CN103700798A - Fiber chemical energy storage power supply and preparation method thereof - Google Patents
Fiber chemical energy storage power supply and preparation method thereof Download PDFInfo
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- CN103700798A CN103700798A CN201310689732.1A CN201310689732A CN103700798A CN 103700798 A CN103700798 A CN 103700798A CN 201310689732 A CN201310689732 A CN 201310689732A CN 103700798 A CN103700798 A CN 103700798A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0431—Cells with wound or folded electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a fiber chemical energy storage power supply and a preparation method thereof. The fiber anode (fiber cathode) comprises a conductive filament substrate and an electrochemical active material coated on the conductive filament. The diaphragm fiber is formed by winding an insulating fiber on the surface of one of the working electrodes at a certain pitch so as to prevent short circuit caused by direct contact of the two electrodes. The fiber anode and the fiber cathode can be mutually wound or arranged in parallel and are arranged in a flexible outer packaging layer, and the electrolyte is filled between the outer packaging layer and the two working electrodes. The fibrous chemical energy storage power supply not only can realize efficient energy storage, but also endows the energy storage battery with good flexibility and portability. It is worth mentioning that the fibrous chemical energy storage power supply structure invented by us is used for all types of chemical energy storage power supplies, and can greatly enrich the power supply forms in our lives.
Description
Technical Field
The invention belongs to the field of chemical energy storage power supplies, and particularly relates to a high-flexibility, weaveable and portable fiber chemical energy storage power supply device.
Background
The human society overuses fossil energy, causes deterioration of environmental problems, and directly affects the sustainable development of human beings. Therefore, it is important to develop green energy sources and efficient energy storage devices. Chemical power sources are receiving increasing attention from scientists and industry as an efficient energy storage device based on redox chemistry. Common chemical power sources include zinc-manganese alkaline primary batteries, zinc-manganese alkaline secondary batteries, nickel-zinc secondary batteries, nickel-hydrogen secondary batteries, lead storage batteries, silver-zinc secondary batteries, widely used lithium ion batteries, and the like. Each of these batteries has its own unique advantages, such as zinc manganese alkaline batteries, which are well known for their low cost, lithium ion batteries, which are widely studied for their high energy storage density, and nickel hydrogen secondary batteries and lead storage batteries, which are widely used in electric vehicles for their safety and stability.
In recent years, the rise of flexible electronics has greatly promoted the development of flexible energy storage devices. The traditional chemical power supply structure is basically based on a sandwich structure and comprises a positive electrode, a negative electrode, electrolyte and a diaphragm which are in two-dimensional planes, and the two-dimensional planes are further curled to form a rigid cylindrical, rectangular or other-shaped chemical power supply. Thus, conventional rigid chemical power sources cannot meet the requirements of flexible electronic energy storage devices. To this end, researchers have further proposed the development of flexible chemical energy storage power sources, such as flexible lithium ion batteries, flexible stretchable zinc-manganese primary batteries, and the like. Compared with the supercapacitor with a rigid structure, the flexible supercapacitor has a wider application range, however, the flexible batteries are still based on a two-dimensional planar sandwich structure, so that the application of the flexible batteries in certain fields is still limited, such as the portability or the special space limitation of the assembly of the flexible batteries.
Disclosure of Invention
In view of the above technical problems, an object of the present invention is to provide a fiber chemical energy storage power supply, which has the advantages of high efficiency, high flexibility, capability of being woven and portable, and can effectively meet the requirement of diversified applications of flexible energy storage devices.
The invention also aims to provide a preparation method of the fiber chemical energy storage power source.
The above purpose of the invention is realized by the following technical scheme:
a fibrous chemical energy storage power supply comprises a fiber anode, a fiber cathode, an electrolyte, diaphragm fibers and an outer packaging layer; the diaphragm fiber is wound on at least one electrode of the fiber anode and the fiber cathode; the electrolyte is filled between the fiber anode and the fiber cathode and is coated in the outer packaging layer together with the fiber anode and the fiber cathode.
Furthermore, the fiber anode and the fiber cathode respectively comprise a conductive filamentous substrate and an electrochemical active material coated outside the conductive filamentous substrate.
Further, the conductive filamentous substrate comprises a metal wire or a non-metal conductive wire or a filamentous structure with a filamentous core and an outer layer wrapping a conductive material.
Specifically, the conductive filamentous substrate can adopt metal wires, including stainless steel fibers and nickel fibers; or non-metallic conductive filaments, such as carbon-based conductive fibers, including carbon fibers, carbon nanofibers, graphene fibers; the conductive polymer fiber comprises PEDOT (Poly ethylene terephthalate) fiber, polyaniline fiber and polythiophene fiber; inorganic conductive compound fibers, organic/inorganic conductive composite fibers, and the like; or the outer layer of the filiform core made of conductive material or non-conductive material is wrapped with the conductive material skin; the composite material can also comprise a core and a plurality of layers of skins, wherein the skins of the core and the inner layer are made of conductive materials or non-conductive materials, the skins wrap the outer side of the core layer by layer, and the outermost skin is made of conductive materials. The conductive material is an organic conductive material or an inorganic conductive material or an organic/inorganic composite conductive material.
Further, the conductive wire-shaped substrate may be a solid structure or a hollow structure, and the cross-sectional shape thereof may be circular, or may be other shapes, such as rectangle, ellipse, etc.
Further, the diameter of the conductive filamentous substrate may be between 1 μm and 1mm, and preferably between 5 μm and 100 μm.
Further, the type of electrochemically active material will depend on the type of cell being produced. For example, for a lithium ion battery, the electrochemically active material of the positive electrode may be LiCoO 2 ,LiMn 2 O 4 ,LiFePO 4 S, etc., the electrochemically active material of the negative electrode may be graphite, silicon, etc. For zinc-manganese cells, the electrochemically active material of the positive electrode is MnO 2 The electrochemically active material of the negative electrode is zinc.
Further, the surface of the fiber positive and negative materials is preferably coated with light, cheap and highly flexible fiber materials such as polymer plastic fiber carbon fiber, carbon nanofiber, graphene fiber, stainless steel fiber and nickel fiber with conductive substances or self-conductivity.
Further, the fiber anode and the fiber cathode can be one or more.
Further, the diaphragm fiber comprises polytetrafluoroethylene fiber, polyvinylidene fluoride plastic fiber, nylon fiber, polyester fiber, acrylic polyester fiber, aramid fiber, enameled wire, fine cotton thread, polypropylene fiber, polyethylene fiber and glass fiber.
Further, the material of the outer packaging layer is a water-proof polymer and comprises polytetrafluoroethylene.
A preparation method of a fiber chemical energy storage power supply comprises the following steps:
1) Respectively coating electrochemical active materials on the conductive filamentous substrate to form a fiber anode and a fiber cathode, namely working electrodes;
2) Winding membrane fiber or wrapping a porous polymer membrane on the surface of at least one electrode in the working electrodes;
3) Assembling the fiber anode and the fiber cathode into a mutually parallel or winding structure;
4) Placing the assembled working electrode in an outer packaging layer;
5) And filling electrolyte between the working electrode and the outer packaging layer to form a fiber chemical energy storage power supply.
For different power systems, the preparation method of the positive and negative electrodes can be any common preparation means, such as preparing slurry of corresponding electrochemical active materials, immersing the electrodes into the slurry, taking out the electrodes, drying and removing the solvent (Czochralski method); or chemical vapor deposition, hydrothermal method, electrochemical method to prepare nanostructured electrochemical active material on electrode substrate, etc.
The preferred electrode preparation method is a Czochralski method, and the coated material generally comprises 50-90 wt% of the electrochemically active material, 1-25 wt% of the conductive agent, and 1-25 wt% of the binder.
The thickness of the electrode clad material can be determined by its own capacitance properties, and the thickness of the clad material is generally preferably 100nm to 50 μm.
In a traditional chemical energy storage power supply, a diaphragm can separate a positive electrode from a negative electrode, so that short circuit (or electric leakage) caused by direct contact of the two electrodes is prevented; moreover, the diaphragm also needs to be a porous film, so that the diffusion of ions in the electrolyte is facilitated; in addition, the separator is required to have a high degree of resistance to corrosion by the electrolyte.
In the fiber chemical energy storage power source designed by the inventor, the design and selection of the diaphragm are also particularly important. Here, we innovatively provide a diaphragm structure for a fiber chemical energy storage power supply, and the structure can effectively avoid the direct contact of two fiber electrodes when the fiber energy storage power supply is bent, and can form a high-efficiency ion transmission channel. The specific design is as follows:
uniformly winding insulated diaphragm fibers such as polytetrafluoroethylene fibers, nylon fibers, enameled wires, fine cotton wires and the like on the surface of a fiber anode (or a fiber cathode); the degree of entanglement can be selected according to the particular electrode diameter and application, such as a preferred separator fiber diameter of between 10 μm and 200 μm for a working electrode diameter of 100 μm, and a preferred winding pitch of between 1 μm and 500 μm.
Compared with the traditional diaphragm material, the diaphragm fiber used by people does not need to have the porous characteristic, and the internal ions can be transmitted through a pitch channel, so that the diaphragm fiber is richer in material selection, and materials which cannot be used by some traditional diaphragms can be used for the diaphragm fiber, such as polytetrafluoroethylene plastic fiber, polyvinylidene fluoride plastic fiber and the like, so that the preparation cost of the diaphragm and the cost of a final chemical energy storage power supply can be effectively reduced.
As mentioned above, there are many varieties of current chemical sources of electrical energy, and their properties are directly related to the material system used. The fiber chemical energy storage power supply proposed by the inventor is the same as the traditional chemical power supply in the working principle, so the structure is also suitable for various chemical power supply systems.
The choice of electrolyte is determined by the type of chemical source of electrical energy specifically employed. For example, in the case of an alkaline secondary battery (zinc-manganese battery, silver-zinc battery, nickel-hydrogen battery, zinc-oxygen battery, etc.), the electrolytic solution is generally an alkaline KOH aqueous solution or an alkaline gel solution containing a polymer (polyvinyl alcohol, polymethacrylic acid, polyvinyl alcohol, etc.). For lithium ion batteries, the typical electrolyte is LiPF 6 The solvent of the acetonitrile/propylene carbonate solution can also be other organic solvents or ionic liquids with low volatility, low toxicity, high boiling point and high ignition point, or quasi-solid electrolyte dissolved with macromolecules (polyvinyl alcohol, polymethacrylic acid, polyvinyl alcohol and the like). From packaging and practical use considerations for fiber energy storage power sources, our preferred materials are as gel electrolytes and solid electrolytes as can be used for this power source type.
Here we illustrate several systems of chemical sources of electrical energy. For zinc-manganese alkaline batteries, the electrochemically active material components used for the fibrous positive electrode are manganese dioxide (50-90% by weight), a conductive agent (1-25%), a binder (1-25%); the electrochemical material used for the fiber negative electrode comprises zinc powder (the weight ratio is 50-90%)Additives (such as zinc oxide, bismuth oxide and the like which are helpful for reducing the precipitation material of hydrogen, 1-25%), and binders (1-25%); the electrolyte is an aqueous solution of alkaline potassium hydroxide or a polymer gel solution; for a nickel-zinc secondary battery, the electrochemical material used by the fiber anode comprises basic nickel hydroxide (the weight ratio of NiOOH is 50-90%), a conductive agent (such as graphite powder, 1-25% of acetylene carbon and the like) and a binder (such as 1-25% of vinylidene fluoride, polymethyl acrylate, tetrafluoroethylene and the like); the electrochemical material used by the fiber negative electrode comprises 50-90 wt% of zinc powder, 1-25 wt% of additives (such as zinc oxide, bismuth oxide and the like which are helpful for reducing the precipitation of hydrogen) and 1-25 wt% of binders; the electrolyte is an aqueous solution of alkaline potassium hydroxide or a polymer gel solution; for silver-zinc secondary batteries, the electrochemically active material component of the fiber positive electrode is silver oxide (50-90% by weight), conductive agent (such as graphite powder, acetylene carbon 1-25%), binder (such as vinylidene fluoride, polymethyl acrylate, tetrafluoroethylene 1-25%); the electrochemical material used by the fiber negative electrode comprises 50-90 wt% of zinc powder, 1-25 wt% of additives (such as zinc oxide, bismuth oxide and the like which are helpful for reducing the precipitation of hydrogen) and 1-25 wt% of binders; the electrolyte is an aqueous solution of alkaline potassium hydroxide or a polymer gel solution; for lithium ion batteries, the electrochemical material used for the fibrous positive electrode is composed of a high-potential lithium ion-intercalated active material (50-90% by weight), such as LiFePO 4 ，LiMn 2 O 4 ，LiCoO 2 Elemental sulfur, etc., conductive agent (such as graphite powder, acetylene carbon 1-25%), binder (such as vinylidene fluoride, polymethyl acrylate, tetrafluoroethylene, etc. 1-25%); the electrochemical material used for the fiber negative electrode is low-potential active material (50-90 wt%) with lithium ions inserted therein, such as graphite and Li 4 Ti 5 O 12 Simple substance silicon and the like, conductive agent (such as graphite powder and acetylene carbon of 1-25 percent), and binder (such as vinylidene fluoride, polymethyl acrylate, tetrafluoroethylene and the like of 1-25 percent); the electrolyte is an organic solution containing lithium ion salts or a polymer gel solution.
The invention has the beneficial effects that:
the invention can further expand the application of the flexible chemical energy storage power supply in the fields of energy and flexible electronics, and realizes a novel high-efficiency energy storage, high flexibility, knittable and portable fibrous flexible energy storage power supply. Through the series-parallel connection of a plurality of fiber energy storage power supplies, various flexible modules can be woven, and the flexible modules can be possibly embedded into clothes, hats or curtains in our lives. In a word, the flexibility of the fiber can realize the diversification of the application, and meanwhile, the large-scale production can be realized by adopting a pulling method on the preparation process of the device, so that the fiber has potential advantages.
In addition, compared with the traditional diaphragm material, the diaphragm fiber used by people does not need to have the characteristic of porosity, and the internal ions can be transmitted through a screw pitch channel, so that the diaphragm fiber is richer in material selection, and materials which cannot be used by the traditional diaphragm, such as polytetrafluoroethylene plastic fiber, polyvinylidene fluoride plastic fiber and the like, can be used as the diaphragm fiber of the invention, and further, the preparation cost of the diaphragm can be effectively reduced.
Drawings
The present invention will be described in detail below with reference to the accompanying drawings.
FIG. 1 is a schematic structural diagram of an axial cross section of a fiber chemical energy storage power supply according to a first embodiment of the invention;
FIG. 2 is a schematic structural diagram of a radial cross section of a fiber chemical energy storage power supply according to a first embodiment of the invention;
FIG. 3 is a constant current discharge curve of the structure of the fiber chemical energy storage power supply according to the first embodiment of the present invention, wherein the current is 50 μ A;
FIG. 4 is a constant current discharge curve of the structure of the fiber chemical energy storage power supply of the third embodiment of the present invention, wherein the current is 0.1mA;
wherein: 1-conductive wire-shaped substrate, 2-electrochemical active material, 3-diaphragm fiber, 4-electrolyte, and 5-outer sleeve.
Detailed Description
In order to facilitate full understanding of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
The first embodiment,
The invention relates to a structure and a preparation method of a fiber chemical energy storage power supply based on a zinc-manganese battery
As shown in fig. 1 and 2, the fibrous chemical energy storage power source comprises a conductive filamentous substrate 1, an electrochemically active material 2, a separator fiber 3, an electrolyte 4, and an outer sleeve 5. The electrochemically active material 2 is typically in the form of a porous active material film that is coated onto the outer surface of the electrically conductive filamentary substrate 1. The insulating separator fibers 3 are uniformly wound around the outer surface of the electrochemically active material 2. The conductive filamentous substrate 1, the electrochemically active material 2 and the membrane fibers 3 together form the main body of the fiber chemical energy storage power source. After the main body of the device is inserted into the outer sleeve 5, the electrolyte 4 is filled in the outer sleeve 5 to form a complete fiber chemical energy storage power supply unit.
In this embodiment, a fiber-shaped chemical energy storage power supply based on a zn-mn battery uses a stainless steel wire as a conductive filamentous substrate, and the stainless steel wire coated with a manganese dioxide film is a fiber anode; the stainless steel wire coated with the metal zinc film is a fiber cathode; insulated enameled wires are used as diaphragm fibers to be uniformly wound on the surface of a fiber anode, a fiber cathode and the fiber anode are arranged in parallel and closely, and electrolyte is filled between the fiber anode and the fiber cathode and is coated in a flexible polytetrafluoroethylene tube together with the fiber anode and the fiber cathode.
The preparation method of the anode of the fiber chemical energy storage power supply based on the zinc-manganese battery comprises the following steps: manganese dioxide slurry was coated and sintered several times (pulling method) on a substrate of a conductive wire-shaped stainless steel wire (diameter 100 μm) having a length of 10cm to obtain a manganese dioxide thin film having a film thickness of 50 μm. The manganese dioxide slurry comprises 75% (by weight) of manganese dioxide, 10% of graphite powder and 15% of polyvinylidene fluoride in N-methylpyrrolidone slurry. The preparation method of the negative electrode of the fiber chemical energy storage power supply based on the zinc-manganese battery comprises the following steps: a metallic zinc paste slurry was coated and sintered several times on a conductive wire-shaped stainless steel wire (diameter 100 μm) substrate having a length of 10cm (pulling method) to obtain a metallic zinc thin film having a film thickness of 50 μm. Wherein the metal zinc paste slurry comprises 75% (by weight) of metal zinc powder, 6% of zinc oxide powder, 4% of bismuth trioxide and 15% of polyvinylidene fluoride in N-methylpyrrolidone slurry. As shown in the structure of FIG. 1, an insulated wire is uniformly wound on the surface of a positive electrode (wire diameter 200 μm, pitch 200 μm), with a negative electrode placed in parallel and in close proximity thereto, and placed in a flexible polytetrafluoroethylene tube. The electrolyte is poured into ammonium chloride: potassium hydroxide: water (weight ratio 26. Under the two-electrode system, the constant current charge-discharge curve was measured, and the charge-discharge curve is shown in fig. 3. The figure shows that the cell continues to discharge for 3.5 hours at a discharge plateau of 1.4V to 1.2V at a discharge current of 50 microamps.
Example II,
The invention relates to a structure and a preparation method of a fiber chemical energy storage power supply based on a nickel-zinc battery
In the fibrous chemical energy storage power supply based on the nickel-zinc battery, the graphene fiber is used as a conductive filamentous substrate, and the graphene fiber coated with the nickel hydroxide film is used as a fiber anode; the graphene fiber coated with the metal zinc film is used as a fiber cathode; insulated enameled wires are used as diaphragm fibers to be uniformly wound on the surface of a fiber anode, three fiber cathodes and one fiber anode are closely placed in parallel, and electrolyte is filled between the fiber anodes and the fiber cathodes and is coated in a flexible polytetrafluoroethylene tube together with the fiber anodes and the fiber cathodes.
The preparation method of the anode of the fiber chemical energy storage power supply based on the nickel-zinc battery comprises the following steps: basic nickel hydroxide slurry was coated and sintered several times (Czochralski method) on a conductive filamentous graphene fiber (diameter 5 μm) substrate having a length of 10cm to obtain a nickel hydroxide thin film having a film thickness of 50 μm. Wherein the basic nickel hydroxide slurry comprises 90% (by weight) of basic nickel hydroxide, 1% of graphite powder and 9% of N-methylpyrrolidone slurry of tetrafluoroethylene. The preparation method of the negative electrode of the fiber chemical energy storage power supply based on the nickel-zinc battery comprises the following steps: a metallic zinc paste slurry was coated and sintered several times on a conductive filamentous graphene fiber (diameter 5 μm) substrate having a length of 10cm (Czochralski method) to obtain a metallic zinc thin film having a film thickness of 50 μm. Wherein the components of the metal zinc paste slurry are 90% (weight ratio) of metal zinc powder, 0.5% of zinc oxide powder, 0.5% of bismuth trioxide and 9% of polyvinylidene fluoride N-methylpyrrolidone slurry. The insulated enameled wire is uniformly wound on the surface of the positive electrode (the diameter of the enameled wire is 100 mu m, the screw pitch is 200 mu m), three negative electrodes are parallelly and closely placed, and the enameled wire is placed in a flexible polytetrafluoroethylene tube. The electrolyte is poured into ammonium chloride: potassium hydroxide: water (weight ratio 26.
Example III,
The invention relates to a structure and a preparation method of a fiber chemical energy storage power supply based on a lithium ion battery
In the embodiment, the fibrous chemical energy storage power supply based on the lithium ion battery takes the stainless steel wire as the conductive filamentous substrate and is coated with LiCoO 2 The stainless steel wire of the film is a fiber anode; coated Li 4 Ti 5 O 12 The stainless steel wire of the film is a fiber cathode; insulated enameled wires are used as diaphragm fibers to be uniformly wound on the surface of a fiber anode, a fiber cathode and the fiber anode are arranged in parallel and closely, and electrolyte is filled between the fiber anode and the fiber cathode and is coated in a flexible polytetrafluoroethylene tube together with the fiber anode and the fiber cathode.
The preparation method of the anode of the fiber chemical energy storage power supply based on the lithium ion battery comprises the following steps: liCoO was coated and sintered several times on a substrate of a conductive wire-like stainless steel wire (diameter 100 μm) having a length of 10cm 2 Slurry (Czochralski method) to obtain LiCoO with a film thickness of 50 μm 2 A film. Among them, liCoO 2 The slurry composition was 70% (by weight) LiCoO 2 A slurry of 20% acetylene carbon and 10% polyvinylidene fluoride in N-methyl pyrrolidone. The preparation method of the negative electrode of the fiber chemical energy storage power supply based on the lithium ion battery comprises the following steps: li4Ti5O12 slurry was coated and sintered several times (Czochralski method) on a conductive wire-shaped stainless steel wire (100 μm) substrate having a length of 10cm to obtain Li having a film thickness of 50 μm 4 Ti 5 O 12 A film. Wherein Li 4 Ti 5 O 12 The slurry had a composition of 70% by weight of Li 4 Ti 5 O 12 A slurry of 20% acetylene carbon and 10% polyvinylidene fluoride in N-methyl pyrrolidone. As shown in the structure of FIG. 1, an insulated wire is uniformly wound on the surface of a positive electrode (the diameter of the wire is 200 μm, and the winding pitch is 500 μm), and a negative electrode is placed in parallel and in close proximity thereto and placed in a flexible polytetrafluoroethylene tube. The electrolyte is poured into LiPF with 1M 6 Acetonitrile/methyl acrylate (volume ratio 1. Under the two-electrode system, the constant current charge-discharge curve was measured, as shown in fig. 4. The figure shows that the cell can continue to discharge for 3 hours at a discharge current of 100 microamperes. The discharge plateau is around 0.9V.
Example four,
The invention relates to a structure and a preparation method of a fiber chemical energy storage power supply based on a silver-zinc battery
In the fibrous chemical energy storage power supply based on the silver-zinc battery, PEDOT (PSS) fibers are used as a conductive filamentous substrate, and PEDOT (PSS) fibers coated with a silver oxide film are used as a fiber anode; the PEDOT coated with the metal zinc film is that PSS fiber is a fiber cathode; insulating polytetrafluoroethylene plastic fibers are used as diaphragm fibers to be uniformly wound on the surface of a fiber anode, a fiber cathode and the fiber anode are closely arranged in parallel, and electrolyte is filled between the fiber anode and the fiber cathode and is coated in a flexible polytetrafluoroethylene tube together with the fiber anode and the fiber cathode.
The preparation method of the positive electrode of the fiber chemical energy storage power supply based on the silver-zinc battery comprises the following steps: silver oxide slurry was coated and sintered several times (Czochralski method) on a conductive filament-shaped PEDOT: PSS fiber (diameter 100 μm) substrate having a length of 10cm to obtain a silver oxide film having a film thickness of 50 μm. Wherein the components of the silver oxide slurry are 50% (weight ratio) of silver oxide, 25% of graphite powder and 25% of polymethyl acrylate N-methyl pyrrolidone slurry. The preparation method of the negative electrode of the fiber chemical energy storage power supply based on the silver-zinc battery comprises the following steps: a metallic zinc paste slurry was coated and sintered several times (Czochralski method) on a conductive filamentous PEDOT: PSS fiber (diameter 100 μm) substrate having a length of 10cm to obtain a metallic zinc thin film having a film thickness of 50 μm. The components of the metal zinc paste slurry are 50% (weight ratio) of metal zinc powder, 15% of zinc oxide powder, 10% of bismuth trioxide and 25% of polymethyl acrylate N-methyl pyrrolidone slurry. As shown in the structure of FIG. 1, an insulated PTFE plastic fiber was uniformly wound around the surface of a positive electrode (PTFE plastic fiber diameter: 10 μm, pitch: 1 μm), and a negative electrode was placed in parallel and in close proximity to the surface of the positive electrode, and the wound material was placed in a flexible PTFE tube. The electrolyte is filled with ammonium chloride: potassium hydroxide: water (weight ratio 26.
In conclusion, the invention discloses a structure of a fiber chemical energy storage power supply. The above-described embodiments and examples are not intended to limit the present invention, and various modifications and alterations can be made by those skilled in the art without departing from the spirit and scope of the present invention.
Claims (10)
1. A fibrous chemical energy storage power source, characterized by: the composite material comprises a fiber anode, a fiber cathode, an electrolyte, diaphragm fibers and an outer packaging layer; the diaphragm fiber is wound on at least one electrode of the fiber anode and the fiber cathode; the electrolyte is filled between the fiber anode and the fiber cathode and is coated in the outer packaging layer together with the fiber anode and the fiber cathode.
2. A fibrous chemical energy storage power source according to claim 1, wherein: the fiber anode and the fiber cathode respectively comprise a conductive filamentous substrate and an electrochemical active material coated outside the conductive filamentous substrate.
3. A fibrous chemical energy storage power source according to claim 2, wherein: the conductive filamentous substrate comprises a filamentous structure of which the outer layer of a metal wire or a non-metal conductive wire or a filamentous core is wrapped with a conductive material; the diameter of the conductive filamentous substrate is 1 mu m-1mm.
4. A fibrous chemical energy storage power source according to claim 1, wherein: the fiber positive grade and fiber negative pole are made of materials selected from polymer plastic fiber carbon fiber, carbon nanofiber, graphene fiber, stainless steel fiber and nickel fiber, the surfaces of which are coated with conductive substances or are conductive.
5. A fibrous chemical energy storage power source according to claim 1, wherein: the separator fiber includes: nylon fiber, polyester fiber, acrylic polyester fiber, aramid fiber, enameled wire, fine cotton thread, polypropylene fiber, polyethylene fiber, polyvinylidene fluoride fiber, polytetrafluoroethylene fiber and glass fiber.
6. A fibrous chemical energy storage power source according to claim 1, wherein: the outer packaging layer is made of water-proof polymer and comprises polytetrafluoroethylene.
7. A fibrous chemical energy storage power source according to claim 1, wherein: the number of the fiber anode and the number of the fiber cathode can be one or more.
8. A method of making a fibrous chemical energy storage power source according to any of claims 1 to 7, comprising the steps of:
1) Respectively coating electrochemical active materials on the conductive filamentous substrate to form a fiber anode and a fiber cathode, namely working electrodes;
2) Winding membrane fiber or wrapping a porous polymer membrane on the surface of at least one electrode in the working electrodes;
3) Assembling the fiber anode and the fiber cathode into a mutually parallel or winding structure;
4) Placing the assembled working electrode in an outer packaging layer;
5) And filling electrolyte between the working electrode and the outer packaging layer to form a fiber chemical energy storage power supply.
9. A method of making a fibrous chemical energy storage power source according to claim 8, wherein: the material coated in the step 1) comprises 50-90% of electrochemical active material, 1-25% of conductive agent and 1-25% of binder by weight percentage, and the coating thickness is 100nm-50 μm.
10. A method of making a fibrous chemical energy storage power source according to claim 8, wherein: for a working electrode with a diameter of 100 μm, the diameter of the separator fiber is 10 μm to 100 μm, and the winding pitch is 1 μm to 500 μm.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104617336A (en) * | 2015-02-12 | 2015-05-13 | 中国工程物理研究院化工材料研究所 | Linear flexible lithium ion battery and preparation method thereof |
| CN107069033A (en) * | 2017-03-21 | 2017-08-18 | 中国科学院福建物质结构研究所 | A kind of battery electrode of graphene-containing fiber and its preparation method and application |
| CN107331533A (en) * | 2017-06-30 | 2017-11-07 | 哈尔滨工业大学 | A kind of preparation method of Kev Rana rice fiber reinforced flexible solid-state linear supercapacitor |
| CN107946522A (en) * | 2017-12-15 | 2018-04-20 | 淄博君行电源技术有限公司 | A kind of graphene oxide is modified nickel-hydrogen battery separator and preparation method thereof |
| CN108321382A (en) * | 2018-03-28 | 2018-07-24 | 中国工程物理研究院化工材料研究所 | Flexible fiber shape lithium carbon dioxide cell positive material and preparation method |
| CN109449370A (en) * | 2018-09-21 | 2019-03-08 | 重庆大学 | One kind can weave Zn-MnO2The preparation method of secondary cell and its power supply fabric |
| CN109760819A (en) * | 2018-12-24 | 2019-05-17 | 中国兵器工业导航与控制技术研究所 | A kind of structure battery component of aircraft and aircraft |
| CN109950639A (en) * | 2019-02-20 | 2019-06-28 | 中国科学院电工研究所 | One metal ion species battery and preparation method thereof |
| CN109979763A (en) * | 2019-04-30 | 2019-07-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Folding stack-type one dimension fibre shape flexibility energy storage device and preparation method thereof |
| CN110729518A (en) * | 2019-09-08 | 2020-01-24 | 复旦大学 | Manganese dioxide/graphene-based water-based zinc ion battery and preparation method thereof |
| CN111430776A (en) * | 2020-04-01 | 2020-07-17 | 中国科学院电工研究所 | Flexible lithium-sulfur battery and preparation method thereof |
| CN112563443A (en) * | 2020-11-20 | 2021-03-26 | 扬州大学 | Flexible battery electrode and manufacturing process thereof |
| CN113161624A (en) * | 2021-05-07 | 2021-07-23 | 哈尔滨工业大学 | Preparation method of elastic lithium battery with woven structure |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104617336A (en) * | 2015-02-12 | 2015-05-13 | 中国工程物理研究院化工材料研究所 | Linear flexible lithium ion battery and preparation method thereof |
| CN107069033B (en) * | 2017-03-21 | 2020-02-21 | 中国科学院福建物质结构研究所 | Battery electrode containing graphene fibers and preparation method and application thereof |
| CN107069033A (en) * | 2017-03-21 | 2017-08-18 | 中国科学院福建物质结构研究所 | A kind of battery electrode of graphene-containing fiber and its preparation method and application |
| CN107331533A (en) * | 2017-06-30 | 2017-11-07 | 哈尔滨工业大学 | A kind of preparation method of Kev Rana rice fiber reinforced flexible solid-state linear supercapacitor |
| CN107946522A (en) * | 2017-12-15 | 2018-04-20 | 淄博君行电源技术有限公司 | A kind of graphene oxide is modified nickel-hydrogen battery separator and preparation method thereof |
| CN107946522B (en) * | 2017-12-15 | 2020-08-28 | 淄博君行电源技术有限公司 | Graphene oxide modified nickel-metal hydride battery diaphragm and preparation method thereof |
| CN108321382A (en) * | 2018-03-28 | 2018-07-24 | 中国工程物理研究院化工材料研究所 | Flexible fiber shape lithium carbon dioxide cell positive material and preparation method |
| CN109449370A (en) * | 2018-09-21 | 2019-03-08 | 重庆大学 | One kind can weave Zn-MnO2The preparation method of secondary cell and its power supply fabric |
| CN109760819A (en) * | 2018-12-24 | 2019-05-17 | 中国兵器工业导航与控制技术研究所 | A kind of structure battery component of aircraft and aircraft |
| CN109950639A (en) * | 2019-02-20 | 2019-06-28 | 中国科学院电工研究所 | One metal ion species battery and preparation method thereof |
| CN109979763A (en) * | 2019-04-30 | 2019-07-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Folding stack-type one dimension fibre shape flexibility energy storage device and preparation method thereof |
| CN109979763B (en) * | 2019-04-30 | 2021-07-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Folding-resistant one-dimensional fibrous flexible energy storage device and preparation method thereof |
| CN110729518A (en) * | 2019-09-08 | 2020-01-24 | 复旦大学 | Manganese dioxide/graphene-based water-based zinc ion battery and preparation method thereof |
| CN110729518B (en) * | 2019-09-08 | 2022-12-20 | 复旦大学 | Manganese dioxide/graphene-based water-based zinc ion battery and preparation method thereof |
| CN111430776A (en) * | 2020-04-01 | 2020-07-17 | 中国科学院电工研究所 | Flexible lithium-sulfur battery and preparation method thereof |
| CN112563443A (en) * | 2020-11-20 | 2021-03-26 | 扬州大学 | Flexible battery electrode and manufacturing process thereof |
| CN112563443B (en) * | 2020-11-20 | 2022-08-12 | 扬州大学 | Flexible battery electrode and manufacturing process thereof |
| CN113161624A (en) * | 2021-05-07 | 2021-07-23 | 哈尔滨工业大学 | Preparation method of elastic lithium battery with woven structure |
| CN113161624B (en) * | 2021-05-07 | 2022-06-21 | 哈尔滨工业大学 | Preparation method of elastic lithium battery with woven structure |
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