KR102819270B1 - Method for manufacturing printed battery and printed battery manufactured therefrom - Google Patents

Abstract

A method for manufacturing a printed battery is provided. The printed battery according to the present invention is implemented by including (1) a step of printing a positive electrode layer on a portion of a first outer layer and a negative electrode layer on a portion of a second outer layer, (2) a step of forming a gel electrolyte layer by printing a gel electrolyte composition having acidity and including an electrolyte component, water, and a gel-forming component that is silicon dioxide (SiO2) on the positive electrode layer or the negative electrode layer, (3) a step of printing an adhesive layer on a border area of the first outer layer or the second outer layer corresponding to an outer side of the border of the printed gel electrolyte layer, and (4) a step of bonding the first outer layer and the second outer layer, each of which is printed, to seal the border portions of the first outer layer and the second outer layer through the adhesive layer. According to this, it is possible to mass-produce a printed battery, which is a primary cell, with excellent quality by using a gel electrolyte composition that has excellent thixotropic properties, excellent repetitive printing workability and mass productivity, does not change the quality of the separator even when printed on a paper-type separator, and does not generate bubbles after printing.

Description

Method for manufacturing printed battery and printed battery manufactured therefrom {Method for manufacturing printed battery and printed battery manufactured therefrom}

The present invention relates to a method for manufacturing a printed battery and a printed battery manufactured thereby.

Recently, the demand for thin batteries is increasing due to the vitality of various sensor tags, RFID tags, smart cards, and medical patch industries related to the Internet of Things.

In particular, the market for label-type sensors is expected to have great potential in the future, and a thin battery with a thickness of several hundred microns or less that is inexpensive is required as a power source to operate the sensor.

A thin battery is a general term for a thin battery in the shape of a film, which includes a positive electrode, a negative electrode, and an electrolyte, and the positive electrode, negative electrode, and electrolyte are sealed inside a thin film-shaped outer packaging material.

Generally, the electrolyte used in thin-cell batteries is a liquid-type electrolyte, which not only takes a long time for the injection process, but also has the disadvantage of rapid depletion in a dry environment when the thin-cell battery is open.

To compensate for such shortcomings, gel-type electrolytes have been developed, but existing gel-type electrolytes have poor surface quality and physical properties when implemented through a printing process, and repetitive printing processes are difficult, resulting in disadvantages in printing workability and mass productivity.

Korean Patent Publication No. 10-2006-0055158

The present invention has been made in consideration of the above points, and its purpose is to provide a method for manufacturing a printed battery, which is a primary battery that can be mass-produced by a printing method, using a gel electrolyte composition having excellent thixotropic properties and capable of printing quality and repeatable printing processes, and a printed battery manufactured thereby.

In addition, another purpose of the present invention is to provide a gel electrolyte composition for a printed battery, which has excellent thixotropic properties, excellent repetitive printing workability and mass productivity, does not change the quality of the separator even when printed on a paper-type separator, and does not generate bubbles or the like after printing, thereby preventing deterioration of printing quality and physical properties due to bubbles.

In order to solve the above-described problem, the present invention provides a method for manufacturing a printed battery, comprising the steps of: (1) printing a positive electrode layer on a portion of a first outer layer and printing a negative electrode layer on a portion of a second outer layer, (2) printing a gel electrolyte composition having acidity and including an electrolyte component, water, and a gel-forming component that is silicon dioxide (SiO ₂ ) on the positive electrode layer or the negative electrode layer to form a gel electrolyte layer, (3) printing an adhesive layer on a border area of the first outer layer or the second outer layer corresponding to an outer side of the border of the printed gel electrolyte layer, and (4) bonding the first outer layer and the second outer layer, each of which is printed, to seal the border portions of the first outer layer and the second outer layer through the adhesive layer.

According to one embodiment of the present invention, in step (3), a separator is disposed on the positive or negative electrode on which the gel electrolyte composition is printed, and the gel electrolyte composition can be printed on the separator.

Additionally, the electrolyte component may include 2 to 10 parts by weight of ammonium chloride (NH ₄ Cl) per 100 parts by weight of zinc chloride (ZnCl ₂ ).

Additionally, water may be included in an amount of 95 to 120 parts by weight per 100 parts by weight of the electrolyte component.

In addition, the gel-forming component may be included in an amount of 2 to 14 parts by weight per 100 parts by weight of the electrolyte component, and more preferably, the gel-forming component may be included in an amount of 6 to 10 parts by weight per 100 parts by weight of the electrolyte component.

In addition, the above silicon dioxide is amorphous fumed silica and may have a BET surface area of 170 to 230 m2/g.

Additionally, the silicon dioxide may have a pH of 3.7 to 4.5 when dispersed in water at 4 wt%.

Additionally, the separator may include kraft paper, and the printing may be screen printing.

In addition, the present invention provides a printed battery including a positive electrode layer, a negative electrode layer, a gel electrolyte layer interposed between the positive electrode layer and the negative electrode layer and including an electrolyte component and a gel-forming component, and an outer material encapsulating the positive electrode layer, the negative electrode layer, and the gel electrolyte layer.

According to one embodiment of the present invention, the anode layer may include manganese dioxide (MnO ₂ ), the cathode layer may include zinc (Zn), and the electrolyte component may include zinc chloride and ammonium chloride.

Additionally, the printed battery may have a thickness of 0.5 to 2.0 mm.

Additionally, the gel electrolyte layer may have a thickness of 0.04 to 0.4 mm.

In addition, the present invention provides a gel electrolyte composition for a printed battery, which is acidic and includes an electrolyte component, water, and a gel-forming component that is silicon dioxide.

According to the present invention, a gel electrolyte composition for a printed battery has excellent thixotropic properties, excellent repetitive printing workability and mass productivity, and even when printed on a paper-type separator, the quality of the separator does not change, and since bubbles and the like do not occur after printing, the printing quality and deterioration of physical properties due to bubbles can be prevented. Accordingly, mass production of a printed battery, which is a primary battery, with excellent quality is possible through the gel electrolyte composition for a printed battery.

Figure 1 is a schematic drawing of a printed battery according to one embodiment of the present invention.
Figure 2 is a cross-sectional view along the AA' boundary line of the printed battery of Figure 1, and
FIGS. 3 and 4 are cross-sectional views of a printed battery according to another embodiment of the present invention.

Hereinafter, with reference to the attached drawings, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. The present invention may be implemented in various different forms and is not limited to the embodiments described herein. In the drawings, parts that are not related to the description are omitted in order to clearly describe the present invention, and the same reference numerals are added to the same or similar components throughout the specification.

Referring to FIGS. 1 and 2, a printed battery (100) according to one embodiment of the present invention may be a primary battery and a plate-shaped battery having a predetermined area.

Specifically, the printed battery (100) includes an outer case (110), a positive electrode layer (120), a negative electrode layer (130), and a gel electrolyte layer (150). In addition, as illustrated in FIG. 3, a separator (140) may be further included between the positive electrode layer (120) and the negative electrode layer (130). In other words, the printed battery (100) according to one embodiment of the present invention may be a printed battery in which the positive electrode layer (120), the negative electrode layer (130), and the gel electrolyte layer (150), or the positive electrode layer (120), the negative electrode layer (130), the gel electrolyte layer (150), and the separator (140) are sealed inside the outer case (110).

The above outer material (110) may be a plate-shaped member having a certain area. The outer material (110) physically protects the positive electrode layer (120), the negative electrode layer (130), the gel electrolyte layer (150), and the separator (140) arranged inside from the external environment, and prevents moisture contained in the gel electrolyte layer (150) inside from evaporating and permeating to the outside.

To this end, the outer covering (110) may include a pair of first outer coverings (111) and second outer coverings (112), as shown in FIGS. 2 and 3, and the first outer coverings (111) and second outer coverings (112) may be mutually bonded through an adhesive layer (160) arranged along edges facing each other.

Alternatively, the first outer material (111) and the second outer material (112) may be formed as a single piece, folded in half along the width or length direction, and the remaining edge portions that are joined may be joined through the adhesive layer (160).

The above outer covering material (110) can be used without limitation as a known outer covering material used in a printed battery. For example, the first outer covering material (111) and the second outer covering material (112) can each be independently composed of a single layer including one type of film selected from the group consisting of a polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc., a polyolefin film such as polyethylene, polypropylene, etc., a polyamide film, a polyimide film, and a polyamide-imide film, or a composite layer including two or more types of films.

Meanwhile, according to one embodiment of the present invention, in the printed battery (100") illustrated in FIG. 4, a battery may use an outer material (111') having a metal layer (111b) provided inside a polymer film (111a, 111c) to prevent evaporated moisture of a gel electrolyte layer (150) from being released to the outside. The metal layer (111b) may be a metal sheet such as a foil, or may be a metal deposition film formed on one surface of the first resin layer (111b) or the second resin layer (112b) by a method such as sputtering or chemical vapor deposition. In addition, the metal layer (111b) may be formed of aluminum, copper, phosphorbronze (PB), aluminum bronze, cupronickel, beryllium-copper, chromium-copper, titanium-copper, iron-copper, It may include at least one selected from a Corson alloy and a chromium-zirconium copper alloy, more preferably may include aluminum, and the aluminum may be an aluminum deposition layer. In addition, the metal layer (111b) may have a thickness of 5 to 50 μm, more preferably 10 to 35 μm, and if the thickness of the metal layer (111b) is less than 5 μm, evaporated moisture derived from the gel electrolyte layer (150) inside the printed battery (100") may leak to the outside. In addition, if the thickness exceeds 50 μm, the hydrogen gas generated inside may not leak properly, which may cause excessive swelling of the printed battery and thus leakage of the gel electrolyte.

In addition, the polymer film (111a, 111c) surrounding the metal layer (111b) may be a film selected from the group consisting of a polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc., a polyolefin film such as polyethylene, polypropylene, etc., a polyamide film, a polyimide film, and a polyamideimide film, and preferably, may be polyethylene terephthalate.

Meanwhile, an outer material (111') having a metal layer (111b) inside a polymer film (111a, 111c) can be used as the outer material of a printed battery. However, in this case, since it is difficult for hydrogen gas generated inside to be released to the outside, excessive component phenomenon may occur during use of the printed battery. Accordingly, it may be preferable that an outer material having a metal layer (111b) inside a polymer film (111a, 111c) is provided only in one of the first outer material and the second outer material so that the discharge of hydrogen gas generated inside is smooth and moisture evaporation of the internal gel electrolyte layer is minimized.

Additionally, the first outer material (111, 111') and the second outer material (112) may each independently have a thickness of 10 to 100 ㎛.

Next, the anode layer (120) and cathode layer (130) will be described.

Each of the positive electrode layer (120) and the negative electrode layer (130) may be provided with a current collector layer (122, 132) and an active material layer (121, 131) formed on the current collector layer (122, 132). In addition, the active material layer (121, 131) may be provided corresponding to the entire area of the current collector layer (122, 132) or may be locally provided only on a portion of the area of the current collector layer (122, 132).

At this time, each of the positive electrode current collector layer (122) and the negative electrode current collector layer (132) can be formed through printing on the inner surface of the outer material (110), specifically, on the inner surface of the first outer material (111, 111') and the inner surface of the second outer material (112). In addition, each of the positive electrode active material layer (121) and the negative electrode active material layer (131) can be formed through printing on one surface of the positive electrode current collector layer (122) and the negative electrode current collector layer (132).

Here, one end of the positive electrode current collector layer (122) and the negative electrode current collector layer (132) can be extended to a predetermined width, and the extended portion can protrude outside the body of the printed battery (100, 100', 100") sealed with each outer material (110) to serve as a positive electrode terminal (123) and a negative electrode terminal (113) for electrical connection with an external device.

In addition, each of the positive electrode current collector layer (122) and the negative electrode current collector layer (132) can be implemented with a known conductive printable paste or ink, and for example, can be formed through printing using a paste or ink containing one or more of copper, aluminum, stainless steel, nickel, titanium, chromium, manganese, iron, cobalt, zinc, molybdenum, tungsten, silver, gold, and metals thereof, or conductive carbon, or conductive polymer.

Additionally, each of the positive electrode current collector layer (122) and the negative electrode current collector layer (132) can be formed to a thickness of 5 to 200 μm.

In addition, the positive electrode active material layer (121) and the negative electrode active material layer (131) may be formed by printing on the positive electrode current collector layer (122) and the negative electrode current collector layer (132), respectively, and a printable ink or paste may be used. The ink or paste may contain a conductive agent, a binder resin, and an active material, and the conductive agent may contain graphite, carbon black, Denka black, or the like. In addition, the binder resin may be a polymer compound such as polytetrafluoroethylene, polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, a copolymer of vinylidene fluoride and trifluoroethylene, a copolymer of vinylidene fluoride and tetrafluoroethylene, polyethylene oxide, polypropylene oxide, polyvinyl chloride, polybutadiene, polystyrene, polyethylene, polypropylene, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polybutylacrylate, polybutyl methacrylate, polyacrylonitrile, cellulose, carboxymethyl cellulose, starch, polyacrylic acid, polyvinyl alcohol, polyvinylacetate, nylon, Nafion, or a copolymer thereof, or a mixture thereof.

In addition, the active material can be used without limitation in the case of positive electrode active material and negative electrode active material materials typically used in primary batteries, and as an example, the positive electrode active material can include one or more of manganese dioxide (MnO ₂ ), nickel oxide, lead oxide, lead dioxide, silver oxide, iron sulfide particles, etc., and the negative electrode active material can include one or more of zinc (Zn), aluminum, iron, lead, magnesium particles, etc. In addition, the average particle diameter of the active material particles used in the positive electrode active material and the negative electrode active material can be about 10 nm to 50 μm.

Meanwhile, the positive electrode active material and the negative electrode active material can be appropriately selected depending on the type of electrolyte component of the gel electrolyte layer (150) described later, and when the electrolyte component includes zinc chloride and ammonium chloride, the positive electrode active material can be manganese dioxide and the negative electrode active material can be zinc.

Additionally, the positive electrode active material layer (121) and the negative electrode active material layer (131) can each be formed to have a thickness of 10 to 200 μm.

Next, the gel electrolyte layer (150) positioned between the positive electrode layer (120) and the negative electrode layer (130) will be described.

The above gel electrolyte layer (150) can be formed by printing a gel electrolyte composition including an electrolyte component, water, and a gel-forming component, and by including silicon dioxide as a gel-forming component, the gel electrolyte composition can have excellent repeatability and excellent thixotropic properties.

The electrolyte component may use a known electrolyte component used in a primary battery, and a component that is acidic in an aqueous solution is preferable, and may preferably include zinc chloride and ammonium chloride. At this time, the electrolyte component includes 2 to 10 parts by weight of ammonium chloride (NH ₄ Cl) per 100 parts by weight of zinc chloride (ZnCl ₂ ), and this may be advantageous in achieving the purpose of the present invention.

In addition, the gel electrolyte composition may contain 95 to 120 parts by weight of water per 100 parts by weight of the electrolyte component, which may be advantageous in achieving the purpose of the present invention, as it may help to exhibit excellent performance as a primary battery and at the same time, help the gel-forming component have excellent thixotropic properties.

In addition, silicon dioxide is contained as the gel-forming component. In addition to the electrolyte components described above, conventionally used electrolyte layers for printed batteries include polymers capable of forming a porous structure, such as polyethylene oxide, polyvinyl alcohol, and polyvinyl pyrrolidone. However, these components have low gel-forming properties, and when a gel electrolyte composition containing these components is directly printed on a separator such as paper, for example, kraft paper or starch-coated kraft paper, there is a concern that the separator may be damaged. Accordingly, the present invention uses silicon dioxide so that the printing method is easy to apply due to excellent thixotropic properties, and the screen mesh or nozzle of the printing device is not blocked or unprinted residues are not left on the printing roller, so that the printing repeatability is excellent, and the flowability after printing is drastically reduced due to the excellent thixotropic properties, so that the printability is excellent in the intended shape in the intended area, and the printing quality is improved because no air bubbles are formed on the surface and inside of the printed gel electrolyte layer. Meanwhile, other types of inorganic materials, such as titanium dioxide and alumina, can form gels, but may be insufficient to express the desired properties when compared to silicon dioxide when considering thixotropic characteristics, repeatability, and print quality.

Preferably, the silicon dioxide may be amorphous. In addition, the silicon dioxide may be fumed silica, and compared to the case where one or more of other types, for example, precitated silica, silica gel, and silica aerogel, is used, it is advantageous in achieving excellent repeatability, printing quality of the surface of the printed gel electrolyte layer, and minimizing membrane damage. In addition, the silicon dioxide may be hydrophilic fumed silica in which silanol groups are not capped, and when hydrophobic fumed silica in which silanol groups are capped with hydrocarbon groups is used, it may be difficult to exhibit the desired effect.

The silicon dioxide may preferably have a BET surface area of 170 to 230 m2/g, and may have a pH of 3.7 to 4.5 when dispersed in water at 4 wt%. By satisfying such property values, it may be advantageous to express the desired effect through silicon dioxide. If the BET surface area and/or the pH value when dispersed in water are out of the above-mentioned range, one or more of the characteristics of print repeatability, post-printing surface quality, post-printing shape implementability, and membrane invasiveness may not be expressed at the desired level.

The gel-forming component, which is the silicon dioxide, may be contained in the gel electrolyte composition in an amount of 2 to 14 parts by weight, more preferably 6 to 10 parts by weight, based on 100 parts by weight of the electrolyte component. If the gel-forming component is contained in an amount of less than 2 parts by weight, the flowability during printing may be strong, printing may occur beyond a specified area, surface quality after printing may be poor, shape realization after printing may be poor, and membrane damage may increase. In addition, if the gel-forming component exceeds 14 parts by weight, it may be difficult to implement a gel electrolyte layer through printing or printing repeatability may be reduced. In addition, there may be unprinted blank areas or recessed areas due to improper printing within the printed gel electrolyte layer area, which may reduce the print quality.

In addition, the gel electrolyte layer (150) may be formed with a thickness of 0.04 to 0.4 mm. If the thickness is less than 0.04 mm, it may be difficult to achieve sufficient battery performance, and if the thickness exceeds 0.4 mm, there is a risk that the gel electrolyte may leak during the battery assembly and sealing process.

*Meanwhile, the gel electrolyte layer (150) implemented with the gel electrolyte composition according to the present invention has excellent thixotropic properties, so it has excellent shape retention after printing, and thus exhibits a separation effect between the positive electrode layer (120) and the negative electrode layer (130), so there is an advantage in that a separate separator can be omitted, and compared to the solid electrolyte layer, it has excellent flexibility and does not generate cracks, so there is an advantage in that it can minimize changes in battery properties due to bending.

In addition, the printed battery (100') of the present invention may further include a separator (140) disposed between the positive electrode layer (120) and the negative electrode layer (130) to prevent short circuiting of the positive electrode layer (120) and the negative electrode layer (130). At this time, a gel electrolyte layer (150) may be disposed between the positive electrode layer (120) and the separator (140) or between the negative electrode layer (130) and the separator (140).

The above separator (140) can be formed as a plate-shaped member having a predetermined area and can be placed between the positive electrode active material layer (121) and the negative electrode active material layer (131).

In addition, the separator (140) can be used without limitation in the case of a known porous layer used in a printed battery, and may be manufactured from a cellulose component that can be generally referred to as paper, or may be manufactured from a synthetic polymer. Preferably, considering lightness, flexibility, etc., the separator may use kraft paper, an example of paper, or kraft paper coated with starch, etc.

In addition, the adhesive layer (160) can be arranged along the edges of the first outer material (111) and the second outer material (112) facing each other, and can mutually bond the edges of the first outer material (111) and the second outer material (112).

Here, the adhesive layer (160) may be a liquid or gel-type adhesive of an inorganic material type, or may be a double-sided tape with adhesive applied to both sides of the substrate.

In addition, the printed battery (100, 100', 100') according to the present invention may have a thickness of 0.5 to 2.0 mm, but is not limited thereto and may be appropriately changed according to the purpose.

In addition, the printed battery (100, 100', 100') according to the present invention described above can be manufactured by the manufacturing method described below, but is not limited thereto.

According to one embodiment of the present invention, a printed battery can be manufactured by including the steps of (1) printing a positive electrode layer on a portion of a first outer casing and printing a negative electrode layer on a portion of a second outer casing, (2) printing a gel electrolyte composition that is acidic and includes an electrolyte component, water, and a gel-forming component that is silicon dioxide (SiO2) on the positive electrode layer or the negative electrode layer to form a gel electrolyte layer, (3) printing an adhesive layer on a border area of the first outer casing or the second outer casing corresponding to an outer side of the border of the printed gel electrolyte layer, and (4) bonding the first outer casing and the second outer casing, each of which is printed, together to seal border portions of the first outer casing and the second outer casing with the adhesive layer.

First, as step (1) of the present invention, a step of printing a positive electrode layer on a portion of a first outer covering material and a negative electrode layer on a portion of a second outer covering material is performed. The printing can be performed through a conventional printing method, for example, screen printing, stencil printing, offset printing, and/or jet printing, and preferably, considering the characteristics of the gel electrolyte composition according to the present invention, can be performed through screen printing. Since specific printing conditions can be performed by appropriately utilizing known conditions and devices for each printing method, a detailed description thereof is omitted in the present invention.

Specifically, in step (1), in order to form a positive electrode layer (120), a positive electrode collector composition is printed on one surface of a first outer material (111), dried to form a positive electrode collector layer (122), and then a positive electrode active material composition is printed on the positive electrode collector layer (122), dried to form a positive electrode active material layer (121), thereby implementing the positive electrode layer (120). In addition, a negative electrode layer (130) can also be implemented by printing a negative electrode collector composition on one surface of a second outer material (112) in the same way, dried to form a negative electrode collector layer (132), and then again printing a negative electrode active material composition on the negative electrode collector layer (132), dried to form a negative electrode active material layer (131). At this time, the drying can be a conventional drying method, for example, natural drying at room temperature.

Next, in step (2) according to the present invention, a step of forming a gel electrolyte layer (150) is performed by printing a gel electrolyte composition that is acidic and includes an electrolyte component, water, and a gel-forming component that is silicon dioxide (SiO ₂ ) on the positive electrode layer (120) or the negative electrode layer (130). Here, the printing can also be performed using the known printing method described above, and preferably, it can be performed through screen printing.

In addition, when the printed battery includes a separator (140), in step (2), the separator is first placed on the positive electrode layer (120) or negative electrode layer (130) on which the gel electrolyte composition is printed, and the gel electrolyte composition can be printed on the separator (140).

Next, as step (3) according to the present invention, a step of printing an adhesive layer (160) on the edge area of the first outer material (111) or the second outer material (112) corresponding to the outer edge of the printed gel electrolyte layer (150) is performed.

The above adhesive layer (160) can be formed using a known adhesive composition designed to be printable, and can be an inorganic adhesive layer made of the adhesive composition or an adhesive layer in which the adhesive composition is placed on both sides of a substrate.

After the adhesive composition is printed, it may undergo a predetermined drying process, and the drying may be performed naturally or by applying heat.

Next, as a step (4) according to the present invention, a step of bonding the first outer material (111) and the second outer material (112) on which each layer is printed and sealing the edge portions of the first outer material (111) and the second outer material (112) through an adhesive layer (160) is performed.

The above sealing can be performed by applying pressure and additionally temperature depending on the type of adhesive composition. At this time, the conditions of pressure and temperature applied can be appropriately changed in consideration of the type and thickness of the adhesive layer (160), and the present invention is not particularly limited thereto.

The present invention will be described more specifically through the following examples, but the following examples do not limit the scope of the present invention, and should be interpreted as helping to understand the present invention.

<Manufacturing Example>

A second outer covering material made of a polyimide film with a thickness of 50 ㎛ as an outer covering material and a first outer covering material with a total thickness of 54 ㎛ in which PET is laminated on and underneath a 20 ㎛ thick aluminum deposition film were respectively prepared. After drying carbon ink (Nippon Graphite, EVERYOHM T-30PLB-U) on each polyimide film, screen printing was performed to a thickness of 150 ㎛, and drying at 150°C was performed to manufacture a positive electrode collector layer and a negative electrode collector layer, respectively. Thereafter, a positive electrode active material ink containing a positive electrode active material, which is manganese dioxide, and a negative electrode active material ink containing a negative electrode active material, which is zinc, were applied onto each positive electrode collector layer and negative electrode collector layer again, dried by applying heat, and screen printing and drying to a thickness of 80 ㎛ was performed to manufacture a positive electrode active material layer and a negative electrode active material layer, respectively. Thereafter, a kraft paper separator coated with starch having a thickness of 150 μm was placed on the cathode active material layer, and a gel electrolyte composition was screen-printed to a thickness of 200 μm to manufacture a gel electrolyte layer. Thereafter, an acrylic adhesive composition was placed on the edge of the first outer material so as to surround each layer formed on the first outer material, and the inner side of the second outer material and the inner side of the first outer material, on which each layer was printed, were laminated so as to face each other, and then pressure was applied to the edge to seal, and a printed battery as shown in Fig. 1 below was manufactured.

At this time, the gel electrolyte composition used was a mixture of 100 parts by weight of an electrolyte component containing 4 parts by weight of ammonium chloride per 100 parts by weight of zinc chloride, 100 parts by weight of water, and 9.5 parts by weight of silicon dioxide A (amorphous hydrophilic fumed silica, BET surface area according to ISO 9277 of 175 to 225 m2/g, dispersed in water at 4 wt%, pH of 3.7 to 4.5, tap density of approximately 50 g/l, average primary particle size of 14 nm, and secondary particle size of 117 to 198 nm).

<Example 1>

A gel electrolyte composition was prepared by mixing 100 parts by weight of an electrolyte component containing 4 parts by weight of ammonium chloride per 100 parts by weight of zinc chloride, 100 parts by weight of water, and 9.5 parts by weight of silicon dioxide A (amorphous hydrophilic fumed silica, BET surface area of 175 to 225 m2/g according to ISO 9277, pH of 3.7 to 4.5 after dispersion in water at 4 wt%, tap density of approximately 50 g/l, average primary particle size of 14 nm, and secondary particle size of 117 to 198 nm).

<Comparative examples 1 ~ 2>

A gel electrolyte composition was manufactured in the same manner as in Example 1, except that silicon dioxide in the gel electrolyte was replaced with polyethylene oxide or polyvinyl alcohol.

<Experimental Example 1>

The following physical properties were evaluated for the gel electrolytes of Example 1 and Comparative Examples 1 to 2, and are shown in Table 1.

1. Print repeatability

The gel electrolyte layer was repeatedly printed 10 times on starch-coated kraft paper (manufacturer, product name) using a screen printer to evaluate whether there were any problems during printing.

2. Print quality

We evaluated whether air bubbles were generated on the surface of the gel electrolyte layer after printing, and if air bubbles were generated, we evaluated them as ○, and if not, we evaluated them as ×.

3. Whether the membrane has been breached

In the case of starch-coated kraft paper, the occurrence of membrane damage was visually observed, and if starch was dissolved or the kraft paper was damaged, it was evaluated as ○, and if not, it was evaluated as ×.

Example 1 Comparative Example 1 Comparative Example 2 Gel-forming ingredient Silicon dioxide A PEO PVA Print repeatability No problem After 4 printings, the screen mesh was blocked and stopped. No problem Whether bubbles occur after printing × ○ ○ Whether the membrane is breached × × ○

As can be seen in Table 1,

In the case of Comparative Examples 1 and 2, which used polymer compounds as gel-forming components, the repeatability of printing was poor, excessive bubbles were generated after printing, which resulted in poor print quality, and it was expected that battery properties would deteriorate as resistance increased due to the bubbles. In addition, in the case of Comparative Example 2, it was confirmed that damage to the separator occurred. However, in the case of Example 1, it was confirmed that there was no problem with the repeatability of printing, the print quality was excellent, and no damage to the separator occurred.

<Examples 2 to 4>

A process for manufacturing a gel electrolyte is the same as in Example 1, except that instead of the silicon dioxide used in the gel electrolyte, another type of silicon dioxide B (amorphous hydrophilic fumed silica, BET surface area of 130 to 170 m2/g according to ISO 9277, pH 3.7 to 4.7 after being dispersed in 4 wt% of water, tap density of approximately 50 g/l), silicon dioxide C (amorphous hydrophilic fumed silica, BET surface area of 270 to 330 m2/g according to ISO 9277, pH 3.7 to 4.7 after being dispersed in 4 wt% of water, tap density of approximately 50 g/l), or silicon dioxide D (amorphous precipitated silicon dioxide, pH 5.5 to 6.5 in a 4 wt% aqueous dispersion, BET surface area of 180 to A gel electrolyte composition was manufactured by changing the content of the electrolyte to 230㎡/g (Kangshin Industrial Co., Ltd., Nipsil AQ).

<Experimental Example 2>

The following physical properties were evaluated for Examples 1 to 4 and are shown in Table 2 below.

1. Shape retention after printing

After printing with the same thickness and area for each example on starch-coated kraft paper, the area of the gel electrolyte layer was calculated after 5 minutes, and after 10 minutes, the area of the gel electrolyte layer was calculated and the area change ratio was calculated using the following formula. Ten specimens were manufactured for each example, and the area change ratio was calculated for each, and then the average value was calculated. Then, the average value of Example 4 was set as 100, and the average area change ratio of the remaining examples was expressed as a relative percentage in the table. If the area change is large, it means that the change is large compared to the designed area and thickness at the time of printing, and the shape maintenance after printing is poor.

[ceremony]

Area change rate (%) = [(Area after 10 minutes (㎟) - Area after 5 minutes (㎟)) × 100] / Area after 5 minutes (㎟)

2. Print quality

To determine whether mass production was possible, the ease of printing was evaluated. Specifically, for each example, after printing 100 times in an area of 200 ㎛ in thickness, 15 mm in width, and 15 mm in length, the surface of the printed gel electrolyte layer was observed under a microscope to check whether there were any unprinted blank or sunken areas in the printed area. If there was one or more blank areas and/or two or more printed but sunken areas, these were counted as defective, and the number of good products out of 100 was expressed as a percentage.

Example 1 Example 2 Example 3 Example 4 Gel-forming ingredient division Silicon dioxide A Silicon dioxide B Silicon dioxide C Silicon dioxide D type Fumed silica Fumed silica Fumed silica precipitated silica BET specific surface area (㎡/g) 175 ~ 225 130 ~ 170 270 ~ 330 180 ~ 230 pH 3.7 ~ 4.5 3.7 ~ 4.7 3.7 ~ 4.7 5.5 ~ 6.5 Content (weight parts) 9.5 9.5 9.5 9.5 Shape retention after printing
(Relative area change rate (%)) 2.4 7.5 2.1 100 Print Quality (%) 100 94 90 68

<Examples 5 to 10>

A gel electrolyte composition was manufactured in the same manner as in Example 1, but the content of silicon dioxide A was changed as shown in Table 3.

<Experimental Example 3>

The following physical properties were evaluated for Examples 1 and 5 to 10 and are shown in Table 3 below.

1. Print blur

After printing 100 times on starch-coated kraft paper with an area of 200 ㎛ in thickness, 15 mm in width, and 15 mm in length for each example, it was evaluated whether the gel electrolyte composition flowed beyond the printing area to form a gel electrolyte layer. Cases in which the gel electrolyte composition flowed beyond the printing area to form a gel electrolyte layer were counted as defects, and the number of defects out of 100 was expressed as a percentage.

2. Print quality

To determine whether mass production was possible, the ease of printing was evaluated. Specifically, for each example, after printing 100 times in an area of 200 ㎛ in thickness, 15 mm in width, and 15 mm in length, the surface of the printed gel electrolyte layer was observed under a microscope to check whether there were any unprinted blank or sunken areas in the printed area. If there was one or more blank areas, two or more printed but sunken areas, and/or if the surface had an uneven area of 10% or more of the total area (15 mm × 15 mm), these were counted as defective, and the number of good products out of 100 was expressed as a percentage.

Example 1 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Gel-forming ingredient division Silicon dioxide A Silicon dioxide A Silicon dioxide A Silicon dioxide A Silicon dioxide A Silicon dioxide A Silicon dioxide A Content
(weight) 9.5 1.5 2.2 5.5 6.2 12.5 16.0 Print smudging (%) 0 28 10 6 0 0 0 Print Quality (%) 100 78 85 92 100 90 73

As can be seen in Table 3,

It can be confirmed that Examples 1 and 6 to 9, which contain the content of silicon dioxide A within the range of a preferred embodiment of the present invention, are superior in printing blurring and printing quality compared to Examples 5 and 10.

Although one embodiment of the present invention has been described above, the spirit of the present invention is not limited to the embodiment presented in this specification, and those skilled in the art who understand the spirit of the present invention will be able to easily suggest other embodiments by adding, changing, deleting, or adding components within the scope of the same spirit, but this will also be considered to fall within the spirit of the present invention.

100,100',100" : Printed Battery 110 : Outer Material
111: First exterior material 112: Second exterior material
120: Cathode layer 121: Cathode active material layer
122: Positive collector layer 123: Positive terminal
130: Negative electrode layer 131: Negative electrode active material layer
132: Negative current collector layer 113: Negative terminal
140: Separator 150: Gel electrolyte layer
160 : Adhesive layer

Claims (14)

(1) A step of printing an anode layer on some areas of the first outer material and printing a cathode layer on some areas of the second outer material;
(2) a step of forming a gel electrolyte layer by printing a gel electrolyte composition comprising an acidic electrolyte component, water, and a gel-forming component that is an amorphous fumed silica (SiO2) having a BET surface area of 170 to 230 m2/g, on a cathode layer or anode layer, wherein the gel-forming component does not contain a polymer and is contained in an amount of 2 to 14 parts by weight per 100 parts by weight of the electrolyte component;
(3) a step of printing an adhesive layer on a border area of the first outer material or the second outer material corresponding to the outer side of the border of the printed gel electrolyte layer; and
(4) A method for manufacturing a printed battery, comprising the step of bonding the first outer material and the second outer material, each layer of which is printed, and sealing the edges of the first outer material and the second outer material through an adhesive layer. In the first paragraph,
A method for manufacturing a printed battery, characterized in that a separator is arranged on a positive or negative electrode on which a gel electrolyte composition is printed in the step (2) above, and the gel electrolyte composition is printed on the separator. In the first paragraph
A method for manufacturing a printed battery, characterized in that the electrolyte component comprises 2 to 10 parts by weight of ammonium chloride (NH ₄ Cl) per 100 parts by weight of zinc chloride (ZnCl ₂ ). In the first paragraph
A method for manufacturing a printed battery, characterized in that water is included in an amount of 95 to 120 parts by weight per 100 parts by weight of electrolyte components. delete In the first paragraph,
A method for manufacturing a printed battery, characterized in that the gel-forming component is included in an amount of 6 to 10 parts by weight per 100 parts by weight of the electrolyte component. delete In the first paragraph,
A method for manufacturing a printed battery, wherein the above fumed silica has a pH of 3.7 to 4.5 when dispersed in water at 4 wt%. In the second paragraph,
A method for manufacturing a printed battery, characterized in that the separator comprises kraft paper and the printing is screen printing. bipolar layer;
cathode layer;
A gel electrolyte layer interposed between the positive electrode layer and the negative electrode layer and comprising an electrolyte component, water, and a gel-forming component that is an amorphous fumed silica (SiO2) having a BET surface area of 170 to 230 m2/g, wherein the gel-forming component does not contain a polymer and is included in an amount of 2 to 14 parts by weight per 100 parts by weight of the electrolyte component; and
A printed battery comprising an outer material encapsulating the positive electrode layer, the negative electrode layer, and the gel electrolyte layer. In Article 10,
The above anode layer contains manganese dioxide (MnO ₂ ),
The above cathode layer contains zinc (Zn),
A printed battery characterized in that the electrolyte component includes zinc chloride and ammonium chloride. In Article 10,
The above printed battery is characterized by a thickness of 0.5 to 2.0 mm. In Article 10,
A printed battery, characterized in that the gel electrolyte layer has a thickness of 0.04 to 0.4 mm. An acidic gel composition comprising an electrolyte component, water, and a gel-forming component which is amorphous fumed silica (SiO2) having a BET surface area of 170 to 230 m2/g.
A gel electrolyte composition for a printed battery, wherein the gel-forming component does not contain a polymer and is included in an amount of 2 to 14 parts by weight based on 100 parts by weight of the electrolyte component.