder and solvent, which are mixed in a mass ratio of (6-9.5):(0.25-3):(0.25-2):(7-30);

[0026] Preferably, the positive electrode active material is one of vanadium oxide, manganese oxide and their derivatives, or a mixture thereof;

[0027] Preferably, the conductive agent is one or a mixture of Ketjen Black, acetylene black, Super P, carbon nanotubes, graphene, vapor-grown carbon fibers;

[0028] Preferably, the adhesive is at least one or a mixture of carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), polybutadiene phenyl rubber (SBR), polyacrylonitrile (PAN), polyacrylic acid (PAA), LA132, and LA133.

[0029] Preferably, the solvent is one of pure water, N-methylpyrrolidone, and ethanol.

[0030] In steps (1) and (2), the solvent of the water-based electrolyte is water, and the solute is one or more of zinc sulfate, manganese sulfate, zinc chloride, zinc borate, zinc nitrate, potassium hydroxide, and zinc oxide.

[0031] In step (3), the warp yarn is a textile yarn, including one or more of cotton yarn, wool yarn, linen yarn, polyester and nylon, and the warp density of the energy storage fabric power supply is 2-20 threads / cm.

[0032] In step (3), at least one textile yarn may be added or omitted between two adjacent weft yarns as needed, and the weft density of the energy storage fabric power supply is 2-10 yarns / cm.

[0033] In step (3), the weaving process includes at least one of plain weave, twill weave and satin weave.

[0034] In step (3), the connection method of the multiple conductive terminals is as follows: according to the required output voltage and current of the fabric battery, the positive and negative terminals of at least two of the fiber batteries are electrically connected in series or in parallel.

[0035] Because the present invention employs the above-mentioned technical means, it has the following beneficial effects:

[0036] (1) The fabric power supply prepared by the present invention has excellent safety and bending resistance. Thanks to the use of water as electrolyte solvent and the semi-solid properties of gel polymer, it will not cause fire, leakage or explosion even when subjected to puncture, short circuit or damage; in addition, the excellent electrode-gel electrolyte interface adhesion and self-healing ability improve the stability of the battery. After 20,000 repeated bending, the discharge capacity retention rate reaches more than 90%, and even after 100,000 cycles of bending, it still has a capacity retention rate of more than 65%.

[0037] (2) The fiber battery used in the fabric power supply of the present invention has good cycle performance. Thanks to the gel electrolyte that is polymerized in situ on the surface of the fiber negative electrode, the multi-polymer network formed effectively reduces the content of free water, which can significantly suppress the side reaction on the surface of the zinc negative electrode, improve dendrite and passivation problems, and the capacity retention rate can reach more than 98% after 100 charge-discharge cycles.

[0038] (3) The fabric power supply prepared by the present invention uses fiber batteries as functional yarns and weaves them directly with textile yarns. Instead of embedding centimeter-level short fiber batteries into existing textiles by sewing or bonding, the present invention designs a “structural” fabric power supply from the yarn level to improve the energy storage capacity of fabric per unit area.

[0039] (4) The fabric power supply prepared by the present invention adopts multi-terminal series / parallel connection technology in electrical connection, which can be connected according to different output voltage / current requirements, and effectively improves the working stability of the fabric power supply. Even if a single battery is accidentally disconnected, it can still maintain stable operation.

[0040] (5) This invention combines gel polymer electrolyte technology (step 1), fiber battery structure design (step 2), and multi-conductive terminal electrical connection technology (step 4) to produce a significant synergistic effect, solving the problems of mechanical stability, electrochemical stability, and circuit reliability that flexible energy storage devices face simultaneously in practical applications. The gel electrolyte inhibits zinc dendrite growth and prevents electrolyte leakage, the fiber structure design gives the battery excellent bending performance, and the multi-terminal connection technology ensures the fault tolerance of the circuit. The synergistic effect of the three enables the fabric power supply to adapt to various complex mechanical deformation conditions while maintaining the flexibility and breathability of the fabric, providing a continuous and stable power output, and providing a safe and reliable energy solution for wearable electronic devices and smart textiles. Attached Figure Description

[0041] Figure 1 This is a photograph of a flexible energy storage fabric power source based on a zinc fiber anode encapsulated in a gel polymer.

[0042] Figure 2This is a real-time voltage curve of a flexible energy storage fabric power supply based on a fiber zinc anode encapsulated in gel polymer, under different mechanical test conditions.

[0043] Figure 3 This refers to the capacity retention rate of a fabric power supply for energy storage based on a zinc fiber anode encapsulated in gel polymer after 100,000 bending cycles.

[0044] Figure 4 The photo shows a charging bag made of energy storage fabric power source based on multiple zinc fiber negative electrodes wrapped in gel polymer, used to charge a mobile phone.

[0045] Figure 5 These are cycle performance test diagrams for zinc wire negative electrodes without gel polymer electrolyte and fiber batteries coated with gel polymer electrolyte.

[0046] Figure 6 This is a schematic diagram showing the connection between a single electrode and an electrode with multiple terminals on one side.

[0047] Figure 7 This is a plan view showing multiple terminals connected on both sides. Detailed Implementation

[0048] The embodiments of the present invention will be described in detail below. Although the present invention will be described and illustrated in conjunction with some specific embodiments, it should be noted that the present invention is not limited to these embodiments. On the contrary, any modifications or equivalent substitutions made to the present invention should be covered within the scope of the claims of the present invention.

[0049] Furthermore, to better illustrate the present invention, numerous specific details are set forth in the following detailed embodiments. Those skilled in the art will understand that the present invention can be practiced without these specific details.

[0050] Unless otherwise specified, all experimental reagents and materials described in the following examples are commercially available; and all experimental methods described are standard operating procedures unless otherwise specified.

[0051] Example 1

[0052] A method for preparing a highly safe, bend-resistant flexible fabric battery, comprising the following steps:

[0053] (1) Before use, zinc wire and stainless steel wire are ultrasonically cleaned for 30 minutes with deionized water, acetone and ethanol respectively to remove surface dirt and then dried for later use.

[0054] (2) The specific preparation process of in-situ polymerization of gel electrolyte is as follows:

[0055] S1: Preparation of the gel precursor solution: The gel precursor solution was prepared by ultrasonic dissolution. First, 0.5 g of sodium dodecyl sulfonate was added to 10 mL of deionized water and stirred at room temperature for 60 min to completely dissolve it. Then, 0.3 g of octadecyl methacrylate was added, and the mixture was vigorously stirred at 800 rpm using a magnetic stirrer and ultrasonically treated for 30 min until a stable microemulsion was formed. 1.8 g of acrylamide monomer and 0.0018 g of N,N-methylenebisacrylamide were added to the microemulsion and stirred until the solution was homogeneous. Then, 0.05 g of Pluronic F127 was added as a photoinitiator for UV polymerization. The mixture was stirred at room temperature in the dark for 15 h to ensure uniform dispersion of the initiator. After that, vacuum degassing was performed for 5 minutes to remove air from the solution.

[0056] S2: In-situ polymerization of gel polymer electrolyte: The high viscosity mixture precursor liquid prepared in step S1 is uniformly coated on the surface of zinc wire, and then placed in an ultraviolet lamp (365nm) irradiation device for 15 minutes. After in-situ polymerization of free radicals initiated by ultraviolet light, a fiber zinc anode wrapped with poly(octadecyl methacrylate-co-acrylamide) gel polymer is prepared.

[0057] S3: Immerse the zinc wire negative electrode obtained in step S2 in a 2M zinc borate electrolyte containing 15% manganese sulfate and zinc oxide for 6 hours to perform secondary ionic cross-linking and achieve ionic equilibrium.

[0058] (3) Vanadium pentoxide, acetylene black, CMC, SBR and water are mixed in a mass ratio of 9:0.25:0.25:0.5:25 and stirred at 700 rpm for 12 h to prepare a positive electrode slurry. Then, the slurry is dip-coated onto a stainless steel wire using a slurry coating device and dried to prepare a fiber positive electrode, which is then collected for later use.

[0059] (4) Wrap a separator around the outer surface of the fiber positive electrode prepared in step (3).

[0060] (5) The fiber negative electrode prepared in step (2) is spirally wound onto the outer surface of the fiber positive electrode prepared in step (4), and then the electrolyte is impregnated and encapsulated to prepare an aqueous fiber zinc-ion battery.

[0061] (6) The fabric is woven using a shuttle weaving process on a loom. The warp yarns are made of wool, the weft yarns are made of fiber batteries, and the weaving is done using a twill structure.

[0062] (7) In the electrical connection of multiple fiber batteries, only two or more positive and negative terminals on one side of the battery are used, while two or more terminals on the other side are not used, such as... Figure 6As shown, the fiber batteries in the fabric power supply are connected in series and parallel; PVC tape is wrapped around the terminal connections for insulation; and a flexible energy storage fabric power supply is prepared.

[0063] In this embodiment, the flexible energy storage fabric power source obtained by weaving a fiber battery based on a fiber zinc anode encapsulated in a gel polymer is as follows: Figure 1 As shown.

[0064] Example 2

[0065] A method for preparing a highly safe, bend-resistant flexible fabric battery, comprising the following steps:

[0066] (1) Before use, zinc wire and titanium wire are ultrasonically cleaned with deionized water, acetone and ethanol for 60 minutes respectively to remove surface dirt and then dried for later use.

[0067] (2) The specific preparation process of in-situ polymerization of gel electrolyte is as follows:

[0068] S1: Preparation of the gel precursor solution: The gel precursor solution was prepared by ultrasonic dissolution. First, 0.4 g of sodium dodecyl sulfonate was added to 15 mL of deionized water and stirred at room temperature for 50 min to completely dissolve it. Then, 0.25 g of bis(methylene octadecylacrylamide)ammonium bromide was added, and the mixture was vigorously stirred at 1000 rpm using a magnetic stirrer and ultrasonically treated for 45 min until a stable microemulsion was formed. 2 g of acrylamide monomer and 0.02 g of N,N-methylenebisacrylamide were added to the microemulsion and stirred until the solution was homogeneous. Then, 0.015 g of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]m-chlorophenylacetone was added as a photoinitiator for UV polymerization. The mixture was stirred at room temperature in the dark for 12 h to ensure uniform dispersion of the initiator. After that, vacuum degassing was performed for 5 minutes to remove air from the solution.

[0069] S2: In-situ polymerization of gel polymer electrolyte: The high viscosity mixture precursor liquid prepared in step S1 is uniformly coated on the surface of zinc wire, and then placed in an ultraviolet lamp (365nm) irradiation device for 10 minutes. After in-situ polymerization of free radicals initiated by ultraviolet light, a fiber zinc anode wrapped with poly(dimethylene octadecylacrylamide ammonium bromide-co-acrylamide) gel polymer is prepared.

[0070] S3: Immerse the zinc wire negative electrode obtained in step S2 in a 2M zinc chloride electrolyte containing 15% manganese sulfate and zinc oxide for 12 hours to perform secondary ionic cross-linking and achieve ionic equilibrium.

[0071] (3) Vanadium pentoxide, graphene, CMC, SBR and water are mixed in a mass ratio of 7:2:0.5:0.5:20 and stirred at 700 rpm for 24 hours to prepare a positive electrode slurry. Then, the slurry is continuously dip-coated onto titanium wire using a slurry coating device. After drying, a continuous fiber positive electrode is prepared and collected for later use.

[0072] (4) Wrap a separator around the outer surface of the fiber positive electrode prepared in step (3).

[0073] (5) The fiber negative electrode prepared in step (2) is spirally wound onto the outer surface of the fiber positive electrode prepared in step (4), and then the electrolyte is impregnated and encapsulated to prepare an aqueous fiber zinc-ion battery.

[0074] (6) The fabric is woven using a shuttle weaving process on a loom. The warp yarns are made of polyester yarn and the weft yarns are made of fiber batteries. The fabric is woven using a satin weave structure.

[0075] (7) In the electrical connection of multiple fiber batteries, any two or more positive and negative terminals on the same side of the battery are used, and the other terminals on different sides are not used. This allows the fiber batteries in the fabric power supply to be connected in series and in parallel, such as... Figure 6 As shown, PVC tape is wrapped around the terminal connections for insulation, thus preparing a flexible energy storage fabric power supply.

[0076] In this embodiment, the real-time voltage of the energy storage fabric power supply based on the gel polymer-encapsulated fiber zinc anode under different mechanical test conditions is as follows: Figure 2 As shown in the figure. The capacity retention rate of the energy storage fabric power supply based on the fiber zinc anode encapsulated by gel polymer after 100,000 bending cycles is as follows. Figure 3 As shown.

[0077] Example 3

[0078] A method for preparing a highly safe, bend-resistant flexible fabric battery, comprising the following steps:

[0079] (1) Before use, zinc wire and 304 stainless steel wire are ultrasonically cleaned with deionized water, acetone and ethanol for 90 minutes respectively to remove surface dirt and then dried for later use.

[0080] (2) The specific preparation process of in-situ polymerization of gel electrolyte is as follows:

[0081] S1: Preparation of the gel precursor solution: The gel precursor solution was prepared by ultrasonic dissolution. First, 0.8 g of sodium dodecyl sulfonate was added to 18 mL of deionized water and stirred at room temperature for 100 min to completely dissolve it. Then, 0.52 g of 2-methylpropanesulfonic acid-2-acrylamide was added, and the mixture was vigorously stirred at 1100 rpm using a magnetic stirrer and ultrasonically treated for 60 min until a stable microemulsion was formed. 3 g of acrylamide monomer and 0.003 g of N,N-methylenebisacrylamide were added to the microemulsion and stirred until the solution was homogeneous. Then, 0.03 g of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-m-chlorophenylacetone was added as a photoinitiator for UV polymerization. 0.4 g of dopamine-grafted sodium alginate was added, and the mixture was stirred at room temperature in the dark for 24 h to ensure uniform dispersion of the initiator. After that, vacuum degassing was performed for 5 minutes to remove air from the solution.

[0082] S2: In-situ polymerization of gel polymer electrolyte: The high-viscosity mixture precursor liquid prepared in step S1 is uniformly coated on the surface of zinc wire, and then placed in an ultraviolet lamp (365nm) irradiation device for 5 minutes. After in-situ polymerization initiated by ultraviolet light, a fiber zinc anode wrapped with poly(2-methylpropanesulfonic acid-2-acrylamide-co-acrylamide) interpenetrating (dopamine-grafted sodium alginate) gel polymer is prepared.

[0083] S3: The zinc wire negative electrode obtained in step S2 is immersed in a 2M ZnSO4 electrolyte containing 15% manganese sulfate, zinc oxide and other additives for 20 hours to perform secondary ionic cross-linking and reach ionic equilibrium.

[0084] (3) Vanadium pentoxide, Super P, carbon nanotubes, CMC, SBR and water are mixed in a mass ratio of 9:0.3:0.2:0.2:0.3:15 and stirred at 700 rpm for 6 hours to prepare a positive electrode slurry. Then, the slurry is dip-coated onto 304 stainless steel wire using a slurry coating device and dried to prepare a fiber positive electrode, which is then collected for later use.

[0085] (4) Wrap a separator around the outer surface of the fiber positive electrode prepared in step (3).

[0086] (5) The fiber negative electrode prepared in step (2) is spirally wound onto the outer surface of the fiber positive electrode prepared in step (4), and then the electrolyte is impregnated and encapsulated to prepare an aqueous fiber zinc-ion battery.

[0087] (6) The fabric is woven using a shuttle weaving process on a loom. The warp yarns are made of cotton thread and the weft yarns are made of fiber batteries. The fabric is woven using a plain weave structure.

[0088] (7) In the electrical connection of multiple fiber batteries, multiple or four positive and negative terminals on both sides of the battery are connected for use, thereby connecting the fiber batteries in the fabric power supply in series and parallel; PVC tape is wrapped around the terminal connection for insulation, such as Figure 7 As shown, a flexible energy storage fabric power source was prepared.

[0089] In this real-time example, a charging bag made of multiple energy storage fabric power supplies based on zinc fiber anodes encapsulated in gel polymers charges a mobile phone. Figure 4 As shown.

[0090] Comparative Example 1

[0091] Compared with Example 3, the only difference is that step 2 is not included. The remaining steps are the same as in Example 3, that is, the zinc wire negative electrode surface does not use polymer electrolyte, but is only wrapped with a diaphragm and then immersed in electrolyte.

[0092] Table 1. Capacity retention rates of Example 3 and Comparative Example 1 after 100 cycles.

[0093]

[0094] Table 1 and Figure 5 The image shows the cycle performance test of a zinc wire negative electrode without gel polymer electrolyte and a fiber battery coated with gel polymer electrolyte. The test results show that the gel polymer electrolyte helps to improve the cycle stability of the fiber battery, and the effect is obvious.

[0095] Comparison table of experimental conditions between the examples and comparative examples

[0096]

[0097] Manganese sulfate, zinc chloride, zinc borate, zinc nitrate, potassium hydroxide, zinc oxide

[0098]

[0099]

[0100]

[0101]

Claims

1. A method for preparing a high-safety, bend-resistant flexible fabric battery, characterized in that, Includes the following steps: Step (1): Preparation of fiber zinc anode: In situ polymerization of interpenetrating network double cross-linked gel electrolyte on the surface of zinc wire to form fiber zinc anode wrapped with gel polymer; Step (2): Preparation of fiber battery: Coat the surface of the fibrous current collector with positive electrode slurry and dry it to obtain fibrous positive electrode; cover the surface of the fibrous positive electrode with a separator, and then spirally wind the fibrous zinc negative electrode obtained in step (1) onto its surface to form a cell; immerse the cell in an aqueous electrolyte and encapsulate it to obtain an aqueous fiber zinc ion battery. Step (3): Weaving of the fabric power source: The aqueous fiber zinc ion battery obtained in step (2) is used as the weft yarn and the textile yarn is used as the warp yarn. The fabric is made by weaving process; wherein, the two ends of the fiber zinc negative electrode and the fibrous positive electrode are used as tabs for electrical connection. Step (4): Electrical connection: Multiple water-based fiber zinc-ion batteries in the fabric are connected in series or in parallel using multi-conductive terminal connection technology, so that the fabric battery can still maintain stable operation after a single battery is damaged.

2. The method for preparing a high-safety, bend-resistant flexible fabric battery according to claim 1, characterized in that, In step (1), The polymer gel electrolyte comprises polymer monomers, crosslinking agents, initiators, emulsifiers, and functional additives.

3. The method for preparing a high-safety, bend-resistant, flexible energy storage fabric power source according to claim 2, characterized in that, The polymer monomers include one or more of acrylamide, acrylic acid, and vinyl alcohol; The crosslinking agent includes one or more of N,N-methylenebisacrylamide, N,N′-ethylidenebisacrylamide, N,N′-hexamethylenebisacrylamide, and bisacryloylcysteine; The initiator includes one or more of 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]m-chlorophenylacetone, potassium persulfate, ammonium persulfate, Pluronic F127, and F127 diacrylate; The emulsifier includes one or more of sodium dodecyl sulfonate, sodium tetradecyl sulfonate, and sodium octyl sulfonate. The functional additives include one or more of the following: sodium alginate, 2-methylpropanesulfonic acid-2-acrylamide, octadecyl methacrylate, dopamine, hexafluorobutyl methacrylate, octadecyl methacrylate, dimethylene octadecylacrylamide ammonium bromide, sodium lignin sulfonate, and chitosan.

4. The preparation method according to claim 1, characterized in that, The current collector is selected from one or more of stainless steel wire, copper wire, titanium wire, and carbon fiber; The positive electrode slurry comprises positive electrode active material, conductive agent, binder and solvent, with a mass ratio of (6-9.5):(0.25-3):(0.25-2):(7-30).

5. The preparation method according to claim 4, characterized in that, The positive electrode active material includes one or a mixture of vanadium oxide, manganese oxide and their derivatives. The conductive agent includes one or a mixture of Ketjen Black, acetylene black, Super P, carbon nanotubes, graphene, and vapor-grown carbon fibers. The adhesive includes at least one or a mixture of carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), polybutadiene phenyl rubber (SBR), polyacrylonitrile (PAN), polyacrylic acid (PAA), LA132, and LA133.

6. The method for preparing a high-safety, bend-resistant, flexible energy storage fabric power source according to claim 2, characterized in that, The specific steps of the in-situ polymerization of the gel electrolyte in step (1) include: Step S1: Preparation of gel precursor solution: Add 0.25-1g of emulsifier to 5-20mL of deionized water and stir at room temperature for 30-120min until it is completely dissolved; Then add 0.15-0.6g of functional additive, stir the mixture vigorously at 800-1200rpm using a magnetic stirrer, and sonicate for 30-60min to form a stable microemulsion. Add 0.9-3.6g of polymer monomer and 0.0009-0.09g of crosslinking agent to the microemulsion and stir until homogeneous; Then add 0.01-0.04g of initiator; stir the mixture at room temperature in the dark for 12-24 hours, and then perform vacuum degassing. Step S2: In-situ polymerization of gel polymer electrolyte: The mixture precursor liquid prepared in step S1 is uniformly coated on the surface of zinc wire, and then placed in an ultraviolet lamp irradiation device or heating device for 5-120 min to initiate free radical in-situ polymerization; Step S3: Immerse the zinc wire negative electrode obtained in step S2 in an aqueous electrolyte for 6-24 hours to perform secondary ion crosslinking.

7. The method for preparing a high-safety, bend-resistant, flexible energy storage fabric power source according to claim 1, characterized in that, The solute in the aqueous electrolyte is selected from one or more of zinc sulfate, manganese sulfate, zinc chloride, zinc borate, zinc nitrate, potassium hydroxide, and zinc oxide.

8. The preparation method according to claim 1, characterized in that, The warp yarns are selected from one or more of cotton, wool, linen, polyester, and nylon, and the warp density of the fabric is 2-20 yarns / cm; 0-3 ordinary textile yarns are set between two adjacent weft yarns containing batteries as a gap, and the weft density of the fabric is 2-10 yarns / cm.

9. The method for preparing a high-safety, bend-resistant, flexible energy storage fabric power source according to claim 1, characterized in that, In step (3), the connection method of the multiple conductive terminals is as follows: according to the output voltage and current required by the fabric power supply, the positive and negative terminals of at least two fiber batteries are electrically connected in series or in parallel.

10. The method for preparing a high-safety, bend-resistant, flexible energy storage fabric power source according to claim 1, characterized in that, The aqueous electrolyte is water as the solvent and one or more of the following: zinc sulfate, manganese sulfate, zinc chloride, zinc borate, zinc nitrate, potassium hydroxide, and zinc oxide.

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