A fiber battery, its preparation method and application

Abstract

This invention discloses a fiber battery, its preparation method, and its application. The fiber battery includes a positive electrode, a negative electrode, and a solid electrolyte. The solid electrolyte encapsulates the positive and negative electrodes, both of which are helical in shape. The positive electrode is nested within the negative electrode. A manganese-based material is disposed on the surface of the positive electrode, and a zinc-based material is disposed on the surface of the negative electrode. The manganese-based material contains manganese dioxide, a conductive agent, and a binder. By using a helical positive electrode nested within a helical negative electrode and a specific manganese-based material, this fiber battery increases the contact area between the manganese-based material and the solid electrolyte. This allows a large amount of manganese-based material to stably adhere to the surface of the positive electrode wire, reducing or preventing the active material and the solid electrolyte interfacial film from detaching from the positive electrode. This allows the manganese-based material to fully exert its function, improving the discharge specific capacity of the fiber battery, and thus improving the discharge specific capacity of flexible zinc-ion batteries using manganese-based materials as the positive electrode material.

Description

Technical Field

[0001] This invention relates to the field of battery technology, and more specifically, to a fiber battery, its preparation method, and its application. Background Technology

[0002] Wearable smart electronic products, with their limitless possibilities, bring immense convenience to humanity and are likely to become an indispensable part of people's lives in the future. For wearable smart electronic products, the use of flexible batteries with high specific capacity, long cycle life, and high safety is one of the most crucial aspects of their practical application. Flexible zinc-ion batteries, as one type of flexible battery, have received widespread attention and research due to their abundant zinc reserves, low redox potential, high theoretical capacity, and high safety in their metallic zinc anode. Currently, researchers and scientists have developed various cathode materials for flexible zinc-ion batteries, such as manganese-based materials, vanadium-based materials, cobalt-based materials, and Prussian blue analogues. Among these, manganese-based materials are considered one of the most promising cathode materials for flexible zinc-ion batteries due to their high theoretical capacity, low cost, and environmental friendliness, and have therefore been widely promoted and applied. However, flexible zinc-ion batteries using manganese-based materials as cathode materials have a relatively low discharge specific capacity, which to some extent restricts their promotion and application.

[0003] Therefore, developing a fiber battery to improve the discharge specific capacity of flexible zinc-ion batteries using manganese-based materials as positive electrodes is of great significance. Summary of the Invention

[0004] The purpose of this invention is to solve the problem of low discharge specific capacity of flexible zinc-ion batteries using manganese-based materials as positive electrode materials in the prior art, and to provide a fiber battery, its preparation method and application.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] In a first aspect, the present invention provides a fiber battery comprising a positive electrode, a negative electrode, and a solid electrolyte, wherein the solid electrolyte encapsulates the positive electrode and the negative electrode, both of which are spiral in shape, the positive electrode being nested within the negative electrode, the positive electrode having a manganese-based material positive electrode wire on its surface, and the negative electrode having a zinc metal negative electrode wire on its surface, wherein the manganese-based material contains manganese dioxide, a conductive agent, and a binder.

[0007] The fiber battery of the present invention can improve the discharge specific capacity of flexible zinc-ion batteries using manganese-based materials as positive electrode materials.

[0008] Specifically, the fiber battery of the present invention, by using a structure in which a spiral positive electrode is nested within a spiral negative electrode, and a specific manganese-based material, can increase the contact area between the manganese-based material and the solid electrolyte. This allows a large amount of manganese-based material to stably adhere to the surface of the positive electrode wire, reducing or preventing the active material and solid electrolyte interphase (SEI) film from detaching from the positive electrode. This enables the manganese-based material to fully exert its function, which helps to improve the discharge specific capacity of the fiber battery, i.e., it is beneficial to improve the discharge specific capacity of flexible zinc-ion batteries using manganese-based materials as the positive electrode material. In addition, the structure in which a spiral positive electrode is nested within a spiral negative electrode improves the discharge specific capacity of the fiber battery by promoting the function of the manganese-based material.

[0009] All commonly used solid electrolytes in this field can be used in this invention.

[0010] Preferably, the solid electrolyte contains guar gum, zinc salt, and manganese salt.

[0011] More preferably, the zinc salt is at least one of zinc sulfate (ZnSO4), zinc chloride, and zinc nitrate.

[0012] More preferably, the manganese salt is at least one of manganese sulfate (MnSO4), manganese chloride, and manganese nitrate.

[0013] Preferably, the manganese-based material contains manganese dioxide, a conductive agent, and a binder in a mass ratio of (6-8):(1-2):(1-2).

[0014] More preferably, the manganese-based material contains manganese dioxide, a conductive agent, and a binder in a mass ratio of (7-8):(1-2):1.

[0015] More preferably, the manganese-based material contains manganese dioxide, a conductive agent, and a binder in a mass ratio of 7:2:1.

[0016] The fiber battery of the present invention, by using a specific ratio of manganese dioxide, conductive agent, and binder, allows manganese dioxide and conductive agent to be uniformly distributed on the surface of the positive electrode wire, and to form a conductive network through contact, which helps to further improve the discharge specific capacity of the fiber battery. At the same time, the specific ratio of manganese dioxide, conductive agent, and binder can further increase the adhesion of manganese-based materials, making them adhere more stably to the surface of the positive electrode wire, further reducing or preventing the active material and solid electrolyte interphase (SEI) film from falling off the positive electrode, allowing the manganese-based materials to fully exert their function, thereby further improving the discharge specific capacity of the fiber battery; that is, it is beneficial to further improve the discharge specific capacity of flexible zinc-ion batteries with manganese-based materials as positive electrode materials.

[0017] Commonly used conductive agents and binders in this field can be used in this invention.

[0018] Preferably, the conductive agent is at least one of carbon nanotubes, graphene, Super P, and acetylene black.

[0019] More preferably, the carbon nanotube is at least one of single-walled carbon nanotube, double-walled carbon nanotube, and multi-walled carbon nanotube.

[0020] More preferably, the carbon nanotubes are at least one of hydroxylated carbon nanotubes, carboxylated carbon nanotubes, and aminated carbon nanotubes.

[0021] Preferably, the adhesive is at least one of polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), and polyacrylic acid (PAA).

[0022] Preferably, the manganese-based material loading per unit area of ​​the positive electrode wire is 0.15-0.4 mg / cm². 2 .

[0023] More preferably, the manganese-based material loading per unit area of ​​the positive electrode wire is 0.15 mg / cm². 2 0.16 mg / cm 2 0.17 mg / cm 2 0.18 mg / cm 2 0.19 mg / cm 2 0.2 mg / cm 2 0.21 mg / cm 2 0.22 mg / cm 2 0.23 mg / cm 2 0.24 mg / cm 2 0.25 mg / cm 2 0.26 mg / cm 2 0.27 mg / cm 2 0.28 mg / cm 2 0.29 mg / cm 2 0.3 mg / cm 2 0.31 mg / cm 2 0.32 mg / cm 2 0.33 mg / cm 2 0.34 mg / cm 2 0.35 mg / cm 2 0.36 mg / cm 2 0.37 mg / cm 2 0.38 mg / cm 2 0.39 mg / cm 2 0.4 mg / cm 2 The range of one or any two of them.

[0024] More preferably, the manganese-based material loading per unit area of ​​the positive electrode wire is 0.18-0.38 mg / cm². 2 .

[0025] Preferably, the zinc loading per unit area of ​​the negative electrode wire is 3.0-20.0 mg / cm². 2 .

[0026] More preferably, the zinc loading per unit area of ​​the negative electrode wire is 3.0 mg / cm². 2 3.5 mg / cm 2 3.6 mg / cm 2 4.0 mg / cm 2 4.4 mg / cm 2 4.5 mg / cm 2 5.0 mg / cm 2 5.5 mg / cm 2 6.0 mg / cm 2 7.0 mg / cm 2 8.0 mg / cm 2 9.0 mg / cm 2 9.5 mg / cm 2 10.0 mg / cm 2 11.0 mg / cm 2 12.0 mg / cm 2 13.0 mg / cm 2 14.0 mg / cm 2 15.0 mg / cm 2 16.0 mg / cm 2 17.0 mg / cm 2 17.7 mg / cm 2 18.0 mg / cm 2 18.5 mg / cm 2 19.0 mg / cm 2 20.0 mg / cm 2 The range of one or any two of them.

[0027] More preferably, the zinc loading per unit area of ​​the negative electrode wire is 4.0-18.0 mg / cm². 2 Specifically, it can be 4.0-9.5 mg / cm³. 2 .

[0028] Preferably, the ratio of the manganese-based material loading per unit area of ​​the positive electrode wire to the zinc loading per unit area of ​​the negative electrode wire is 0.2:(4.0-18.0).

[0029] In this invention, the ratio of the specific positive electrode wire's manganese-based material loading per unit area to the negative electrode wire's zinc loading per unit area can improve the specific discharge capacity of the fiber battery, which is beneficial to improving the specific discharge capacity of flexible zinc-ion batteries using manganese-based materials as positive electrode materials.

[0030] When the ratio of manganese-based material loading per unit area of ​​the positive electrode wire to zinc loading per unit area of ​​the negative electrode wire is too large, i.e., the zinc loading per unit area of ​​the negative electrode wire is too low, the active material of the positive electrode cannot react fully, resulting in a decrease in the discharge specific capacity of the fiber battery. When the ratio of manganese-based material loading per unit area of ​​the positive electrode wire to zinc loading per unit area of ​​the negative electrode wire is too small, i.e., the zinc loading per unit area of ​​the negative electrode wire is too high, the zinc layer on the surface of the negative electrode wire is too thick, and the zinc at the bottom cannot fully contact the solid electrolyte, resulting in a smaller discharge specific capacity of the fiber battery.

[0031] More preferably, the ratio of the manganese-based material loading per unit area of ​​the positive electrode wire to the zinc loading per unit area of ​​the negative electrode wire is 0.2:(4.0-9.5).

[0032] Preferably, the positive electrode wire and / or negative electrode wire are made of at least one of stainless steel and carbon fiber.

[0033] Secondly, the present invention provides a method for preparing a fiber battery, comprising the following steps:

[0034] S1. Coating and / or spraying manganese-based material onto the surface of the positive electrode wire to obtain the positive electrode, for later use;

[0035] S2. Electroplating zinc onto the surface of the negative electrode wire yields the negative electrode, which is then set aside.

[0036] S3. Wrap the positive and negative electrodes with a solid electrolyte, with the positive electrode nested inside the negative electrode, to obtain a fiber battery.

[0037] Electroplating solutions used in the field for electroplating metallic zinc can be used in this invention. For example, in step S2, the electroplating solution for electroplating metallic zinc contains zinc sulfate, sodium sulfate, and boric acid.

[0038] Preferably, in step S2, the electroplating time of the electroplated zinc is ≥5 min.

[0039] More preferably, in step S2, the electroplating time of the electroplated zinc is one or any two of the following: 5 min, 8 min, 10 min, 12 min, 15 min, 18 min, 20 min, 22 min, 25 min, 28 min, and 30 min.

[0040] More preferably, the electroplating time for the electroplated zinc is 5-30 minutes, specifically 8-30 minutes.

[0041] Thirdly, the present invention provides an application of fiber batteries in wearable smart electronic products.

[0042] Wearable smart electronic products in this field can be used in this invention, such as in-situ monitoring devices with hydrogel on the surface of fiber batteries, etc.

[0043] Fourthly, the present invention provides an in-situ monitoring device, comprising a fiber battery and a hydrogel, wherein the surface of the fiber battery is provided with the hydrogel.

[0044] The in-situ monitoring device of this invention utilizes a temperature-sensitive or strain-sensitive hydrogel as a sensing layer, and monitors the temperature or deformation of the fiber battery in real time by monitoring the resistance change of the hydrogel. Since temperature changes and deformation during battery operation are important factors affecting battery life and safety, non-destructive, real-time monitoring of fiber batteries using an in-situ monitoring device can provide a reliable solution for battery life management and safety assurance.

[0045] Preferably, the hydrogel is prepared by:

[0046] (1) Mix polyvinyl alcohol, carbon nanotubes and water to obtain solution A;

[0047] (2) Mix chitosan, acetic acid and water to obtain solution B;

[0048] (3) Mix solutions A and B, let stand to form a gel, and you will get a hydrogel.

[0049] More preferably, in step (1), the mass ratio of polyvinyl alcohol, carbon nanotubes and water is (2-6):(0.1-0.3):20.

[0050] More preferably, in step (2), the mass ratio of chitosan, acetic acid and water is (0.4-0.8):(0.6-0.9):(20-22).

[0051] Preferably, the thickness of the hydrogel is ≥0.8mm.

[0052] More preferably, the thickness of the hydrogel is 0.8-2.8 mm.

[0053] More preferably, the thickness of the hydrogel is 0.8-1.6 mm.

[0054] In this invention, the in-situ monitoring device with hydrogel of a specific thickness has better sensitivity, can detect the temperature or deformation of the fiber battery more accurately and in real time, and also has a longer service life.

[0055] Fifthly, the present invention provides a method for fabricating an in-situ monitoring device, comprising the following steps:

[0056] By encapsulating the fiber battery with hydrogel, an in-situ monitoring device can be obtained.

[0057] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0058] The fiber battery of the present invention can improve the discharge specific capacity of flexible zinc-ion batteries using manganese-based materials as positive electrode materials.

[0059] Specifically, the fiber battery of the present invention, by using a structure in which a spiral positive electrode is nested within a spiral negative electrode, and a specific manganese-based material, can increase the contact area between the manganese-based material and the solid electrolyte. This allows a large amount of manganese-based material to stably adhere to the surface of the positive electrode wire, reducing or preventing the active material and solid electrolyte interphase (SEI) film from detaching from the positive electrode. This enables the manganese-based material to fully exert its function, which helps to improve the discharge specific capacity of the fiber battery, i.e., it is beneficial to improve the discharge specific capacity of flexible zinc-ion batteries using manganese-based materials as the positive electrode material. In addition, the structure in which a spiral positive electrode is nested within a spiral negative electrode improves the discharge specific capacity of the fiber battery by promoting the function of the manganese-based material.

[0060] The fiber battery of the present invention, by using a specific ratio of manganese dioxide, conductive agent, and binder, allows manganese dioxide and conductive agent to be uniformly distributed on the surface of the positive electrode wire, and to form a conductive network through contact, which helps to further improve the discharge specific capacity of the fiber battery. At the same time, the specific ratio of manganese dioxide, conductive agent, and binder can further increase the adhesion of manganese-based materials, making them adhere more stably to the surface of the positive electrode wire, further reducing or preventing the active material and solid electrolyte interphase (SEI) film from falling off the positive electrode, allowing the manganese-based materials to fully exert their function, thereby further improving the discharge specific capacity of the fiber battery; that is, it is beneficial to further improve the discharge specific capacity of flexible zinc-ion batteries with manganese-based materials as positive electrode materials. Attached Figure Description

[0061] Figure 1 This is a schematic diagram of the fiber battery structure in Example 1;

[0062] Figure 2 This is a schematic diagram showing the positional relationship between the positive and negative electrodes of the fiber battery in Comparative Example 3.

[0063] Figure 3 This is a schematic diagram showing the positional relationship between the positive and negative electrodes of the fiber battery in Comparative Example 4.

[0064] Figure 4 The image shows the actual positive electrode of the fiber battery in Comparative Example 5.

[0065] Figure 5 This is a schematic diagram showing the positional relationship between the positive and negative electrodes of the fiber battery in Comparative Example 6.

[0066] Figure 6 This is a schematic diagram of the structure of the in-situ monitoring device in Application Example 1;

[0067] Figure 7 This is a side view of the hydrogel used in Example 1.

[0068] Figure 8 This is a side view of the hydrogel used in Example 3;

[0069] Figure 9 The following are the rate performance graphs for Examples 1-2 and Comparative Example 1;

[0070] Figure 10 The following are the rate performance graphs for Examples 1, 3-5, and Comparative Example 2;

[0071] In the diagram: 1-positive electrode, 2-negative electrode, 3-solid electrolyte, 4-hydrogel. Detailed Implementation

[0072] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0073] The experimental methods in the following examples, comparative examples, application examples and comparative application examples, unless otherwise specified, are generally performed under conventional conditions in the art or under conditions recommended by the manufacturer; the raw materials and reagents used, unless otherwise specified, are all commercially available from the conventional market.

[0074] The use of reagents in the various embodiments, comparative examples, application examples, and comparative application examples of this invention is as follows:

[0075] Carbon nanotubes (conductive agent), hydroxylated multi-walled carbon nanotubes, length: 0.5-2μm, item number: 100788, Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.

[0076] Polyvinylidene fluoride (PVDF, adhesive), item number: 768740, Shanghai Maclean Biochemical Technology Co., Ltd.

[0077] Guar gum, product number: G109238, Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0078] Polyvinyl alcohol, product number: S30196, Shanghai Yuanye Biotechnology Co., Ltd.;

[0079] Chitosan, product number: C299272, Shanghai Aladdin Biochemical Technology Co., Ltd.

[0080] Example 1

[0081] This embodiment provides a fiber battery, the structural schematic diagram of which is shown below. Figure 1As shown, it includes a positive electrode, a negative electrode, and a solid electrolyte. The solid electrolyte encapsulates the positive and negative electrodes, both of which are spiral-shaped. The positive electrode is nested inside the negative electrode. The surface of the positive electrode is provided with a positive electrode wire of manganese-based material, and the surface of the negative electrode is provided with a negative electrode wire of metallic zinc. The manganese-based material contains manganese dioxide, carbon nanotubes (conductive agent), and polyvinylidene fluoride (PVDF, binder) in a mass ratio of 7:2:1.

[0082] The manganese-based material loading per unit area of ​​the positive electrode wire is 0.2 mg / cm². 2 The zinc loading per unit area of ​​the negative electrode wire is 9.0 mg / cm². 2 The positive and negative electrode wires are made of 304 stainless steel; the ratio of the manganese-based material loading per unit area of ​​the positive electrode wire to the zinc loading per unit area of ​​the negative electrode wire is 0.2:9.0; the solid electrolyte contains guar gum, zinc sulfate (ZnSO4), and manganese sulfate (MnSO4).

[0083] The above-mentioned method for preparing fiber batteries includes the following steps:

[0084] S1. Manganese dioxide, carbon nanotubes, and polyvinylidene fluoride were mixed in a mass ratio of 7:2:1 to obtain a manganese dioxide mixture; 0.1 g of the manganese dioxide mixture was dissolved in 0.5 mL of N-methylpyrrolidone (NMP) to obtain a manganese-based material; the mass m0 of the positive electrode wire before coating was weighed; the manganese-based material was coated onto the surface of a spiral positive electrode wire (a 304 stainless steel spring with a wire diameter of 0.2 mm, an outer diameter of 1 mm, a length of 25 mm, and 55 turns), and dried in a vacuum drying oven at 70 °C for 2 h; the mass m of the positive electrode wire after drying was weighed, and the surface area S of the positive electrode wire was calculated based on its inner diameter and length. The manganese-based material loading (m-m0) / S = 0.2 mg / cm² 2 The positive electrode is for backup;

[0085] S2. Immerse a spiral negative electrode wire (304 stainless steel spring, with a wire diameter of 0.2 mm, an outer diameter of the spring coil of 2 mm, a spring length of 25 mm, and 23 turns of the spring) in 25 mL of electroplating solution [0.43 mol / L zinc sulfate (ZnSO4), 0.88 mol / L sodium sulfate (Na2SO4), 0.32 mol / L boric acid (H3BO3)] at 40 mA / cm 2 Electroplating was performed at a current of 36.28mA for 15 minutes to plate the surface of the negative electrode wire with metallic zinc. The wire was then cleaned with deionized water and dried in a vacuum drying oven at room temperature for 2 hours to obtain the negative electrode for later use.

[0086] S3. Add 0.6g guar gum, 0.02mol zinc sulfate (ZnSO4), and 0.001mol manganese sulfate (MnSO4) to 10mL of water to obtain a solid electrolyte solution. First, immerse the positive electrode prepared in step S1 in the solid electrolyte solution for 1min, remove it and let it stand for 0.5h. Then, nest the positive electrode inside the negative electrode and immerse it in the remaining solid electrolyte solution. Let it stand for 1h to form a gel, so that the solid electrolyte encapsulates the positive and negative electrodes. Encapsulate to obtain the fiber battery.

[0087] Example 2 and Comparative Example 1

[0088] Example 2 and Comparative Example 1 provide different fiber batteries. The difference between them and Example 1 lies in the mass ratio of manganese dioxide, carbon nanotubes, and polyvinylidene fluoride in the manganese-based material. All other aspects are the same as in Example 1, as shown in the table below:

[0089] Table 1. Mass ratios of manganese dioxide, carbon nanotubes, and polyvinylidene fluoride in manganese-based materials in Examples 1-2 and Comparative Example 1.

[0090] The mass ratio of manganese dioxide, carbon nanotubes, and polyvinylidene fluoride Example 1 7:2:1 Example 2 8:1:1 Comparative Example 1 6:2:2

[0091] Examples 3-5 and Comparative Example 2

[0092] Examples 3-5 and Comparative Example 2 provide different fiber batteries, which differ from Example 1 in that the zinc loading per unit area of ​​the negative electrode wire is different, i.e., the electroplating time in step S2 is different. The rest are the same as in Example 1, as shown in the table below:

[0093] Table 2. Zinc loading per unit area of ​​the negative electrode wire in Examples 1, 3-5 and Comparative Example 2

[0094]

[0095] Comparative Example 3

[0096] This comparative example provides a fiber battery, which differs from Example 1 in that the positive and negative electrodes are positioned parallel to each other, as shown in the schematic diagram below. Figure 2 As shown, the positive electrode is nested inside the negative electrode, unlike in Example 1, but otherwise it is the same as in Example 1, as detailed below:

[0097] The fiber battery includes a positive electrode, a negative electrode, and a solid electrolyte. The solid electrolyte encapsulates the positive and negative electrodes, both of which are spiral-shaped. The positive and negative electrodes are parallel. The positive electrode has a manganese-based material positive electrode wire on its surface, and the negative electrode has a zinc metal negative electrode wire on its surface. The manganese-based material contains manganese dioxide, carbon nanotubes (conductive agent), and polyvinylidene fluoride (PVDF, binder) in a mass ratio of 7:2:1.

[0098] The manganese-based material loading per unit area of ​​the positive electrode wire is 0.2 mg / cm². 2 The zinc loading per unit area of ​​the negative electrode wire is 9.0 mg / cm². 2 The positive and negative electrode wires are made of 304 stainless steel; the ratio of the manganese-based material loading per unit area of ​​the positive electrode wire to the zinc loading per unit area of ​​the negative electrode wire is 0.2:9.0; the solid electrolyte contains guar gum, zinc sulfate (ZnSO4), and manganese sulfate (MnSO4).

[0099] The above-mentioned method for preparing fiber batteries includes the following steps:

[0100] S1. Manganese dioxide, carbon nanotubes, and polyvinylidene fluoride were mixed in a mass ratio of 7:2:1 to obtain a manganese dioxide mixture; 0.1 g of the manganese dioxide mixture was dissolved in 0.5 mL of N-methylpyrrolidone (NMP) to obtain a manganese-based material; the mass m0 of the positive electrode wire before coating was weighed; the manganese-based material was coated onto the surface of a spiral positive electrode wire (a 304 stainless steel spring with a wire diameter of 0.2 mm, an outer diameter of 1 mm, a length of 25 mm, and 55 turns), and dried in a vacuum drying oven at 70 °C for 2 h; the mass m of the positive electrode wire after drying was weighed, and the surface area S of the positive electrode wire was calculated based on its inner diameter and length. The manganese-based material loading (m-m0) / S = 0.2 mg / cm² 2 The positive electrode is for backup;

[0101] S2. Immerse a spiral negative electrode wire (304 stainless steel spring, with a wire diameter of 0.2 mm, an outer diameter of the spring coil of 2 mm, a spring length of 25 mm, and 23 turns of the spring) in 25 mL of electroplating solution [0.43 mol / L zinc sulfate (ZnSO4), 0.88 mol / L sodium sulfate (Na2SO4), 0.32 mol / L boric acid (H3BO3)] at 40 mA / cm 2 Electroplating was performed at a current of 36.28mA for 15 minutes to plate the surface of the negative electrode wire with metallic zinc. The wire was then cleaned with deionized water and dried in a vacuum drying oven at room temperature for 2 hours to obtain the negative electrode for later use.

[0102] S3. Add 0.6 g guar gum, 0.02 mol zinc sulfate (ZnSO4), and 0.001 mol manganese sulfate (MnSO4) to 10 mL of water to obtain a solid electrolyte solution; then insert the positive and negative electrodes, ensuring they are parallel (e.g., ...). Figure 2 As shown in the figure, let it stand for 1 hour to form a gel, so that the solid electrolyte wraps around the positive and negative electrodes, and then encapsulate it to obtain the fiber battery.

[0103] Comparative Example 4

[0104] This comparative example provides a fiber battery, which differs from Example 1 in that the positive and negative electrodes are parallel in position and both the positive and negative electrodes are linear in shape, as shown in the schematic diagram below. Figure 3 As shown, in the non-Example 1, the positive electrode is nested inside the negative electrode, and both the positive and negative electrodes are spiral-shaped. All other aspects are consistent with Example 1, as detailed below:

[0105] The fiber battery includes a positive electrode, a negative electrode, and a solid electrolyte. The solid electrolyte encapsulates the positive and negative electrodes. Both the positive and negative electrodes are linear in shape. The positive and negative electrodes are parallel. The positive electrode has a manganese-based material wire on its surface, and the negative electrode has a zinc-based material wire on its surface. The manganese-based material contains manganese dioxide, carbon nanotubes (conductive agent), and polyvinylidene fluoride (PVDF, binder) in a mass ratio of 7:2:1.

[0106] The manganese-based material loading per unit area of ​​the positive electrode wire is 0.2 mg / cm². 2 The zinc loading per unit area of ​​the negative electrode wire is 9.0 mg / cm². 2 The positive and negative electrode wires are made of 304 stainless steel; the ratio of the manganese-based material loading per unit area of ​​the positive electrode wire to the zinc loading per unit area of ​​the negative electrode wire is 0.2:9.0; the solid electrolyte contains guar gum, zinc sulfate (ZnSO4), and manganese sulfate (MnSO4).

[0107] The above-mentioned method for preparing fiber batteries includes the following steps:

[0108] S1. Manganese dioxide, carbon nanotubes, and polyvinylidene fluoride were mixed in a mass ratio of 7:2:1 to obtain a manganese dioxide mixture; 0.1 g of the manganese dioxide mixture was dissolved in 0.5 mL of N-methylpyrrolidone (NMP) to obtain a manganese-based material; the mass m0 of the positive electrode wire before coating was weighed; the manganese-based material was coated onto the surface of a linear positive electrode wire (a linear 304 stainless steel wire with an outer diameter of 0.2 mm and a length of 25 mm), and dried in a vacuum drying oven at 70 °C for 2 h; the mass m of the dried positive electrode wire was weighed, and the surface area S of the positive electrode wire was calculated based on its inner diameter and length. The manganese-based material loading (m-m0) / S = 0.2 mg / cm² 2 The positive electrode is for backup;

[0109] S2. Immerse a linear negative electrode wire (304 stainless steel wire, 0.2 mm outer diameter, 25 mm length) in 25 mL of electroplating solution [0.43 mol / L zinc sulfate (ZnSO4), 0.88 mol / L sodium sulfate (Na2SO4), 0.32 mol / L boric acid (H3BO3)] at 40 mA / cm². 2Electroplating was performed at a current of 6.28mA for 15 minutes to plate the surface of the negative electrode wire with metallic zinc. The wire was then cleaned with deionized water and dried in a vacuum drying oven at room temperature for 2 hours to obtain the negative electrode for later use.

[0110] S3. Add 0.6 g guar gum, 0.02 mol zinc sulfate (ZnSO4), and 0.001 mol manganese sulfate (MnSO4) to 10 mL of water to obtain a solid electrolyte solution; then insert the positive and negative electrodes, ensuring they are parallel (e.g., ...). Figure 3 As shown in the figure, let it stand for 1 hour to form a gel, so that the solid electrolyte wraps around the positive and negative electrodes, and then encapsulate it to obtain the fiber battery.

[0111] Comparative Example 5

[0112] This comparative example provides a fiber battery, which differs from Example 1 in that the positional relationship between the positive and negative electrodes is such that the negative electrode is nested inside the positive electrode, instead of the positive electrode being nested inside the negative electrode as in Example 1. All other aspects are the same as in Example 1, as detailed below:

[0113] The fiber battery includes a positive electrode, a negative electrode, and a solid electrolyte. The solid electrolyte encapsulates the positive and negative electrodes, both of which are spiral-shaped. The negative electrode is nested inside the positive electrode. The positive electrode has a manganese-based material positive electrode wire on its surface, and the negative electrode has a zinc metal negative electrode wire on its surface. The manganese-based material contains manganese dioxide, carbon nanotubes (conductive agent), and polyvinylidene fluoride (PVDF, binder) in a mass ratio of 7:2:1.

[0114] The manganese-based material loading per unit area of ​​the positive electrode wire is 0.2 mg / cm². 2 The zinc loading per unit area of ​​the negative electrode wire is 9.0 mg / cm². 2 The positive and negative electrode wires are made of 304 stainless steel; the ratio of the manganese-based material loading per unit area of ​​the positive electrode wire to the zinc loading per unit area of ​​the negative electrode wire is 0.2:9.0; the solid electrolyte contains guar gum, zinc sulfate (ZnSO4), and manganese sulfate (MnSO4).

[0115] The above-mentioned method for preparing fiber batteries includes the following steps:

[0116] S1. Manganese dioxide, carbon nanotubes, and polyvinylidene fluoride were mixed in a mass ratio of 7:2:1 to obtain a manganese dioxide mixture; 0.1 g of the manganese dioxide mixture was dissolved in 0.5 mL of N-methylpyrrolidone (NMP) to obtain a manganese-based material; the mass m0 of the positive electrode wire before coating was weighed; the manganese-based material was coated onto the surface of a spiral positive electrode wire (a 304 stainless steel spring with a wire diameter of 0.2 mm, an outer diameter of 2 mm, a length of 25 mm, and 23 turns), and dried in a vacuum drying oven at 70 °C for 2 h; the mass m of the dried positive electrode wire was weighed, and the surface area S of the positive electrode wire was calculated based on its inner diameter and length. The manganese-based material loading (m-m0) / S = 0.2 mg / cm² 2 The positive electrode is for backup;

[0117] S2. Immerse a spiral negative electrode wire (304 stainless steel spring, with a wire diameter of 0.2 mm, an outer diameter of the spring coil of 1 mm, a spring length of 25 mm, and 55 turns of the spring) in 25 mL of electroplating solution [0.43 mol / L zinc sulfate (ZnSO4), 0.88 mol / L sodium sulfate (Na2SO4), 0.32 mol / L boric acid (H3BO3)] at 40 mA / cm². 2 Electroplating was performed at a current of 43.38mA for 15 minutes to plate the surface of the negative electrode wire with metallic zinc. The wire was then cleaned with deionized water and dried in a vacuum drying oven at room temperature for 2 hours to obtain the negative electrode for later use.

[0118] S3. Add 0.6g guar gum, 0.02mol zinc sulfate (ZnSO4), and 0.001mol manganese sulfate (MnSO4) to 10mL of water to obtain a solid electrolyte solution. First, immerse the negative electrode prepared in step S2 in the solid electrolyte solution for 1min, remove it and let it stand for 0.5h. Then, nest the negative electrode inside the positive electrode. At this point, it is found that the negative electrode cannot be nested inside the positive electrode. The reason is: when preparing the positive electrode using the coating method in step S1, if... Figure 4 As shown, manganese-based materials can seep into the interior of a 304 stainless steel spring, resulting in the spring being filled with manganese-based materials. This hinders the embedding of the negative electrode into the positive electrode, making it impossible to fabricate a fiber battery in which the negative electrode is nested within the positive electrode.

[0119] Comparative Example 6

[0120] This comparative example provides a fiber battery, which differs from Example 1 in that the positive and negative electrodes are intertwined and both are linear in shape, as shown in the schematic diagram below. Figure 5 As shown, in the non-Example 1, the positive electrode is nested inside the negative electrode, and both the positive and negative electrodes are spiral-shaped. All other aspects are consistent with Example 1, as detailed below:

[0121] The fiber battery includes a positive electrode, a negative electrode, and a solid electrolyte. The solid electrolyte encapsulates the positive and negative electrodes, both of which are linear in shape and intertwined. The positive electrode has a manganese-based material wire on its surface, and the negative electrode has a zinc-based material wire on its surface. The manganese-based material contains manganese dioxide, carbon nanotubes (conductive agent), and polyvinylidene fluoride (PVDF, binder) in a mass ratio of 7:2:1.

[0122] The manganese-based material loading per unit area of ​​the positive electrode wire is 0.2 mg / cm². 2 The zinc loading per unit area of ​​the negative electrode wire is 9.0 mg / cm². 2 The positive and negative electrode wires are made of 304 stainless steel; the ratio of the manganese-based material loading per unit area of ​​the positive electrode wire to the zinc loading per unit area of ​​the negative electrode wire is 0.2:9.0; the solid electrolyte contains guar gum, zinc sulfate (ZnSO4), and manganese sulfate (MnSO4).

[0123] The above-mentioned method for preparing fiber batteries includes the following steps:

[0124] S1. Manganese dioxide, carbon nanotubes, and polyvinylidene fluoride were mixed in a mass ratio of 7:2:1 to obtain a manganese dioxide mixture; 0.1 g of the manganese dioxide mixture was dissolved in 0.5 mL of N-methylpyrrolidone (NMP) to obtain a manganese-based material; the mass m0 of the positive electrode wire before coating was weighed; the manganese-based material was coated onto the surface of a linear positive electrode wire (a linear 304 stainless steel wire with an outer diameter of 0.2 mm and a length of 25 mm), and dried in a vacuum drying oven at 70 °C for 2 h; the mass m of the dried positive electrode wire was weighed, and the surface area S of the positive electrode wire was calculated based on its inner diameter and length. The manganese-based material loading (m-m0) / S = 0.2 mg / cm² 2 The positive electrode is for backup;

[0125] S2. Immerse a linear negative electrode wire (304 stainless steel wire, 0.2 mm outer diameter, 25 mm length) in 25 mL of electroplating solution [0.43 mol / L zinc sulfate (ZnSO4), 0.88 mol / L sodium sulfate (Na2SO4), 0.32 mol / L boric acid (H3BO3)] at 40 mA / cm². 2 Electroplating was performed at a current of 6.28mA for 15 minutes to plate the surface of the negative electrode wire with metallic zinc. The wire was then cleaned with deionized water and dried in a vacuum drying oven at room temperature for 2 hours to obtain the negative electrode for later use.

[0126] S3. Add 0.6g guar gum, 0.02mol zinc sulfate (ZnSO4), and 0.001mol manganese sulfate (MnSO4) to 10mL of water to obtain a solid electrolyte solution. First, immerse the positive and negative electrodes separately in the solid electrolyte solution for 1min, remove them and let them stand for 0.5h. Then, allow the positive and negative electrodes to intertwine. At this point, it is observed that when the positive and negative electrodes intertwine, as... Figure 5 As shown, the manganese-based material and solid electrolyte on the surface of the positive electrode have been severely detached due to the entanglement of the positive and negative electrodes, causing the stainless steel wires of the positive and negative electrodes to come into direct contact. This results in a short circuit in the fiber battery prepared using the entangled positive and negative electrodes, making it impossible to prepare a fiber battery with the positive and negative electrodes entangled together.

[0127] Application Example 1

[0128] This application example provides an in-situ monitoring device, the schematic diagram of which is shown below. Figure 6 As shown, the invention includes a fiber battery prepared in Example 1 and a hydrogel, wherein the surface of the fiber battery is provided with hydrogel;

[0129] The preparation method of the above-mentioned in-situ monitoring device includes the following steps:

[0130] (1) Mix 4g of polyvinyl alcohol, 0.15g of carbon nanotubes and 20mL of water, and stir at 120℃ for 2h to obtain solution A;

[0131] (2) Mix 0.8g chitosan, 2.8mL of 30% acetic acid aqueous solution and 20mL of water, stir for 2h to obtain solution B;

[0132] (3) Mix solutions A and B, pour into a mold with a thickness of 0.8 mm, and let stand at -20℃ for 12 hours to form a gel, resulting in a hydrogel with a thickness of 0.8 mm, as shown below. Figure 7 As shown, the hydrogel has a uniform thickness distribution;

[0133] (4) The hydrogel from step (3) encapsulates the fiber battery of Example 1 to obtain the in-situ monitoring device.

[0134] The mass ratio of polyvinyl alcohol, carbon nanotubes, and water in step (1) is 4:0.15:20.

[0135] In step (2), the mass ratio of chitosan, acetic acid, and water is 0.8:0.84:21.96.

[0136] In this invention, the density of both a 30% acetic acid aqueous solution and water is considered to be 1 g / mL.

[0137] Application Example 2

[0138] This application example provides an in-situ monitoring device, which differs from Application Example 1 in that the thickness of the hydrogel is 1.6 mm. All other aspects are the same as in Example 1, as detailed below:

[0139] The in-situ monitoring device includes a fiber battery and a hydrogel prepared in Example 1, wherein the surface of the fiber battery is provided with hydrogel;

[0140] The preparation method of the above-mentioned in-situ monitoring device includes the following steps:

[0141] (1) Mix 4g of polyvinyl alcohol, 0.15g of carbon nanotubes and 20mL of water, and stir at 120℃ for 2h to obtain solution A;

[0142] (2) Mix 0.8g chitosan, 2.8mL of 30% acetic acid aqueous solution and 20mL of water, stir for 2h to obtain solution B;

[0143] (3) Mix solutions A and B, pour them into a mold with a thickness of 1.6 mm, and let them stand at -20℃ for 12 h to form a gel, resulting in a hydrogel with a thickness of 1.6 mm. The thickness of the hydrogel is uniformly distributed.

[0144] (4) The hydrogel from step (3) encapsulates the fiber battery of Example 1 to obtain the in-situ monitoring device.

[0145] The mass ratio of polyvinyl alcohol, carbon nanotubes, and water in step (1) is 4:0.15:20.

[0146] In step (2), the mass ratio of chitosan, acetic acid, and water is 0.8:0.84:21.96.

[0147] In this invention, the density of both a 30% acetic acid aqueous solution and water is considered to be 1 g / mL.

[0148] Application Example 3

[0149] This application example provides an in-situ monitoring device, which differs from Application Example 1 in that the thickness of the hydrogel is 2.8 mm. All other aspects are the same as in Example 1, as detailed below:

[0150] The in-situ monitoring device includes a fiber battery and a hydrogel prepared in Example 1, wherein the surface of the fiber battery is provided with hydrogel;

[0151] The preparation method of the above-mentioned in-situ monitoring device includes the following steps:

[0152] (1) Mix 4g of polyvinyl alcohol, 0.15g of carbon nanotubes and 20mL of water, and stir at 120℃ for 2h to obtain solution A;

[0153] (2) Mix 0.8g chitosan, 2.8mL of 30% acetic acid aqueous solution and 20mL of water, stir for 2h to obtain solution B;

[0154] (3) Mix solutions A and B, pour into a mold with a thickness of 2.8 mm, and let stand at -20℃ for 12 hours to form a gel, resulting in a hydrogel with a thickness of 2.8 mm. Figure 8 As shown, the hydrogel has a uniform thickness distribution;

[0155] (4) The hydrogel from step (3) encapsulates the fiber battery of Example 1 to obtain the in-situ monitoring device.

[0156] The mass ratio of polyvinyl alcohol, carbon nanotubes, and water in step (1) is 4:0.15:20.

[0157] In step (2), the mass ratio of chitosan, acetic acid, and water is 0.8:0.84:21.96.

[0158] In this invention, the density of both a 30% acetic acid aqueous solution and water is considered to be 1 g / mL.

[0159] Application Example 4

[0160] This application example provides an in-situ monitoring device, including a fiber battery and a hydrogel prepared in Example 1, wherein the surface of the fiber battery is provided with hydrogel;

[0161] The preparation method of the above-mentioned in-situ monitoring device includes the following steps:

[0162] (1) Mix 4g of polyvinyl alcohol, 0.15g of carbon nanotubes and 20mL of water, and stir at 120℃ for 2h to obtain solution A;

[0163] (2) Mix 0.8g chitosan, 2.8mL of 30% acetic acid aqueous solution and 20mL of water, stir for 2h to obtain solution B;

[0164] (3) Mix solutions A and B, pour them into a mold with a thickness of 0.3 mm, and let them stand at -20℃ for 12 h to form a gel, resulting in a hydrogel with a thickness of 0.3 mm and a uniform thickness distribution.

[0165] (4) The hydrogel from step (3) encapsulates the fiber battery of Example 1 to obtain the in-situ monitoring device.

[0166] The mass ratio of polyvinyl alcohol, carbon nanotubes, and water in step (1) is 4:0.15:20.

[0167] In step (2), the mass ratio of chitosan, acetic acid, and water is 0.8:0.84:21.96.

[0168] In this invention, the density of both a 30% acetic acid aqueous solution and water is considered to be 1 g / mL.

[0169] It is worth noting that the in-situ monitoring device prepared in this application example is easily damaged due to the excessively thin thickness of the hydrogel used, which reduces the service life of the in-situ monitoring device.

[0170] In addition, to ensure the service life of in-situ monitoring devices, the thickness of the hydrogel is generally required to be at least 0.6 mm.

[0171] Performance testing

[0172] 1. Discharge specific capacity tests were performed on the fiber batteries of each embodiment and comparative example:

[0173] Under 25℃ conditions, the discharge specific capacity of the fiber batteries in each embodiment and comparative example was tested at different current densities using the Landian Battery Testing System (model: CT3002A, Wuhan Landian Electronics Co., Ltd.). During the test, the fiber batteries were activated with a small current density of 0.1 A / g. Since the first charge-discharge cycle after activation with a small current and change of current density is unstable, the discharge specific capacity data of the second cycle at a current density of 0.2 A / g was taken as the discharge specific capacity data of the fiber batteries in each embodiment and comparative example. The experimental results are shown in Table 3.

[0174] Table 3. Discharge specific capacity of fiber batteries in each embodiment and comparative example.

[0175]

[0176]

[0177] Figure 9 The graphs show the rate performance of Examples 1-2 and Comparative Example 1. Figure 10 The above figures show the rate performance of Examples 1, 3-5, and Comparative Example 2.

[0178] From Table 3 and Figure 9-10 It is understood that the fiber battery of the present invention can improve the discharge specific capacity of flexible zinc-ion batteries using manganese-based materials as positive electrode materials.

[0179] Specifically, the fiber battery of the present invention, by using a structure in which a spiral positive electrode is nested within a spiral negative electrode, and a specific manganese-based material, can increase the contact area between the manganese-based material and the solid electrolyte. This allows a large amount of manganese-based material to stably adhere to the surface of the positive electrode wire, reducing or preventing the active material and solid electrolyte interphase (SEI) film from detaching from the positive electrode. This enables the manganese-based material to fully exert its function, which helps to improve the discharge specific capacity of the fiber battery, i.e., it is beneficial to improve the discharge specific capacity of flexible zinc-ion batteries using manganese-based materials as the positive electrode material. In addition, the structure in which a spiral positive electrode is nested within a spiral negative electrode improves the discharge specific capacity of the fiber battery by promoting the function of the manganese-based material.

[0180] In particular, as can be seen from Examples 1-2 and Comparative Example 1, the fiber battery of the present invention, by using a specific ratio of manganese dioxide, conductive agent, and binder, can make manganese dioxide and conductive agent uniformly distributed on the surface of the positive electrode wire, and form a conductive network through contact with each other, which helps to further improve the discharge specific capacity of the fiber battery; at the same time, the specific ratio of manganese dioxide, conductive agent, and binder can further increase the adhesion of manganese-based materials, making them adhere more stably to the surface of the positive electrode wire, further reducing or preventing the active material and solid electrolyte interphase (SEI) film from falling off the positive electrode, allowing the manganese-based material to fully play its role, thereby further improving the discharge specific capacity of the fiber battery; that is, it is beneficial to further improve the discharge specific capacity of flexible zinc-ion batteries with manganese-based materials as positive electrode materials.

[0181] In addition, in this invention, the ratio of the specific positive electrode wire's manganese-based material loading per unit area to the negative electrode wire's zinc loading per unit area can improve the specific discharge capacity of the fiber battery, which is beneficial to improving the specific discharge capacity of the flexible zinc-ion battery with manganese-based material as the positive electrode material.

[0182] As can be seen from Examples 1, 3-5 and Comparative Example 2, when the ratio of the manganese-based material loading per unit area of ​​the positive electrode wire to the zinc loading per unit area of ​​the negative electrode wire is too large, that is, when the zinc loading per unit area of ​​the negative electrode wire is too low, the active material of the positive electrode cannot react fully, resulting in a decrease in the discharge specific capacity of the fiber battery; when the ratio of the manganese-based material loading per unit area of ​​the positive electrode wire to the zinc loading per unit area of ​​the negative electrode wire is too small, that is, when the zinc loading per unit area of ​​the negative electrode wire is too high, the zinc layer on the surface of the negative electrode wire is thicker, and the zinc at the bottom cannot fully contact the solid electrolyte, resulting in a smaller discharge specific capacity of the fiber battery.

[0183] 2. Sensitivity tests were performed on the in-situ monitoring devices for each application example:

[0184] Under 25℃ conditions, the fiber batteries were charged and discharged using the Landian Battery Testing System (model: CT3002A, Wuhan Landian Electronics Co., Ltd.). A high-precision current and voltage test source (Keithley 2635B) was used to monitor the resistance change of the sensing layer in each application example during the battery charging and discharging process. The resistance change rate ΔR / R0 during the charging and discharging process was calculated, where R0 is the initial resistance of the sensing layer without applied strain. The absolute value of the maximum resistance change rate during the charging and discharging process (|ΔR / R0|) was used to characterize the sensitivity of the in-situ monitoring device in each application example. A larger absolute value of the maximum resistance change rate during the charging and discharging process indicates a greater sensitivity of the in-situ monitoring device. The experimental results are shown in Table 4.

[0185] Table 4. Sensitivity of in-situ monitoring devices in various application examples

[0186] Hydrogel thickness (mm) Sensitivity (∣ΔR / R0∣) Application Example 1 0.8 15.63 Application Example 2 1.6 6.21 Application Example 3 2.8 3.48

[0187] As shown in Table 4, in this invention, the in-situ monitoring device with hydrogel of a specific thickness has better sensitivity, can detect the temperature or deformation of the fiber battery more accurately and in real time, and also has a longer service life.

[0188] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A fiber battery, characterized in that, It includes a positive electrode, a negative electrode, and a solid electrolyte. The solid electrolyte encapsulates the positive and negative electrodes, both of which are spiral-shaped. The positive electrode is nested inside the negative electrode. The surface of the positive electrode is provided with a positive electrode wire of manganese-based material, and the surface of the negative electrode is provided with a negative electrode wire of metallic zinc. The manganese-based material contains manganese dioxide, a conductive agent, and a binder. The manganese-based material contains manganese dioxide, a conductive agent, and a binder in a mass ratio of (7-8):(1-2):1, and the zinc loading per unit area of ​​the negative electrode wire is 4.0-18.0 mg / cm². 2 The ratio of the manganese-based material loading per unit area of ​​the positive electrode wire to the zinc loading per unit area of ​​the negative electrode wire is 0.2:(4.0-18.0).

2. The fiber battery as described in claim 1, characterized in that, The manganese-based material loading per unit area of ​​the positive electrode wire is 0.15-0.4 mg / cm². 2 .

3. The fiber battery as described in claim 2, characterized in that, The manganese-based material loading per unit area of ​​the positive electrode wire is 0.18-0.38 mg / cm². 2 .

4. The fiber battery as described in claim 1, characterized in that, Includes at least one of the following (1)-(4): (1) The solid electrolyte contains guar gum, zinc salt and manganese salt; (2) The conductive agent is at least one of carbon nanotubes, graphene, Super P, and acetylene black; (3) The adhesive is at least one of polyvinylidene fluoride, carboxymethyl cellulose, and polyacrylic acid; (4) The material of the positive electrode wire and / or negative electrode wire is at least one of stainless steel and carbon fiber.

5. A method for preparing a fiber battery according to any one of claims 1-4, characterized in that, Includes the following steps: S1. Coating and / or spraying manganese-based material onto the surface of the positive electrode wire to obtain the positive electrode, for later use; S2. Electroplating zinc onto the surface of the negative electrode wire yields the negative electrode, which is then set aside. S3. Wrap the positive and negative electrodes with a solid electrolyte, with the positive electrode nested inside the negative electrode, to obtain a fiber battery.

6. The application of the fiber battery according to any one of claims 1-4 in a wearable smart electronic product.

7. An in-situ monitoring device, characterized in that, Includes the fiber battery and hydrogel according to any one of claims 1-4, wherein the surface of the fiber battery is provided with hydrogel.

8. The in-situ monitoring device as described in claim 7, characterized in that, The thickness of the hydrogel is ≥0.8mm.

9. A method for preparing the in-situ monitoring device according to any one of claims 7-8, characterized in that, Includes the following steps: By encapsulating the fiber battery with hydrogel, an in-situ monitoring device can be obtained.

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