A fiber battery and a large-scale preparation method thereof

Abstract

The present invention belongs to the technical field of fiber batteries, and discloses a fiber battery and a method for large-scale preparation thereof, wherein the method comprises: uniformly coating a layer of positive electrode active slurry on the surface of a positive electrode substrate by a roller device to obtain a positive electrode material; tightly weaving a diaphragm-like layer on the axial surface of the positive electrode material by a lower weaving area of ​​a double-layer weaving machine to form a positive electrode material with a diaphragm-like layer on the surface; and tightly winding a layer of negative electrode material on the surface of the diaphragm-like layer by an upper weaving area to form a structure of positive electrode, diaphragm, and negative electrode from the inside to the outside, to obtain a fiber battery. The present invention provides a simple, scalable, and industrialized fiber battery preparation process, which can realize the one-time molding of the overall structure of the fiber battery and the continuous and large-scale preparation of the whole battery.

Description

Technical Field

[0001] The present invention relates to the technical field of fiber batteries, and in particular to a fiber battery and a large-scale preparation method thereof. Background Art

[0002] Fiber batteries are considered to be the most promising research and development targets for wearable flexible power sources because of their high flexibility, high energy density, and as a one-dimensional material, they have more subsequent processing feasibility and can be perfectly integrated with the substrate material.

[0003] However, although researchers are currently working hard to explore the molding and preparation process of high-energy storage fiber batteries, the fiber batteries they obtain are often only a few centimeters long, and the total energy storage of shorter fiber batteries is low, making it difficult to meet the output power requirements of actual electronic devices. Therefore, the continuous and large-scale preparation process of small-diameter and low-scale fiber batteries needs to be solved urgently.

[0004] In order to break through the barriers of high energy density, long service life, safety, flexibility and comfort requirements of flexible batteries, the existing solution technology is the most effective fiber-shaped battery preparation process. Peng Huisheng's team proposed a dip-coating and winding scheme, that is, the positive and negative electrode substrates of the fiber battery are coated with active material slurry respectively, and then the diaphragm is wrapped on the production line process, and finally the positive and negative electrodes are wound to complete the battery packaging. Through this technical solution, the large-scale production of fiber batteries has been successfully realized, and the obtained fiber batteries have good energy density and cycle stability, but this method still has the following defects: 1) The active material slurry of the dip-coating method has low loading fastness on the surface of the metal fiber and poor loading uniformity of the active material, and the regularity of charge storage in large scale, large scale and long distance needs to be improved; 2) The battery system constructed with graphite as the negative electrode and cobalt oxide as the positive electrode still has a low energy density and a high interface charge impedance, which leads to serious internal friction and a large impact on the output power; 3) Using metal fibers as current collectors, the fiber batteries prepared continuously have inevitable problems such as large rigidity and poor resilience, which makes it difficult to achieve perfect integration with flexible carriers, affecting their wearing or comfort.

[0005] To this end, the present invention provides a fiber battery and a large-scale preparation method thereof. Summary of the invention

[0006] In order to solve the problems of low loading fastness of active material slurry on the surface of metal fiber, poor loading uniformity of active material, low energy density and poor resilience when preparing fiber battery by dip-coating and winding method in the above-mentioned prior art, the present invention provides a fiber battery and its large-scale preparation method. The present invention adopts the technology of pressure coating loading of active material, and combines the layer-by-layer weaving process to realize the one-time molding self-assembly of positive electrode, negative electrode and diaphragm of battery. On the one hand, the method has high universality, a wide range of raw materials can be selected, and the fineness of positive and negative electrode fibers and diaphragm layer fibers involved in weaving can be changed according to the fineness of fiber electrode and the energy demand of battery, so as to ensure its high flexibility and strength weavability. On the other hand, the centripetal force of weaving process makes the inner electrode, diaphragm layer and outer electrode form a tight coaxial structure, which is conducive to improving the loading fastness of active material, reducing the interface charge transfer impedance between electrode and electrolyte, and increasing the energy storage capacity of battery; therefore, the present invention develops a new type of high flexibility, drapability, high energy density, low charge transfer resistance and small-scale continuous fiber battery construction strategy.

[0007] A fiber battery and a large-scale preparation method thereof of the present invention are realized by the following technical scheme:

[0008] The first object of the present invention is to provide a large-scale preparation method of a fiber battery, comprising the following steps:

[0009] Step 1, conveying the positive electrode substrate fiber to a roller device, and the roller device evenly coats a layer of positive electrode active slurry on the surface of the conveyed positive electrode substrate to form a positive electrode material;

[0010] Wherein, the positive electrode substrate is conductive fiber;

[0011] The positive electrode active slurry is composed of active material, slurry binder and conductive agent;

[0012] Step 2, the positive electrode material enters the lower weaving area of ​​the double-layer weaving machine in a vertical state, and the diaphragm-like layer is tightly woven on the axial surface of the positive electrode material through the lower weaving area to form a positive electrode material with a diaphragm-like layer coated on the surface;

[0013] Step 3, the positive electrode material with the diaphragm-like layer on the surface is still kept in a vertical state and enters the upper weaving area of ​​the double-layer weaving machine, and a layer of negative electrode material is tightly wound on the surface of the diaphragm-like layer through the upper weaving area to form a structure of positive electrode, diaphragm, and negative electrode from the inside to the outside, thereby obtaining a fiber battery;

[0014] Wherein, the lower braided area is coaxially arranged with the upper braided area.

[0015] Furthermore, the conductive fibers are carbon fibers or metal fibers.

[0016] Furthermore, the membrane-like layer is any one of cotton fiber, viscose fiber, acetate fiber and polymer fiber.

[0017] Furthermore, the negative electrode material is zinc wire.

[0018] Furthermore, the coating thickness of the positive electrode active slurry is 10 to 20 μm;

[0019] The active material may be ammonium vanadate; the slurry binder may be polyvinylidene fluoride; and the conductive agent may be carbon black.

[0020] Furthermore, the mass ratio of the active material, the slurry binder and the conductive agent is 6.5-7.5:1.5-2.5:1.

[0021] Furthermore, the lower braided area uses a plurality of spindles to load the bobbins of the diaphragm layer material to be wound in an eight-shaped circular motion; wherein the number of spindles used in the lower braided area can be adjusted according to the requirements of the thickness, tightness and type of diaphragm layer fiber, and has strong universality;

[0022] The upper weaving area uses a plurality of ingots to load the negative electrode material into a bobbin and wind it in an eight-shaped circular motion; wherein, the number of ingots used in the upper weaving area can be adjusted according to the thickness, tightness and type requirements of the diaphragm layer, and the diaphragm fiber type has strong universality.

[0023] Furthermore, the winding device A is a winding shaft, and the positive electrode substrate fiber is wound on the winding shaft. The positive electrode substrate is transported to the roller device by rotating the winding shaft.

[0024] Furthermore, the method further comprises step 4, wherein the obtained fiber battery is transported to an electrolytic cell containing an electrolyte for electrolyte immersion, and then the fiber battery is packaged with a packaging material, and the packaged fiber battery product is wound on a winding device B;

[0025] Wherein, the electrolyte impregnation is a slurry dipping process, and the packaging material is nylon plastic.

[0026] Furthermore, the winding device B rotates synchronously with the winding device A to provide power for material transportation in the entire process through the conveying of the winding device A and the winding reception of the winding device B, so as to realize that the positive electrode substrate is coated with the positive electrode active slurry through the roller device in turn, and then the diaphragm-like layer is tightly woven on the surface of the positive electrode active slurry through the lower weaving area, and then the negative electrode material is tightly wound on the surface of the diaphragm-like layer through the upper weaving area, and then the electrolyte is impregnated through the electrolytic cell of the electrolyte, and then it is packaged through the packaging device, and finally the finished fiber battery after the packaging process is wound on the winding device B, so that each process is carried out in sequence to realize the large-scale preparation of fiber batteries.

[0027] The second object of the present invention is to provide a fiber battery prepared by the above-mentioned large-scale preparation method.

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

[0029] The present invention provides a full-process process for the preparation of large-scale and industrialized fiber batteries, thereby realizing the continuous and large-scale preparation of fiber-shaped full batteries.

[0030] Moreover, the fiber battery prepared by the present invention is the basic unit of textiles, and can be perfectly integrated with textiles (such as fabrics) in a low dimension to become the basic component of textiles. It does not need to be assembled through external equipment or materials, has higher consistency, and can better guarantee the style and other characteristics of the original textiles.

[0031] The present invention adopts the technology of pressure coating loading of active materials, and combines the layer-by-layer weaving process to realize the one-time molding self-assembly of the positive electrode, negative electrode and diaphragm of the battery. On the one hand, this method has high universality, a wide range of raw materials to choose from, and can change the fineness of the positive and negative electrode fibers and the diaphragm layer fibers involved in the weaving according to the fineness of the fiber electrode and the energy demand of the battery to ensure its high flexibility and strength weavability. On the other hand, the centripetal force of the weaving process enables the inner electrode, the diaphragm layer, and the outer electrode to form a tight coaxial structure, which is conducive to improving the loading fastness of the active material, reducing the interface charge transfer impedance between the electrode and the electrolyte, and increasing the battery energy storage capacity; therefore, the present invention develops a new type of high flexibility, drapability, high energy density, low charge transfer resistance and small-scale continuous fiber battery construction strategy. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 It is a schematic diagram of the preparation process of the present invention;

[0033] Figure 2 It is a schematic structural diagram of a positive electrode material with a diaphragm-like layer coated on the surface of the present invention;

[0034] Figure 3 It is a schematic diagram of the structure of "positive electrode, diaphragm, negative electrode" formed by winding zinc wire on the diaphragm-like layer;

[0035] Figure 4 The electrochemical energy storage cyclic voltammetric performance test results of the fiber battery prepared in Example 1. DETAILED DESCRIPTION

[0036] The technical solutions in the embodiments of the present invention will be described clearly and completely below.

[0037] See also Figure 1 The present invention provides a fiber battery that can be prepared on a large scale, and the large-scale preparation method thereof is as follows:

[0038] Step 1, conveying the positive electrode substrate fiber to the roller device 2 through the winding device A1, and uniformly coating a layer of positive electrode active slurry on the surface of the conveyed positive electrode substrate material through the roller device 2 to form a positive electrode material;

[0039] Wherein, the positive electrode active slurry is composed of active material, slurry binder and conductive agent;

[0040] It should be noted that the positive electrode substrate of the present invention can be selected as conductive fiber, and the corresponding conductive fiber material can be selected according to actual needs. The present invention takes into account factors such as the positive electrode material must be a conductive material and have excellent flexibility, and carbon fiber or metal fiber can be preferably used as the positive electrode substrate.

[0041] In addition, the present invention takes into account that the coating thickness of the positive electrode fiber slurry has a great influence on the performance of the fiber battery, and adopts Figure 1 The roller device 2 shown accurately controls the active material loading thickness and fastness to achieve the coating of the positive electrode active slurry.

[0042] Among them, the roller device used in the present invention adopts roller coating technology to coat the active material on the positive electrode substrate, and the roller coating technology belongs to the prior art, and those skilled in the art should know its principle: the active material is placed in the feeding part of the roller device in the form of a coating or slurry. The feeding part of the roller coater generally includes a container for storing the coating or slurry, and a coating supply system for delivering the coating or slurry to the feeding roller of the roller device. During the coating process, the positive electrode substrate is usually conveyed through a set of rollers, one of which is a feeding roller and the other is a pressing roller. The coating or slurry is placed on the feeding roller, and when the positive electrode substrate passes through the roller device, the pressing roller compacts the active material and evenly coats it on the positive electrode substrate. This coating method can achieve an efficient, continuous and uniform coating process, and can be suitable for large-scale production.

[0043] In order to achieve high energy density, low cost, long service life and other factors, the positive electrode active slurry used in the present invention is composed of active material, slurry binder and conductive agent, and the mass ratio of active material, slurry binder and conductive agent is 6.5-7.5:1.5-2.5:1. Among them, the active material is preferably ammonium vanadate, the slurry binder can be polyvinylidene fluoride, and the conductive agent can be carbon black.

[0044] Step 2, the positive electrode material enters the lower weaving area 3 of the double-layer weaving machine in a vertical state, and the positive electrode material is tightly woven and coated along its axial surface through the lower weaving area 3 as a diaphragm-like layer to form a positive electrode material 4 with a surface coated with a diaphragm-like layer, and its structure is as follows Figure 2 As shown;

[0045] It should be noted that the diaphragm-like material used in the present invention can be adjusted according to the type of fiber adjusted by the electrolyte. For example, for aqueous batteries, its diaphragm layer can be cellulose fibers or hydrophilic fibers such as cotton fibers, viscose fibers and acetate fibers; for organic electrolytes, its diaphragm-like material can be selected from hydrophobic fibers such as polymer fibers. And the number of braided roots and fiber fineness can be adjusted according to the thickness of the diaphragm. For example, taking cotton fiber as an example, when cotton fiber is selected as the diaphragm-like material for aqueous batteries, cotton fiber with a fineness of 10 to 20 Tex can be selected as the diaphragm-like material, and the lower braided area 3 is coaxially wound with the positive electrode material to form a diaphragm-like layer.

[0046] Step 3, the positive electrode material 4 with the diaphragm-like layer on the surface is still kept in a vertical state and enters the upper weaving area 5 of the double-layer weaving machine, and a layer of negative electrode material is tightly wound around the diaphragm-like layer through the upper weaving area 5 to form a structure of positive electrode, diaphragm, and negative electrode from the inside to the outside, and a fiber battery 6 is obtained. Figure 3 As shown;

[0047] It should be noted that the present invention takes into account the one-time molding process of the positive electrode, the separator layer, and the negative electrode, avoids multiple fiber transfers, and reduces the interface impedance between the electrode-electrolyte and the positive electrode-negative electrode, thereby improving the external output power of the fiber battery and the overall structural stability. The present invention preferably Figure 1 The double-layer weaving machine shown is used to weave the diaphragm layer and the negative electrode material, and the lower weaving area 3 is coaxially arranged with the upper weaving area 5, so as to realize the synchronous operation of the lower weaving area 3 and the upper weaving area 5, so that the positive electrode material 4 coated with a diaphragm-like layer on the surface can still maintain a vertical state and be transported upward to the upper weaving area 5, and then the negative electrode material can be continuously and tightly wound on the diaphragm surface output through the lower weaving area 3 through the upper weaving area 5.

[0048] The present invention can select corresponding negative electrode materials according to actual needs, for example, zinc wire with a fineness of 0.1 to 0.2 mm can be selected as the negative electrode material.

[0049] Step 4, in order to obtain a finished battery, the obtained fiber battery is transported to an electrolytic cell 7 containing an electrolyte for electrolyte immersion;

[0050] In order to prevent oxidation of the surface negative electrode material, a packaging device is used to package the fiber battery obtained in step 8, and the packaging material used in the packaging process is nylon plastic. The finished fiber battery after packaging is wound on a winding device B9;

[0051] Wherein, the electrolyte impregnation is a slurry impregnation process, and the packaging material is nylon plastic;

[0052] It should be noted that the present invention preferably rotates the winding device B9 synchronously with the winding device A1, so as to realize the coating of the positive electrode substrate with the positive electrode active slurry through the roller device 2 in turn through the conveying of the winding device A1 and the winding reception of the winding device B9, and then the diaphragm-like layer is tightly woven on the surface of the positive electrode active slurry through the lower weaving area 3, and then the negative electrode material is tightly wound on the surface of the diaphragm-like layer through the upper weaving area 5, and then the electrolyte is impregnated through the electrolytic cell 7 of the electrolyte, and then the packaging device 8 is used for packaging, and finally the finished fiber battery after packaging is wound on the winding device B9, so as to realize the large-scale preparation of fiber batteries.

[0053] Example 1

[0054] This embodiment provides a fiber battery that can be prepared on a large scale, and its large-scale preparation method is as follows:

[0055] 1. Continuous preparation of fiber battery positive electrode

[0056] See also Figure 1 The carbon fiber is used as the positive electrode substrate and is wound on a winding device A1. One end of the carbon fiber is horizontally input into a pair of rollers 2, and a layer of active material slurry with a thickness of 15 μm is coated on the surface of the carbon fiber through the pair of rollers 2.

[0057] The active material slurry used in this embodiment is composed of ammonium vanadate (NH4V4O 10 ), polyvinylidene fluoride (PVDF) and carbon black (C) are prepared in a ratio of 7:2:1, wherein NH4V4O 10 is the active material, PVDF is the slurry binder, and C is the conductive agent.

[0058] 2. Continuous preparation of fiber battery separator

[0059] See also Figure 1 In this embodiment, cotton fiber with a fineness of 15Tex is used as a diaphragm-like layer material, which is loaded into the bobbin of the lower woven area 3, and 12 bobbins loaded with cotton fiber are wound in an eight-shaped circular motion to achieve a tight wrapping of the cotton fiber on the positive electrode to form a diaphragm-like layer, and a positive electrode material 4 with a diaphragm-like layer on the surface is obtained, and the effect is as follows Figure 2 shown.

[0060] 3. Continuous assembly of fiber batteries

[0061] In this embodiment, zinc wire with a fineness of 0.15 mm is used as the negative electrode material, which is loaded into the bobbin of the upper woven area 5, and 12 bobbins loaded with zinc wire are wound in an eight-shaped circular motion, and a layer of zinc wire is tightly wound on the diaphragm-like layer of the positive electrode material 4 output from the lower woven area 3, which is coated with a diaphragm-like layer on the surface, to form a structure of positive electrode, diaphragm, and negative electrode from the inside to the outside, to obtain a fiber battery 6, such as Figure 3 shown.

[0062] 4. Making fiber batteries into finished products

[0063] The fiber battery 6 obtained above is transported to an electrolytic cell 7 containing electrolyte for electrolyte immersion. In order to avoid oxidation of the surface negative electrode material, a packaging device 8 is used to package a layer of nylon plastic material on the surface of the fiber battery. The finished fiber battery after packaging is wound on a winding device B9.

[0064] The winding device B9 is rotated synchronously with the winding device A1, so that the positive electrode substrate is coated with the positive electrode active slurry in turn through the roller device 2 through the conveying of the winding device A1 and the winding reception of the winding device B9, and then a diaphragm-like layer is tightly woven on the surface of the positive electrode active slurry through the lower weaving area 3, and then the negative electrode material is tightly wound on the surface of the diaphragm-like layer through the upper weaving area 5 to obtain a fiber battery 6.

[0065] Then, the fiber battery 6 is placed in an electrolytic cell 7 containing electrolyte for electrolyte immersion, and then packaged by a packaging device 8. Finally, the packaged fiber battery product is wound on a winding device B9, thereby realizing large-scale preparation of fiber batteries.

[0066] Example 2

[0067] This embodiment provides a fiber battery that can be prepared on a large scale, and its large-scale preparation method is as follows:

[0068] 1. Continuous preparation of fiber battery positive electrode

[0069] The carbon fiber is used as the positive electrode substrate and is wound on a winding device A1. One end of the carbon fiber is horizontally input into a roller device 2. A layer of active material slurry with a thickness of 10 μm is coated on the surface of the carbon fiber through the roller device 2.

[0070] The active material slurry used in this embodiment is prepared by mixing ammonium vanadate, polyvinylidene fluoride and carbon black in a ratio of 6.5:2.5:1, wherein NH4V4O 10 is the active material, PVDF is the slurry binder, and C is the conductive agent.

[0071] 2. Continuous preparation of fiber battery separator

[0072] In this embodiment, cotton fiber with a fineness of 10Tex is used as the diaphragm-like layer material, which is loaded into the bobbin of the lower woven area 3, and 12 bobbins loaded with cotton fiber are wound in an eight-shaped circular motion to achieve tight wrapping of the cotton fiber on the positive electrode to form a diaphragm-like layer, and obtain the positive electrode material 4 with a diaphragm-like layer coated on the surface.

[0073] 3. Continuous assembly of fiber batteries

[0074] In this embodiment, zinc wire with a fineness of 0.1 mm is used as the negative electrode material, which is loaded into the bobbin of the upper weaving area 5, and 12 bobbins loaded with zinc wire are wound in an eight-shaped circular motion to tightly wind a layer of zinc wire on the diaphragm-like layer of the positive electrode material 4 output from the lower weaving area 3 and coated with a diaphragm-like layer on the surface, thereby forming a structure of positive electrode, diaphragm, and negative electrode from the inside to the outside, thereby obtaining a fiber battery 6.

[0075] 4. Making fiber batteries into finished products

[0076] The fiber battery 6 obtained above is transported to an electrolytic cell 7 containing electrolyte for electrolyte immersion. In order to avoid oxidation of the surface negative electrode material, a packaging device 8 is used to package a layer of nylon plastic material on the surface of the fiber battery. The finished fiber battery after packaging is wound on a winding device B9.

[0077] The winding device B9 is rotated synchronously with the winding device A1, so that the positive electrode substrate is coated with the positive electrode active slurry in turn through the roller device 2 through the conveying of the winding device A1 and the winding reception of the winding device B9, and then a diaphragm-like layer is tightly woven on the surface of the positive electrode active slurry through the lower weaving area 3, and then the negative electrode material is tightly wound on the surface of the diaphragm-like layer through the upper weaving area 5 to obtain a fiber battery 6.

[0078] Then, the fiber battery 6 is placed in an electrolytic cell 7 containing electrolyte for electrolyte immersion, and then packaged by a packaging device 8. Finally, the packaged fiber battery product is wound on a winding device B9, thereby realizing large-scale preparation of fiber batteries.

[0079] Example 3

[0080] This embodiment provides a fiber battery that can be prepared on a large scale, and its large-scale preparation method is as follows:

[0081] 1. Continuous preparation of fiber battery positive electrode

[0082] The carbon fiber is used as the positive electrode substrate and is wound on a winding device A1. One end of the carbon fiber is horizontally input into a double-roll device 2. A layer of active material slurry with a thickness of 20 μm is coated on the surface of the carbon fiber through the double-roll device 2.

[0083] The active material slurry used in this embodiment is composed of ammonium vanadate (NH4V4O 10 ), polyvinylidene fluoride (PVDF) and carbon black (C) are prepared in a ratio of 7.5:1.5:1, wherein NH4V4O 10 is the active material, PVDF is the slurry binder, and C is the conductive agent.

[0084] 2. Continuous preparation of fiber battery separator

[0085] In this embodiment, cotton fiber with a fineness of 20Tex is used as the diaphragm-like layer material, which is loaded into the bobbin of the lower woven area 3, and 12 bobbins loaded with cotton fiber are wound in an eight-shaped circular motion to achieve tight wrapping of the cotton fiber on the positive electrode to form a diaphragm-like layer, and obtain the positive electrode material 4 with a diaphragm-like layer coated on the surface.

[0086] 3. Continuous assembly of fiber batteries

[0087] In this embodiment, zinc wire with a fineness of 0.2 mm is used as the negative electrode material, which is loaded into the bobbin of the upper weaving area 5, and 12 bobbins loaded with zinc wire are wound in an eight-shaped circular motion to tightly wind a layer of zinc wire on the diaphragm-like layer of the positive electrode material 4 output from the lower weaving area 3 and coated with a diaphragm-like layer on the surface, thereby forming a structure of positive electrode, diaphragm, and negative electrode from the inside to the outside, thereby obtaining a fiber battery 6.

[0088] 4. Making fiber batteries into finished products

[0089] The fiber battery 6 obtained above is transported to an electrolytic cell 7 containing electrolyte for electrolyte immersion. In order to avoid oxidation of the surface negative electrode material, a packaging device 8 is used to package a layer of nylon plastic material on the surface of the fiber battery. The finished fiber battery after packaging is wound on a winding device B9.

[0090] The winding device B9 is rotated synchronously with the winding device A1, so that the positive electrode substrate is coated with the positive electrode active slurry in turn through the roller device 2 through the conveying of the winding device A1 and the winding reception of the winding device B9, and then a diaphragm-like layer is tightly woven on the surface of the positive electrode active slurry through the lower weaving area 3, and then the negative electrode material is tightly wound on the surface of the diaphragm-like layer through the upper weaving area 5 to obtain a fiber battery 6.

[0091] Then, the fiber battery 6 is placed in an electrolytic cell 7 containing electrolyte for electrolyte immersion, and then packaged by a packaging device 8. Finally, the packaged fiber battery product is wound on a winding device B9, thereby realizing large-scale preparation of fiber batteries.

[0092] Example 4

[0093] This embodiment provides a fiber battery that can be prepared on a large scale, and its large-scale preparation method is as follows:

[0094] 1. Continuous preparation of fiber battery positive electrode

[0095] The metal copper fiber is used as the positive electrode substrate, which is wound on the winding device A1, and one end of the metal copper fiber is input into the roller device 2 in the horizontal direction. A layer of active material slurry with a thickness of 15 μm is coated on the surface of the carbon fiber through the roller device 2.

[0096] The active material slurry used in this embodiment is composed of ammonium vanadate (NH4V4O 10 ), polyvinylidene fluoride (PVDF) and carbon black (C) are prepared in a ratio of 7:2:1, wherein NH4V4O 10 is the active material, PVDF is the slurry binder, and C is the conductive agent.

[0097] 2. Continuous preparation of fiber battery separator

[0098] In this embodiment, acetate fiber is used as the diaphragm-like layer material, which is loaded into the bobbin of the lower woven area 3, and 12 bobbins loaded with acetate fiber are wound in an eight-shaped circular motion to achieve the tight wrapping of acetate fiber on the positive electrode to form a diaphragm-like layer, and obtain the positive electrode material 4 with the diaphragm-like layer coated on the surface.

[0099] 3. Continuous assembly of fiber batteries

[0100] In this embodiment, zinc wire with a fineness of 0.15 mm is used as the negative electrode material, which is loaded into the bobbin of the upper weaving area 5, and 12 bobbins loaded with zinc wire are wound in an eight-shaped circular motion, so that a layer of zinc wire is tightly wound on the diaphragm-like layer of the positive electrode material 4 output from the lower weaving area 3 and coated with a diaphragm-like layer on the surface, to form a structure of positive electrode, diaphragm, and negative electrode from the inside to the outside, thereby obtaining a fiber battery 6.

[0101] 4. Making fiber batteries into finished products

[0102] The fiber battery 6 obtained above is transported to an electrolytic cell 7 containing electrolyte for electrolyte immersion. In order to avoid oxidation of the surface negative electrode material, a packaging device 8 is also used to encapsulate a layer of nylon plastic material on the surface of the fiber battery. The finished fiber battery after packaging is wound on a winding device B9.

[0103] The winding device B9 is rotated synchronously with the winding device A1, so that the positive electrode substrate is coated with the positive electrode active slurry through the roller device 2 in sequence through the conveying of the winding device A1 and the winding reception of the winding device B9, and then the diaphragm-like layer is tightly woven on the surface of the positive electrode active slurry through the lower weaving area 3, and then the negative electrode material is tightly wound on the surface of the diaphragm-like layer through the upper weaving area 5 to obtain the fiber battery 6.

[0104] Then, the fiber battery 6 is placed in an electrolytic cell 7 containing electrolyte for electrolyte immersion, and then packaged by a packaging device 8. Finally, the packaged fiber battery product is wound on a winding device B9, thereby realizing large-scale preparation of fiber batteries.

[0105] Experimental part

[0106] The fiber battery of Example 1 of the present invention was subjected to electrochemical energy storage tests using different scanning rates. The test results are as follows: Figure 4 shown.

[0107] The test method is: cyclic voltammetry (CV) two-electrode test system, voltage range 0.2 ~ 1.6V.

[0108] Depend on Figure 4 It can be seen that the fiber battery has large energy storage capacity, a specific capacity of up to 620F / g, and an output current of up to 1mA, which meets the power output requirements of wearable textile microelectronic components.

[0109] And with the increase of scanning rate, the CV graph of the fiber battery in Example 1 remains stable, that is to say, the fiber battery prepared in Example 1 of the present invention has a highly reversible and rapid battery kinetic reaction process. It also proves that the "positive electrode, diaphragm, negative electrode" structure constructed by the present invention is beneficial to improve the loading fastness of active materials, reduce the interface charge transfer impedance between electrodes and electrolytes, and increase the energy storage capacity of batteries, thereby making the prepared fiber-bottom battery have higher energy storage performance and stable energy storage performance.

[0110] Obviously, the above embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

Claims

1. A large-scale preparation method of fiber batteries, characterized in that: The following steps are involved: Step 1, conveying the positive electrode substrate to a roller device (2), and the roller device (2) evenly coats a layer of positive electrode active slurry on the surface of the conveyed positive electrode substrate to form a positive electrode material; Wherein, the positive electrode substrate is conductive fiber; The positive electrode active slurry is composed of active material, slurry binder and conductive agent; Step 2, the positive electrode material enters the lower weaving area (3) of the double-layer weaving machine in a vertical state, and the diaphragm-like layer is tightly woven on the axial surface of the positive electrode material through the lower weaving area (3) to form a positive electrode material (4) with a diaphragm-like layer coated on the surface; Step 3, the positive electrode material (4) coated with a diaphragm-like layer on the surface is still kept in a vertical state and enters the upper weaving area (5) of the double-layer weaving machine, and a layer of negative electrode material is tightly wound on the surface of the diaphragm-like layer through the upper weaving area (5), forming a structure of positive electrode, diaphragm, and negative electrode from the inside to the outside, thereby obtaining a fiber battery (6); Wherein, the lower braided area (3) and the upper braided area (5) are coaxially arranged.

2. The large-scale preparation method of fiber batteries according to claim 1, characterized in that: The conductive fibers are carbon fibers or metal fibers.

3. The large-scale preparation method of fiber batteries according to claim 1, characterized in that: The membrane-like layer is any one of cotton fiber, viscose fiber, acetate fiber and polymer fiber.

4. The large-scale preparation method of fiber batteries according to claim 1, characterized in that: The negative electrode material is zinc wire.

5. The large-scale preparation method of fiber batteries according to claim 1, characterized in that: The coating thickness of the positive electrode active slurry is 10 to 20 μm; The active material is ammonium vanadate; the slurry binder is polyvinylidene fluoride; and the conductive agent is carbon black; The mass ratio of the active material, the slurry binder and the conductive agent is 6.5-7.5:1.5-2.5:

1.

6. The large-scale preparation method of fiber batteries according to claim 1, characterized in that: The lower braided area (3) is wound with a plurality of bobbins loaded with diaphragm-like material in a figure eight circumferential motion; The upper braided area (5) is wound with a plurality of bobbins loaded with negative electrode materials in a figure eight circumferential motion.

7. The large-scale preparation method of fiber batteries according to claim 1, characterized in that: The positive electrode substrate fiber is conveyed to a roller device (2) through a winding device A (1); The winding device A (1) is a winding shaft, and the positive electrode substrate fiber is wound on the winding shaft. The positive electrode substrate is transported to the roller device (2) by rotating the winding shaft.

8. The large-scale preparation method of fiber batteries according to claim 7, characterized in that: The method further comprises step 4, wherein the obtained fiber battery (6) is transported to an electrolytic cell (7) containing an electrolyte for electrolyte immersion, and then a packaging device (8) is used for packaging, and the fiber battery product after packaging is wound on a winding device B (9); Wherein, the electrolyte impregnation is a slurry dipping process, and the packaging material used by the packaging device is nylon plastic.

9. The large-scale preparation method of fiber batteries according to claim 8, characterized in that: The winding device B (9) rotates synchronously with the winding device A (1).

10. A fiber battery prepared by the large-scale preparation method according to any one of claims 1 to 9.

Images