KR100753824B1 - All-solid-state primary film battery and method of manufacturing the same - Google Patents

Abstract

An all-solid film primary battery and a manufacturing method thereof are disclosed. The film primary battery according to the present invention includes a first polymer current collector film composed of a first polymer film and a first conductive layer, a first electrode layer formed on the first conductive layer, a second polymer film and a second conductive layer. A second polymer current collector film constituted, a second electrode layer formed on the second conductive layer, and a polymer electrolyte layer formed between the first electrode layer and the second electrode layer and containing an aqueous electrolyte solution.

Film, Primary Battery, Polymer Current Collector Film, Aqueous Electrolyte, All Solid, Polymer Electrolyte

Description

All-solid-state primary film battery and method of manufacturing the same {All-solid-state primary film battery and method of manufacturing the same}

1 is a view schematically showing the structure of a film primary battery according to a preferred embodiment of the present invention.

2 is a flowchart illustrating a method of manufacturing a film primary battery according to a preferred embodiment of the present invention.

3 is a graph showing the discharge characteristics of the film primary battery unit cell according to a preferred embodiment of the present invention.

4 is a graph showing a discharge capacity of a film primary battery according to preferred embodiments of the present invention with a comparative example.

FIG. 5 is a graph illustrating a change of an OCV (open circuit voltage) value over time at room temperature of a film primary battery according to exemplary embodiments of the present invention with a comparative example.

6 is a graph showing a change in internal resistance over time at room temperature of a film primary battery according to preferred embodiments of the present invention with a comparative example.

<Explanation of symbols for main parts of the drawings>

10: first polymer current collector film, 12: first polymer film, 14: first conductive layer, 16: anode layer, 20: second polymer current collector film, 22: second polymer film, 24: second conductive layer 26: negative electrode layer, 30: polymer electrolyte layer, 100: film primary battery.

The present invention relates to a primary battery and a method for manufacturing the same, and more particularly to an all-solid film primary battery and a method for manufacturing the same.

Active Radio Frequency Identification (RFID) and Sensor Node (Technical Node) technologies, which are being actively researched recently, are very large and have a huge ripple effect along with digital TV, home networks, and intelligent robots. As technology that surpasses Access technology, it is expected to become a core industry in the future. In other words, the reader not only increases the recognition distance of the tag, but also senses the object information and the environment information around the tag by deviating from the existing passive function of reading the information contained in the tag through the reader. Ultimately, it is expected that the area of information flow can be extended from communication between people and things through networking to communication between things. Therefore, in order to drive the radio wave identification tag and the sensor node, it is important to secure a self-power source completely independent of the reader by using a power element having a small size, light weight, and long lifespan suitable for the tag or node standard.

To date, lithium secondary batteries are one of the power devices that have been applied to RFID tags and sensor nodes. The lithium secondary battery includes a positive electrode or a negative electrode manufactured by using a material capable of intercalation and deintercalation of lithium ions as an active material, and an organic electrolyte or a polymer electrolyte capable of moving lithium ions between the positive electrode and the negative electrode includes: It is inserted. Here, the positive electrode has a structure in which an active material is coated on an aluminum current collector having a thickness of about 20 mm and, in the case of the negative electrode, on a copper current collector. Lithium secondary battery is applied to some sensor nodes, but it is not suitable for active RFID tag price and performance, and it is not easy to recharge after discharge due to the characteristics of tag. Applying a lithium secondary battery to an active tag is problematic because the current collector may cause interference problems when electromagnetic waves are generated from the antenna in the tag.

The present invention is to solve the above-mentioned problems in the prior art, it is possible to further reduce the weight and thickness of the lithium primary battery compared to the prior art, and to improve the flexible properties to have a high energy density and at the same time suitable for applying to the tag Eggplant is to provide a film primary battery.

Another object of the present invention is to provide a method for manufacturing a film primary battery, which is simple, easy to manufacture, and relatively relaxed, by applying a relatively relaxed process condition, to facilitate a complete continuous process and mass production, and to lower manufacturing cost.

In order to achieve the above object, the film primary battery according to the present invention includes a first polymer current collector film composed of a first polymer film and a first conductive layer, a first electrode layer formed on the first conductive layer, and a second polymer A polymer comprising a second polymer current collector film composed of a film and a second conductive layer, a second electrode layer formed on the second conductive layer, and the first electrode layer and the second electrode layer, and containing an aqueous electrolyte solution. An electrolyte layer is included.

Preferably, the first polymer film and the second polymer film are each composed of a polyester polymer, a polyolefin polymer, a cellulose polymer, nylon, polyimide, or a combination thereof. The first polymer film and the second polymer film may each have a single layer or a multilayer structure made of a single kind of polymer material, or a multilayer structure including at least two kinds of polymer materials different from each other.

Each of the first conductive layer and the second conductive layer may be formed of a conductive carbon paste coating layer, a nano metal particle paste coating layer, a conductive polymer coating layer, an ITO (indium tin oxide) paste coating layer, or a conductive carbon tape.

In addition, the first electrode layer may be formed of a mixture of a first conductive agent, a first polymer binder, and a positive electrode active material, and the second electrode layer may be formed of a mixture of a second conductive agent, a second polymer binder, and a negative electrode active material. .

The first conductive agent and the second conductive agent may be made of one conductive carbon selected from the group consisting of graphite, carbon black, denka black, lonza carbon, super-P, and activated carbon MSC30, respectively.

The first polymer binder and the second polymer binder are polytetrafluoroethylene, polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, and air of vinylidene fluoride and trifluoroethylene, respectively. Copolymer, copolymer of vinylidene fluoride and tetrafluoroethylene, polyethylene oxide, polypropylene oxide, polyvinyl chloride, polybutadiene, polystyrene, polyethylene, polypropylene, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate With latex, polyethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polyacrylonitrile, cellulose, carboxymethyl cellulose, starch, polyacrylic acid, polyvinyl alcohol, polyvinylacetate, nylon, and Nafion Any mound selected from the group consisting of Now, or a blend thereof.

The cathode active material may be made of manganese oxide having a particle size of 10 nm to 50 μm, electrolytic manganese dioxide (EMD), nickel oxide, lead oxide, lead dioxide, silver oxide, iron sulfide, or conductive polymer particles. It may be composed of zinc, aluminum, iron, lead, or magnesium particles having a particle diameter of 10 nm to 50 μm.

The polymer electrolyte layer includes an aqueous electrolyte solution containing a polymer matrix, an inorganic additive, and a salt.

The polymer matrix is polyethylene, polypropylene, polyimide, polysulfone, polyurethane, polyvinyl chloride, polystyrene, polyethylene oxide, polypropylene oxide, polybutadiene, cellulose, carboxymethylcellulose, nylon, polyacrylonitrile, polyvinylidene Fluoride, polytetrafluoroethylene, copolymer of vinylidene fluoride and hexafluoropropylene, copolymer of vinylidene fluoride and trifluoroethylene, copolymer of vinylidene fluoride and tetrafluoroethylene, polymethyl In the group consisting of acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polyvinylacetate, polyvinyl alcohol, starch, agar, and nafion Any one selected, or A may be formed of a copolymer, or blends thereof.

The inorganic additive may be made of at least one material selected from the group consisting of silica, talc, alumina (Al ₂ O ₃ ), TiO ₂ , clay, and zeolite.

Preferably, the aqueous electrolyte solution comprises distilled water, the salt in the aqueous electrolyte solution is potassium hydroxide (KOH), potassium bromide (KBr), potassium chloride (KCl), zinc chloride (ZnCl ₂ ), ammonium chloride (NH ₄ Cl) And, and may be composed of at least one selected from the group consisting of sulfuric acid (H ₂ SO ₄ ).

In order to achieve the above another object, in the method of manufacturing a film primary battery according to the present invention, a first polymer film and a second polymer film are prepared. A first conductive layer is formed on the first polymer film to form a first polymer current collector film. A second conductive layer is formed on the second polymer film to form a second polymer current collector film. A first electrode layer is formed on the first polymer current collector film. A second electrode layer is formed on the second polymer current collector film. A polymer electrolyte layer including an aqueous electrolyte is formed between the first electrode layer and the second electrode layer.

The forming of the first conductive layer may include coating a conductive carbon paste, a nanometal particle paste, a conductive polymer, or an ITO paste on the first polymer film, or attaching a conductive carbon tape on the first polymer film. Can be done by. The forming of the second conductive layer may include coating a conductive carbon paste, a nanometal particle paste, a conductive polymer, or an ITO paste on the second polymer film, or attaching a conductive carbon tape on the first polymer film. It can be done by the method.

Film primary battery according to the present invention can be significantly reduced in weight by minimizing the amount of metal used compared to the conventional metal current collector. In addition, due to the characteristics of the polymer film, the bending characteristics are very excellent, and it is possible to eliminate the phenomenon that the electrode layer is peeled or broken when the film is folded. In addition, the film primary battery according to the present invention can be easily applied to a wearable PC or the like since it is possible to implement a battery that can be rolled or bent like a roll. In addition, according to the manufacturing method of the film primary battery according to the present invention, the process conditions such as tension during continuous production is also significantly reduced compared to when using a conventional metal current collector, it is easy to mass the cells.

Next, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a view schematically showing the structure of a film primary battery 100 according to a preferred embodiment of the present invention.

Referring to FIG. 1, the all-solid film primary battery 100 according to the present invention includes a first polymer current collector film 10 and a second polymer current collector film 20.

The first polymer current collector film 10 is composed of a first polymer film 12 and a first conductive layer 14. In addition, the second polymer current collector film 20 includes a second polymer film 22 and a second conductive layer 24.

The first polymer film 12 and the second polymer film 22 serve to prevent moisture and oxygen permeation into the battery, respectively. The first polymer film 12 and the second polymer film 22 may be composed of a single layer film or a multilayer film made of a specific polymer material, which may be selected according to characteristics such as mechanical strength, moisture, and oxygen permeability, respectively. For example, the first polymer film 12 and the second polymer film 22 may each be a polyester-based polymer such as polyethylene terephthalate, polybutylene terephthalate, or the like; Polyolefin-based polymers such as polyethylene and polypropylene; Or it may be formed by laminating a polymer film made of a combination of these in a single layer or multiple layers. Alternatively, the first polymer film 12 and the second polymer film 22 may be formed by laminating a multilayer film by combining a polyester polymer film and a polyolefin polymer film, respectively. The first polymer film 12 and the second polymer film 22 may each have a thickness of about 5 to 100 μm.

The first conductive layer 14 and the second conductive layer 24 are thin films formed by coating a conductive material on one side of the first polymer film 12 and the second polymer film 22, respectively. The first conductive layer 14 and the second conductive layer 24 are conductive carbon paste, nano metal particles (metal particles having a particle size of several tens to tens of nanometers) paste, conductive polymer, or ITO (indium tin oxide) can be obtained by coating a paste or by attaching a conductive carbon tape. The first conductive layer 14 and the second conductive layer 24 may each have a thickness of about 10 μm to 50 μm, preferably about 5 to 150 μm.

In the first polymer current collector film 10 and the second polymer current collector film 20, the first conductive layer 14 and the second conductive layer 24 serve as current collectors, respectively. The polymer film 12 and the second polymer film 22 perform a packaging material function. The first polymer current collector film 10 and the second polymer current collector film 20 are configured by not using any metal or minimizing the use of metal, and compared with the case of the metal current collector according to the prior art. In the manufacturing process, the thickness can be made thinner and the weight can be greatly reduced with little difference from the existing process. In addition, by using the first polymer film 12 and the second polymer film 22, the bending property is very excellent, there is no folding phenomenon, and also serves as a packaging material that can protect the battery from moisture or oxygen transmission from the outside. It is also possible to manufacture a sealed battery.

The positive electrode layer 16 is coated on the first polymer current collector film 10, and the negative electrode layer 26 is coated on the second polymer current collector film 20.

The positive electrode layer 16 may be formed by coating a slurry including a mixture of a conductive agent, a polymer binder, and a positive electrode active material on the first conductive layer 14 of the first polymer current collector film 10.

The anode layer 16 may be formed to a thickness of about 5 ~ 200 ㎛. The total thickness of the first polymer current collector film 10 and the positive electrode layer 16 may be formed to a thickness of about 10 to 350 μm.

Conductive carbon such as graphite, carbon black, denka black, Lonza carbon, Super-P, MSC30, etc. may be used as a conductive agent suitable for forming the anode layer 16.

In addition, polymer binders suitable for forming the anode layer 16 include polytetrafluoroethylene, polyvinylidene fluoride, copolymers of vinylidene fluoride and hexafluoropropylene, vinylidene fluoride and trifluoro. Copolymer of ethylene, copolymer of vinylidene fluoride and tetrafluoroethylene, polyethylene oxide, polypropylene oxide, polyvinyl chloride, polybutadiene, polystyrene, polyethylene, polypropylene, polymethyl acrylate, polyethyl acrylate, poly Methyl methacrylate, polyethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polyacrylonitrile, cellulose, carboxymethyl cellulose, starch, polyacrylic acid, polyvinyl alcohol, polyvinylacetate, nylon, b Polymers such as pion or copolymers thereof, or Blends of these may be used.

In addition, suitable cathode active materials for constituting the anode layer 16 may include manganese oxide, electrolytic manganese dioxide (EMD), nickel oxide, lead oxide, lead dioxide, silver oxide, iron sulfide, conductive polymer particles, and the like. The preferred particle size of the positive electrode active material is about 10 nm to 50 μm.

The negative electrode layer 26 may be formed by coating a slurry including a mixture of a conductive agent, a polymer binder, and a negative electrode active material on the second conductive layer 24 of the second polymer current collector film 20.

The cathode layer 26 may be formed to a thickness of about 5 ~ 200 ㎛. The total thickness of the second polymer current collector film 20 and the negative electrode layer 26 may be formed to a thickness of about 10 to 350 μm.

Conductive carbon such as graphite, carbon black, denka black, lonza carbon, super-P, activated carbon MSC30, etc. may be used as a conductive agent suitable for forming the negative electrode layer 26.

In addition, polymer binders suitable for forming the negative electrode layer 26 include polytetrafluoroethylene, polyvinylidene fluoride, copolymers of vinylidene fluoride and hexafluoropropylene, vinylidene fluoride and trifluoro. Copolymer of ethylene, copolymer of vinylidene fluoride and tetrafluoroethylene, polyethylene oxide, polypropylene oxide, polyvinyl chloride, polybutadiene, polystyrene, polyethylene, polypropylene, polymethyl acrylate, polyethyl acrylate, poly Methyl methacrylate, polyethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polyacrylonitrile, cellulose, carboxymethyl cellulose, starch, polyacrylic acid, polyvinyl alcohol, polyvinylacetate, nylon, b Polymers such as pion or copolymers thereof, or Blends of these may be used.

In addition, zinc, aluminum, iron, lead, magnesium particles and the like may be used as the negative electrode active material suitable for forming the negative electrode layer 26. The preferred particle size of the negative electrode active material is about 10 nm to 50 μm.

A polymer electrolyte layer 30 is formed between the anode layer 16 and the cathode layer 26 to bond them together and provide a path of movement of ions therebetween.

The polymer electrolyte layer 30 is made of a polymer film containing an aqueous electrolyte solution. The polymer electrolyte layer 30 is positioned between the positive electrode layer 16 and the negative electrode layer 26 to enhance the adhesion between the two electrodes, thereby integrating the film battery. In addition, the thickness of the battery may be significantly reduced by using the polymer electrolyte layer 30 of the thin film to serve as an electrolyte and a separator. In addition, it is free to bend, can reduce the process conditions during the lamination and winding of the battery, can not only improve the price competitiveness, but also improve the energy density per weight.

The polymer electrolyte layer 30 may be formed to a thickness of about 5 ~ 200 ㎛.

The polymer electrolyte layer 30 includes a polymer matrix, an inorganic additive, and an aqueous electrolyte solution.

Polymer matrix suitable for constituting the polymer electrolyte layer 30 is polyethylene, polypropylene, polyimide, polysulfone, polyurethane, polyvinyl chloride, polystyrene, polyethylene oxide, polypropylene oxide, polybutadiene, cellulose, carboxymethyl cellulose , Nylon, polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene, copolymer of vinylidene fluoride and hexafluoropropylene, copolymer of vinylidene fluoride and trifluoroethylene, vinylidene fluoride Copolymers of tetrafluoroethylene with polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polyvinyl acetate, polyvinyl alcohol , Starch, agar, nafion or their It may be made of a polymer, or a blend.

The inorganic additive suitable for constituting the polymer electrolyte layer 30 may be selected from silica, talc, alumina (Al ₂ O ₃ ), TiO ₂ , clay, zeolite, or a blend thereof. The inorganic additive in the polymer electrolyte layer 30 may be included in an amount of about 1 to 100% by weight based on the total weight of the polymer constituting the polymer matrix.

Aqueous electrolyte suitable for constituting the polymer electrolyte layer 30 may be made of distilled water. The aqueous electrolyte in the polymer electrolyte layer 30 may be included in an amount of about 1 to 500% by weight based on the total weight of the polymer constituting the polymer matrix.

The salt in the aqueous electrolyte solution consists of potassium hydroxide (KOH), potassium bromide (KBr), potassium chloride (KCl), zinc chloride (ZnCl ₂ ), ammonium chloride (NH ₄ Cl), and sulfuric acid (H ₂ SO ₄ ). It may be composed of at least one selected from the group. As the aqueous electrolyte solution constituting the polymer electrolyte layer 30, an aqueous solution in which the salt is dissolved at a concentration of about 0.1 to 10 M can be used.

2 is a flowchart illustrating a method of manufacturing the film primary battery 100 according to the preferred embodiment of the present invention. 1 and 2, a method of manufacturing an exemplary film primary cell 100 of the present invention will be described.

First, in step 210, the first polymer film 12 and the second polymer film 22 are prepared, respectively.

In operation 220, a first conductive layer 14 is formed on the first polymer film 12, and a second conductive layer 24 is formed on the second polymer film 22 to form a first polymer current collector film ( 10) and the second polymer current collector film 20 are formed, respectively.

In operation 230, a cathode active material slurry is coated on the first conductive layer 14 of the first polymer current collector film 10 to form a cathode layer 16. The negative electrode active material slurry is coated on the second conductive layer 24 of the second polymer current collector film 20 to form the negative electrode layer 26.

The cathode active material slurry for forming the cathode layer 16 may be formed of a mixture of a conductive agent, a polymer binder, and a cathode active material. In addition, the negative electrode active material slurry for forming the negative electrode layer 26 may be formed of a mixture of a conductive agent, a polymer binder, and a negative electrode active material. Details of exemplary materials that may be used to construct the positive electrode active material slurry and the negative electrode active material slurry are as described with reference to FIG. 1.

In step 240, the polymer electrolyte layer 30 including the aqueous electrolyte is formed between the anode layer 16 and the cathode layer 26 to complete the structure as illustrated in FIG. 1. To this end, a method of coating or laminating a polymer film containing an organic electrolyte on the upper surface of each of the anode layer 16 and the cathode layer 26 may be used.

In step 250, the edge portion of the structure as shown in FIG. 1 obtained through steps 210 to 240 is sealed with heat fusion or adhesive to complete the film primary battery according to the present invention.

In the film primary battery 100 according to an exemplary embodiment of the present invention as described with reference to FIGS. 1 and 2, the interface adhesion between the electrode and the electrolyte may be improved, and long life and durability may be improved. In addition, the film primary battery 100 according to the present invention can implement an ultra-thin and hermetic single cell, can simplify the manufacturing process during winding and lamination and its manufacturing process is easy.

Hereinafter, the manufacturing method of the film primary battery according to the present invention will be described in more detail with reference to specific manufacturing examples. However, the following preparation examples are illustrated to aid the understanding of the present invention, and the scope of the present invention should not be construed as being limited thereto, and various modifications and changes may be made from the following preparation examples without departing from the spirit of the present invention. It is possible.

Production Example  One

A 15 μm thick transparent polyethylene terephthalate film was laminated with a 35 μm thick opaque polyethylene terephthalate film to form a polyester film of a two-layer film. At this time, each of the two films used a surface treatment of both surfaces by the corona discharge method before the lamination. A polymer collector film for a positive electrode was prepared by coating a conductive carbon paste having a thickness of 10 μm on one side of the bilayer film prepared as described above.

Production Example  2

A polymer current collector film for a positive electrode was prepared in the same manner as in Preparation Example 1, except that a transparent polyethylene terephthalate film having a thickness of 5 μm and an opaque polyethylene terephthalate film having a thickness of 10 μm were used.

Production Example  3

A 15 μm thick transparent polyethylene terephthalate film was laminated with a 35 μm thick opaque polyethylene terephthalate film to form a polyester film of a two-layer film. At this time, the two films were surface-treated on both sides by corona discharge before each lamination. One side of the bilayer film prepared as described above was coated with a conductive carbon paste having a thickness of 10 μm to finally prepare a polymer current collector film for the negative electrode.

Production Example  4

A polymer current collector film for negative electrode was prepared in the same manner as in Preparation Example 4, except that a transparent polyethylene terephthalate film having a thickness of 5 μm and an opaque polyethylene terephthalate film having a thickness of 10 μm were used.

Production Example  5

A slurry of an EMD positive electrode active material having an average particle diameter of about 2 μm was coated to a thickness of 60 μm on the surface of the conductive layer of the 60 μm thick polymer film for positive electrode manufactured in Preparation Example 1, and Preparation Example 4 Electrode films were prepared by coating a slurry of a zinc negative electrode active material having an average particle diameter of about 300 nm on the surface of the conductive layer of the polymer collector film for a negative electrode polymer collector film having a thickness of 60 μm. At this time, 80% by weight of the EMD oxide mixture powder (90% by weight EMD oxide + 5% by weight 6M calcium hydroxide electrolyte + 5% by weight carboxymethylcellulose), 12% by weight graphite, and 8% by weight polyvinyl chloride as a positive electrode active material slurry Was prepared by mixing. In addition, 80% by weight of zinc mixture powder (90% by weight zinc + 5% by weight 6M calcium hydroxide electrolyte + 5% by weight carboxymethylcellulose), 12% by weight graphite, and 8% by weight polyvinyl chloride were mixed as the negative electrode active material slurry. Was prepared. A 25 μm thick film based on a blend of 60 wt% copolymer of vinylidene fluoride and hexafluoropropylene and 40 wt% polyethylene oxide polymer was inserted between the prepared two electrode films, and then laminated with 6M hydroxide. The potassium solution was impregnated to prepare a 1.5 V class primary cell having a electrode area of 2 cm × 2 cm.

Production Example  6

A film primary battery unit cell was manufactured in the same manner as in Preparation Example 5, except that a slurry of the EMD positive electrode active material having an average particle diameter of about 0.5 μm and a slurry of the zinc negative electrode active material having an average particle diameter of about 60 nm were used.

Comparative example

Two 15 µm thick SUS current collectors were prepared for comparing the characteristics with the film primary batteries obtained in Production Examples 5 and 6, respectively, and the average particle diameter of the EMD positive electrode active material A slurry and a slurry of zinc anode active material having an average particle diameter of about 75 μm were coated to a thickness of 60 μm, respectively, to prepare a cathode and an anode film.

At this time, a positive electrode active material slurry and a negative electrode active material slurry having the same composition as in Production Example 5 and Production Example 6 were used. An alkaline battery separator was inserted between the prepared electrode films to adjust the lamination to the same thickness as that of the polymer electrolyte layer in Preparation Example 5, followed by injecting the same electrolyte solution as in Preparation Example 5 to prepare a primary battery unit cell.

Evaluation example

The film primary batteries prepared in Preparation Example 5 and Preparation Example 6 and the primary batteries prepared in Comparative Example were each discharged to 1.0 V at a current density of 1 mA.

3 is a graph showing the discharge characteristics of the film primary battery unit cell of Preparation Example 5 according to the present invention.

Figure 4 is a graph showing the discharge capacity of the film primary battery of Preparation Example 5 (□) and Preparation Example 6 (■) according to the present invention with a comparative example (●). In FIG. 4, it can be seen that in the case of the film primary batteries according to the present invention, the discharge capacity and the energy density are excellent due to the improvement in the interfacial adhesion between the electrode and the electrolyte and the thinning of the thin film.

FIG. 5 is a graph showing a change in OCV (open circuit voltage) value over time at room temperature of the film primary batteries obtained in Preparation Example 5 (□) and Preparation Example 6 (■) of the present invention with Comparative Example (●). to be.

In Figure 5, it can be seen that in the case of Preparation Example 5 and Preparation Example 6 which is the film primary battery according to the present invention, the voltage drop and the self-discharge are suppressed as compared with the case of the comparative example. In the case of the film primary battery according to the present invention, the introduction of the polymer electrolyte in the use of the aqueous electrolyte prevents the phenomenon of the direct contact between the aqueous electrolyte between the electrodes or between the electrodes / electrolytes, thereby suppressing corrosion of the negative electrode and consequent polarization. It is due to being.

6 is a graph showing a change in internal resistance over time at room temperature of the film primary battery obtained in Preparation Example 5 (□) and Preparation Example 6 (■) of the present invention with Comparative Example (●). .

In Figure 6, in the case of the manufacturing examples 5 and 6 which are the film primary batteries according to the present invention, the change in the internal resistance is smaller than in the case of the comparative example. From the results of FIG. 6, in the case of the film primary battery according to the present invention, the polymer electrolyte is introduced in the use of an aqueous electrolyte solution, and thus, the moisture is changed depending on the interaction between the polymer matrix and a few minutes and the interaction between the inorganic additive and the supported inorganic additive in the electrolyte. It can be seen that the evaporation and leakage of is suppressed for a long time. That is, even if the film primary battery according to the present invention is stored for a long time can be applied without deteriorating performance is excellent aging stability.

The film primary battery according to the present invention uses a polymer current collector prepared by coating a conductive carbon paste, a nanoparticle metal paste, a conductive polymer, or an ITO paste with a thin film on a thin polymer film or by attaching a conductive carbon adhesive tape. Therefore, the weight of the metal can be significantly reduced by minimizing the amount of metal used compared to the existing metal current collector. In addition, due to the characteristics of the polymer film, the bending characteristics are very excellent, and it is possible to eliminate the phenomenon that the electrode layer is peeled or broken when the film is folded. The film primary battery according to the present invention can be easily applied to a wearable PC or the like by enabling the implementation of a battery that can be rolled or bent like a roll. In addition, when the battery is implemented by lamination and winding, it shows excellent charge density characteristics, and the energy density per weight may be improved.

According to the manufacturing method of the film primary battery according to the present invention, the process conditions such as tension during continuous production is also significantly reduced compared to when using a conventional metal current collector, it is easy to mass the cells. In addition, since the current collector film may also serve as a packaging material, it is particularly useful for constructing a single cell or a small sealed film thin film primary battery, in particular, a battery for a radio frequency identification tag or a battery for cosmetic. In addition, by using a polymer electrolyte, there is no fear of leakage compared to a conventional liquid electrolyte / membrane system, which is very advantageous in terms of stability.

In the above, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications and changes by those skilled in the art within the spirit and scope of the present invention. This is possible.

Claims (19)

A first polymer current collector film composed of a first polymer film and a first conductive layer, A first electrode layer formed on the first conductive layer, A second polymer current collector film composed of a second polymer film and a second conductive layer, A second electrode layer formed on the second conductive layer, And a polymer electrolyte layer formed between the first electrode layer and the second electrode layer and containing an aqueous electrolyte solution. The method of claim 1, Each of the first polymer film and the second polymer film is made of a polyester polymer, a polyolefin polymer, a cellulose polymer, nylon, polyimide, or a combination film thereof. The method of claim 1, Each of the first polymer film and the second polymer film has a single layer or a multilayer structure made of a single kind of polymer material, or a film primary battery comprising a multilayer structure including at least two kinds of different polymer materials. The method of claim 1, Each of the first conductive layer and the second conductive layer is a film primary battery comprising a conductive carbon paste coating layer, a nano metal particle paste coating layer, a conductive polymer coating layer, an indium tin oxide (ITO) paste coating layer, or a conductive carbon tape. . The method of claim 1, The first electrode layer is made of a mixture of the first conductive agent, the first polymer binder and the positive electrode active material, The second electrode layer is a film primary battery, characterized in that made of a mixture of a second conductive agent, a second polymer binder and a negative electrode active material. The method of claim 5, Wherein the first conductive agent and the second conductive agent each comprise one conductive carbon selected from the group consisting of graphite, carbon black, denka black, lonza carbon, super-P, and activated carbon MSC30. The method of claim 5, The first polymer binder and the second polymer binder are polytetrafluoroethylene, polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, and air of vinylidene fluoride and trifluoroethylene, respectively. Copolymer, copolymer of vinylidene fluoride and tetrafluoroethylene, polyethylene oxide, polypropylene oxide, polyvinyl chloride, polybutadiene, polystyrene, polyethylene, polypropylene, polymethyl acrylate, polyethyl acrylate, polymethyl meth Acrylate, polyethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polyacrylonitrile, cellulose, carboxymethyl cellulose, starch, polyacrylic acid, polyvinyl alcohol, polyvinylacetate, nylon, and Nafion Any one selected from the group consisting of Here, a primary cell or a film which comprises a blend thereof. The method of claim 5, The cathode active material is a film primary battery comprising manganese oxide having a particle diameter of 10 nm to 50 μm, electrolytic manganese dioxide (EMD), nickel oxide, lead oxide, lead dioxide, silver oxide, iron sulfide, or conductive polymer particles. . The method of claim 5, The anode active material is a film primary battery, characterized in that consisting of particles of zinc, aluminum, iron, lead, or magnesium having a particle diameter of 10 nm to 50 μm. The method of claim 1, The polymer electrolyte layer is a film primary battery comprising an aqueous electrolyte containing a polymer matrix, an inorganic additive, and a salt. The method of claim 10, The polymer matrix is polyethylene, polypropylene, polyimide, polysulfone, polyurethane, polyvinyl chloride, polystyrene, polyethylene oxide, polypropylene oxide, polybutadiene, cellulose, carboxymethylcellulose, nylon, polyacrylonitrile, polyvinylidene Fluoride, polytetrafluoroethylene, copolymer of vinylidene fluoride and hexafluoropropylene, copolymer of vinylidene fluoride and trifluoroethylene, copolymer of vinylidene fluoride and tetrafluoroethylene, polymethyl In the group consisting of acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polyvinylacetate, polyvinyl alcohol, starch, agar, and nafion Any one selected, or these The film primary battery which consists of a copolymer of these, or these blends. The method of claim 10, The inorganic additive is a film primary battery, characterized in that made of at least one material selected from the group consisting of silica, talc, alumina (Al ₂ O ₃ ), TiO ₂ , clay (Clay), and zeolite. The method of claim 10, The aqueous electrolyte solution film primary battery, characterized in that it comprises distilled water. The method of claim 10, The salt in the aqueous electrolyte solution is selected from the group consisting of potassium hydroxide (KOH), potassium bromide (KBr), potassium chloride (KCl), zinc chloride (ZnCl ₂ ), ammonium chloride (NH ₄ Cl), and sulfuric acid (H ₂ SO ₄ ). The film primary battery, characterized in that at least one selected. Preparing a first polymer film and a second polymer film; Forming a first polymer current collector film by forming a first conductive layer on the first polymer film; Forming a second polymer current collector film by forming a second conductive layer on the second polymer film; Forming a first electrode layer on the first polymer current collector film; Forming a second electrode layer on the second polymer current collector film; And forming a polymer electrolyte layer including an aqueous electrolyte between the first electrode layer and the second electrode layer. The method of claim 15, The forming of the first conductive layer may include coating a conductive carbon paste, a nanometal particle paste, a conductive polymer, or an ITO paste on the first polymer film, or attaching a conductive carbon tape on the first polymer film. It is performed by the manufacturing method of the film primary battery. The method of claim 15, The forming of the second conductive layer may include coating a conductive carbon paste, a nanometal particle paste, a conductive polymer, or an ITO paste on the second polymer film, or attaching a conductive carbon tape on the first polymer film. It is performed by the manufacturing method of the film primary battery. The method of claim 15, The forming of the first electrode layer may include coating a cathode active material slurry on the first conductive layer of the first polymer current collector film. The method of claim 15, The second electrode layer is a method of manufacturing a film primary battery, characterized in that formed by a method of coating a negative electrode active material slurry on the second conductive layer of the second polymer current collector film.

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