KR20210076830A - Method for manufacturing electrode using open cell type metal foam - Google Patents

Abstract

The present invention relates to a method for manufacturing an electrode using an open cell metal foam to increase output and lifespan characteristics. According to the present invention, the method comprises the following steps: preparing an open cell metal foam in which a plurality of pores are formed; forming a pretreatment layer by applying a pretreatment ink to the surface of the open cell metal foam when open cell metal foam is prepared; and forming an electrode active material layer by applying an electrode active material to the open cell metal foam when the pretreatment ink is applied to the surface of the open cell metal foam. The step of forming the pretreatment layer comprises the following steps: preparing an additive by mixing isopropyl alcohol and pyromellitic acid; preparing a binder by mixing pure water, maleic acid, and a conductive resin; mixing the additive and the binder to prepare a mixture of the additive and the binder; forming a pretreatment ink by mixing a conductive resin and a first electrode active material in the mixture of the additive and the binder; and forming a pretreatment layer by applying the pretreatment ink to the surface of the open cell metal foam when the pretreatment ink is formed.

Description

Method for manufacturing electrode using open cell type metal foam

The present invention relates to a method for manufacturing an electrode using an open-cell foamed metal, and in particular, by applying a metal to the surface of a urethane foam sheet having a plurality of pores to produce an open-celled foamed metal used as a current collector of the electrode, the upper and lower It relates to a method of manufacturing an electrode using an open-cell foamed metal that can accurately and easily form a plurality of pores through which the surface passes.

An electric double layer capacitor uses activated carbon as an electrode as one supercapacitor, and a technology related to activated carbon is disclosed in Korean Patent Application Laid-Open No. 10-2011-0063472 (Patent Document 1).

Korean Patent Application Laid-Open No. 10-2011-0063472 discloses a method for manufacturing activated carbon used for electrodes of electric double-layer capacitors, and is for manufacturing activated carbon having a small average particle diameter, uniform particle size, and relatively large specific surface area in an easy and productive manner. The method for producing activated carbon used for an electrode of an electric double layer capacitor described in Korean Patent Application Laid-Open No. 10-2011-0063472 uses an easily graphitizable carbon material such as petroleum coke or coal coke as a starting material, and the carbon material is an oxidizing gas It is prepared by calcining the starting material under the atmosphere, controlling the particle size of the carbon material and activating it.

As described in Korean Patent Application Laid-Open No. 10-2011-0063472, the current collector used for an electrode such as an electric double layer capacitor or a secondary battery uses a metal foil, etc., and has a plurality of penetrations to increase the surface area or improve the adhesion of the electrode. In the case of forming the ball, a physical operation such as drilling or an operation such as etching are used, but the physical operation may damage the electrode because it is not easy to form an accurate through hole due to the physical drilling. There is a problem in that the manufacturing process is complicated because a process is required.

: Korea Patent Publication No. 10-2011-0063472

An object of the present invention is to solve the above-mentioned problems, by coating a metal on the surface of a urethane foam sheet having a plurality of pores to produce an open-celled foamed metal used as a current collector of an electrode, so that the upper and lower surfaces are penetrated An object of the present invention is to provide a method for manufacturing an electrode using an open-cell foamed metal that can accurately and easily form a plurality of pores.

Another object of the present invention is to prepare an open-cell foamed metal used as a current collector of an electrode by coating a metal on the surface of a urethane foam sheet having a plurality of pores, so that the electrode active material formed on the surface of one side and the other side of the open-cell foamed metal is It is connected through a plurality of pores, and the surface of the open-celled foamed metal is pretreated with a pretreatment ink to improve the adhesion between the open-celled foamed metal and the electrode active material, thereby preventing the electrode active material from peeling off, thereby preventing an increase in interfacial resistance. An object of the present invention is to provide a method for manufacturing an electrode using an open-cell foamed metal capable of improving output and lifespan characteristics.

An electrode manufacturing method using an open cell foam metal of the present invention comprises the steps of preparing an open cell type foam metal having a plurality of pores; forming a pretreatment layer by applying a pretreatment ink to the surface of the open cell foamed metal when the open cell foamed metal is prepared; and forming an electrode active material layer by applying an electrode active material to the open cell foamed metal when the pretreatment ink is applied to the surface of the open cell foamed metal, wherein the forming of the pretreatment layer is isopropyl alcohol ) and pyromellitic acid to prepare an additive, pure water, maleic acid, and a conductive resin to prepare a binder, and mixing the additive and the binder to form an additive Preparing a mixture of the binder, mixing the conductive powder and the first electrode active material in the mixture of the additive and the binder to form a pretreatment ink, and when the pretreatment ink is formed, the open cell foamed metal is applied to the surface of the pretreatment ink Forming the electrode active material layer comprises the step of forming a pretreatment layer by applying a second electrode active material through the pretreatment layer so that a plurality of pores are filled, respectively, forming a plurality of pore buried layers; , Forming a cover electrode layer by applying the first active material electrode to the surface of the upper or lower surface of the open-cell foamed metal to cover the plurality of pore buried layers in a state connected to the plurality of pore buried layers via a pretreatment layer, respectively. , Carbon or activated carbon is used as the first electrode active material, silicon (Si) powder is used as the second electrode active material, and the conductive resin is selected from among acrylic, nitrocellulose and chitosan. characterized by being one.

The electrode manufacturing method using the open-cell foamed metal of the present invention is to prepare an open-celled foamed metal used as a current collector of the electrode by coating the metal on the surface of the urethane foam sheet having a plurality of pores, so that the upper and lower surfaces penetrate There is an advantage of being able to accurately and easily form a plurality of pores, and by coating a metal on the surface of a urethane foam sheet having a plurality of pores to prepare an open-celled foamed metal used as a current collector of an electrode, The electrode active material formed on the surface of one side and the other side is connected through a plurality of pores, and the electrode active material is peeled off by pre-treating the surface of the open-celled foamed metal with a pretreatment ink to improve the adhesion between the open-celled foamed metal and the electrode active material There is an advantage in that it is possible to improve the output and lifespan characteristics by preventing an increase in interfacial resistance by preventing

1 is a process flow diagram showing a method for manufacturing an electrode using an open-cell foamed metal of the present invention;
2 is a process flow diagram showing in detail the method of manufacturing the open-cell foamed metal shown in FIG. 1;
3 is a cross-sectional view of an electrode manufactured by the electrode manufacturing method using the open-cell foamed metal shown in FIG. 1;
Figure 4 is a schematic front view of the roll-to-roll (roll to roll) process equipment for forming the open-cell foamed metal or electrode active material layer shown in Figure 1;

Hereinafter, an embodiment of an electrode manufacturing method using an open-cell foamed metal of the present invention will be described with reference to the accompanying drawings.

1 and 3, the electrode manufacturing method using the open-cell foamed metal 111 of the present invention includes the steps of preparing an open-cell type foamed metal 111 in which a plurality of pores 111a are formed ( S10) is performed. When the open-celled foamed metal 111 is prepared in step S10, a step (S20) of forming a pretreatment layer 112 by applying a pretreatment ink to the surface of the open-celled foamed metal 111 is performed. When the pretreatment ink is applied to the surface of the open-cell foamed metal 111 in step S20, the electrode active material is applied to the open-cell foamed metal 111 to form the electrode active material layer 113 (S30) An electrode active material layer 113 is formed on the surface of the mold foam metal 111 .

A specific embodiment of the method of forming the electrode 110 using the open-cell foamed metal 111 of the present invention will be described as follows.

The step of preparing the open-cell foamed metal 111 (S10) is, as in FIGS. 2 to 4, first, positioned between the first conveying sheet 11 and the second conveying sheet 21 so that the thickness of the first conveying A step (S11) of applying the foam mixture to be regulated by the sheet 11 and the second conveying sheet 21 is performed. That is, the application method of the foamed mixture is performed using the roll-to-roll process equipment shown in FIG. 4 shown in FIG. 4, and the roll-to-roll process equipment includes the foamed mixture in the foamed mixture supply tank 30 and the first transfer sheet ( 11), the first transfer sheet 11 coated with the foam mixture is guided by the auxiliary roller 10a and transferred to the lower portion of the second transfer sheet 21 . When the first transfer sheet 11 is transferred to the lower part of the second transfer sheet 21, the foamed mixture is applied with a thickness defined by the gap between the first transfer sheet 11 and the second transfer sheet 21, The first conveying sheet 11 and the second conveying sheet 21 are regulated by a pair of auxiliary rollers 20a, respectively, to maintain a constant distance therebetween. For example, in the roll-to-roll equipment shown in FIG. 4, the foamed mixture is coated on the upper surface of the first transfer sheet 11, and the first transfer sheet 11 is disposed at a distance from each other in the vertical direction and The thickness is defined and applied by the interval of the second transfer sheet 21 .

The foamed mixture coated with a thickness defined by the first transfer sheet 11 and the second transfer sheet 21 is formed by mixing a foaming polyurethane resin and a foaming agent. The polyurethane resin for foaming is used including a polyol and a diisocyanate compound. Polyol is used at least one of polyester glycol (polyesterglycol), polyether glycol (polyetherglycol), polycarbonate glycol (polycarbonateglycol). The diisocyanate compound is diisocyanate, methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate, tetra methylene diisocyanate, isoholone diisocyanate ( iso holon diisocyanate), naphthalene diisocyanate and triphenyl methane triisocyanate are used, and the blowing agent is CO ₂ , pure water (H ₂ O), hydrochlorofluorocarbons, Two or more of perfluorocarbons and chlorofluorocarbons are used.

When the foamed mixture is applied to be positioned between the first conveying sheet 11 and the second conveying sheet 21, the first conveying sheet 11 and the second conveying sheet 21 are transferred to the dryer 40 for the first conveyance A step (S12) of drying the foam mixture positioned between the sheet 11 and the second conveying sheet 21 is performed. When the foam mixture is dried, the first conveying sheet 11 and the second conveying sheet 21 are transferred to the heater 50, positioned between the first conveying sheet 11 and the second conveying sheet 21, and the dried foam By heating the mixture is foamed to form a urethane foam sheet (S13) is performed. Here, the urethane foam sheet is formed with a plurality of foam sheet pores (not shown). A plurality of foam sheet pores are formed to penetrate from the surface of one side of the urethane foam sheet to the surface of the other side, respectively. When the urethane foam sheet is formed, the urethane foam sheet is transferred to the electroless plating tank 70, metal is plated on the entire surface of the urethane foam sheet, and a plurality of pores 111a through which the upper surface and the lower surface penetrate are formed. A step (S14) of forming the type foamed metal 111 is performed. That is, the open-cell foamed metal 111 forms a plurality of pores 111a by plating the metal on the entire surface of the urethane foam sheet, including the surface of a plurality of foam sheet pores formed in the urethane foam sheet when the urethane foam sheet is formed. do. For example, the plurality of pores 111a are each formed to penetrate from the surface of one side to the surface of the other side of the open-celled foamed metal 111, and are formed by plating the metal on the surface of the plurality of foamed sheet pores, and the plating is By using a metal material, the open-cell foamed metal 111 can be wound and used, and electrical conductivity of the open-celled foamed metal 111 is improved. Here, as the metal material, copper (Cu) or aluminum (Al) is used.

When the open-cell foamed metal 111 is formed, the step of forming the pretreatment layer 112 (S20) is performed. Forming the pretreatment layer 112 (S20), as in FIGS. 1 and 3, first, mixing isopropyl alcohol and pyromellitic acid to prepare an additive (S21) carry out When the additive is prepared, a step of preparing a binder by mixing pure water, maleic acid, and a conductive resin (S22) is performed. When the binder is prepared, the step (S23) of preparing a mixture of the additive and the binder is performed by mixing the additive and the binder. When the mixture of the additive and the binder is prepared, a step (S24) of forming a pretreatment ink by mixing the conductive resin and the first electrode active material in the mixture of the additive and the binder is performed. Here, as the conductive resin mixed in the mixture of the additive and the binder, one of acrylic, nitrocellulose, and chitosan is used, and the first electrode material is carbon or activated carbon for the first electrode material. used

When the pretreatment ink is formed, the step (S25) of forming the pretreatment layer 112 by applying the pretreatment ink to the surface of the open-cell foamed metal 111 is performed, and the method of forming the pretreatment layer 112 is shown in FIG. As shown, a pair of pretreatment ink ejectors 60 and 61 is used, and one pretreatment ink ejector 60 among the pair of pretreatment ink ejectors 60 and 61 is the surface of one side of the open-cell foamed metal 111 . The other pretreatment ink ejector 61 is disposed on the surface of the other side of the foamed metal 111 to spray and apply the pretreatment ink to the open-cell foamed metal 111 . This pretreatment ink is dried by a dryer (not shown) at the front end of the electroless plating tank 70 to form the pretreatment layer 112 .

A specific embodiment of the method of manufacturing the pretreatment ink used for the pretreatment layer 112 is first, in the step of preparing an additive by mixing isopropyl alcohol and pyromellitic acid (S21), the additive is 80 to 90 wt% of isopropyl alcohol and It is prepared by mixing 10 to 20 wt% of pyromellitic acid at 350 to 500 RPM (revolutions per minute) using a stirrer at room temperature (25° C.) for 5 to 10 minutes. When the additive is prepared, in the step of preparing a binder by mixing pure water, maleic acid, and conductive resin (S21), the binder is prepared by mixing pure water and maleic acid to prepare a mixture of pure water and maleic acid, and then adding the conductive resin to the mixture of pure water and maleic acid. A mixture of conductive resin is prepared by mixing, and the mixture of pure water and maleic acid is 80 to 90 wt% of pure water and 10 to 20 wt% of maleic acid 5 to 10 at 350 to 500 RPM at room temperature using a pre-mixer. Mix for a minute. Here, the mixture of the conductive resin is prepared by mixing 80 to 90 wt% of a mixture of pure water and maleic acid and 10 to 20 wt% of the conductive resin at 1500 to 2000 RPM for 10 to 30 minutes using a pre-mixer, As the resin, at least one of graphene and carbon nanotubes is used.

When the binder is prepared, in the step of preparing a mixture of the additive and the binder by mixing the additive and the binder (S23), the mixture of the additive and the binder is prepared by mixing 10 to 15 wt% of the additive and 85 to 90 wt% of the binder in a pre-mixer. It is prepared by mixing for 5 to 10 minutes at 350 to 500 RPM at room temperature. When the mixture of the additive and the binder is prepared, in the step of mixing the conductive resin and the first electrode active material in the mixture of the additive and the binder (S24), the conductive resin and the first electrode active material are each added to 80 to 90 wt% of the mixture of the additive and the binder. It is prepared by mixing 5 to 10 wt% of the resin and 5 to 10 wt% of the first electrode active material at 800 to 1000 RPM at room temperature using a pre-mixer for 5 to 10 minutes. Here, one of acrylic, nitrocellulose, and chitosan is used, and the first electrode active material is 80 to 90 wt% of carbon, activated carbon, and activated carbon among activated carbon, 8 to 15 wt% of a conductive agent, and a binder 5 to 12wt%, the conductive agent is one of Super-P, ketjen black, and carbon black, and the binder is PVDF (polyvinylidene difluoride), PTFE (polytetrafluoroethylene) , one of SBR (styrene butadiene rubber) and CMC (carboxymethylcellulose) is used.

In the step (S30) of forming the electrode active material layer 113, the second electrode active material is applied via the pretreatment layer 112 so that the plurality of pores 111a are respectively filled as shown in FIGS. 1 to 3 to form a plurality of pores. A step S31 of forming the buried layer 113a is performed. Silicon (Si) powder is used as the second electrode active material for forming the plurality of pore filling layers 113a. That is, the energy density of the plurality of pores 111a can be improved by filling the inside of the silicon (Si) powder as the second electrode active material, and by using the silicon (Si) powder having the same particle size, each silicon (Si) ) space is generated between the powders, and it can be used as a buffer space when the silicon (Si) powder is expanded by this space, thereby preventing damage to the electrode active material layer 113 due to the expansion of the silicon (Si) powder. there will be

When a plurality of pore filling layers 113a are formed, a plurality of pore filling layers 113a are connected to the plurality of pore filling layers 113a via the pretreatment layer 112 on the upper or lower surface of the open-celled foamed metal 111, respectively. ) to cover (cover) the first active material electrode is applied to form a cover electrode layer 113b (S32) is performed. For the cover electrode layer 113b, carbon or activated carbon is used as the first active material electrode. That is, the cover electrode layer 113b uses the same first electrode active material used for the pretreatment layer 112 to form a plurality of pore buried layers 113a formed of silicon (Si) powder with the pretreatment layer 112 and the cover electrode layer 113b. It is possible to prevent damage to the electrode active material layer 113 due to the expansion of the silicon (Si) powder by being positioned therebetween. For example, when carbon is used as the first electrode active material in the cover electrode layer 113b, carbon is used as the first electrode active material in the pretreatment layer 112, and when activated carbon is used as the first electrode active material in the cover electrode layer 113b, pretreatment Layer 112 In addition, activated carbon is used as the first electrode active material to cover the plurality of pore-buried layers 113a, thereby improving energy density and preventing damage to the electrode active material layer 113 due to expansion of silicon (Si) powder. .

The roll-to-roll process equipment applied to the electrode manufacturing method using the open-cell foamed metal of the present invention will be described with reference to the accompanying FIG. 4 as follows.

The roll-to-roll process equipment shown in FIG. 4 is a first conveying sheet winding roll 10, a second conveying sheet winding roll 20, a foamed mixture supply tank 30, a dryer 40, a heater 50 ), a pair of pretreatment ink ejectors 60 and 61 , an electroless plating bath 70 and an open cell foam metal recovery roll 80 .

A guide roller for guiding the first conveying sheet winding roll 10 on which the first conveying sheet 11 is wound is disposed on one side and the first conveying sheet 11 conveyed to the other side of the first conveying sheet winding roll 10 (10a) is arranged. The second conveying sheet winding roll 20 is disposed to be positioned above the first conveying sheet winding roll 10 on the other side of the first conveying sheet winding roll 10 to supply the foamed mixture to the first conveying sheet 11 . When the foamed mixture is applied by (30), the foamed mixture is pressed with the second conveying sheet 21 to maintain a constant thickness, and for this purpose, the first conveying sheet 11 and the second conveying sheet 21 are one It is pressed by the pair of auxiliary rollers (20a) so that a constant interval is maintained.

The foamed mixture supply tank 30 is disposed to be positioned on one side of the second conveying sheet take-up roll 20 to be positioned on the first conveying sheet take-up roll 10 and wound on the first conveying sheet take-up roll 10 . When the first transfer sheet 11 is transferred, the foamed mixture is applied on the first transfer sheet 11 . The first conveying sheet 11 to which the foaming mixture is applied and the second conveying sheet 21 for regulating the thickness of the foaming mixture are formed by the first conveying sheet recovery roll 10c and the second conveying sheet recovery roll 20c, respectively. recovered and transported The first conveyance sheet recovery roll 10c and the second conveyance sheet recovery roll 20c are disposed to be spaced apart from the first conveyance sheet take-up roll 10 and the second conveyance sheet take-up roll 20, respectively, and the first conveyance wound up The sheet 11 or the second conveyance sheet 21 is wound up and collected.

The dryer 40 is positioned between the second conveying sheet winding roll 20 and the second conveying sheet recovery roll 20c to produce a foamed mixture located between the first conveying sheet 11 and the second conveying sheet 21 . To dry, a pair of heating blocks 41 and 42 are provided on the inside, and the pair of heating blocks 41 and 42 are respectively disposed on the upper and lower sides of the dryer 40, respectively. The heater 50 is disposed between the dryer 40 and a pair of pre-treatment ink ejectors 60 and 61 , and includes a pair of auxiliary rollers 20b between the dryer 40 and the heater 50 to provide the first By regulating the conveying sheet 11 or the second conveying sheet 21, the thickness can be maintained until the foam mixture is sufficiently dried through the dryer 40. The heater 50 for supplying heat for foaming the foamed mixture positioned between the first conveying sheet 11 or the second conveying sheet 21 that has passed through the pair of auxiliary rollers 20b has a pair of inside Heating blocks 51 and 52 are disposed, and a pair of heating blocks 51 and 52 are respectively disposed on the upper and lower sides of the inner side and dried through the first conveying sheet 11 and the second conveying sheet 21 . By transferring heat to the foam mixture, the foam mixture is foamed to form a urethane foam sheet. In order to easily form a urethane foam sheet, the first conveying sheet 11 and the second conveying sheet 21 covering the upper and lower portions of the dried foam mixture are respectively a first conveying sheet recovery roll 10c and a second When it is collected by the conveyance sheet collection roll 20c, the first conveyance sheet collection roll 10c and the second conveyance sheet collection roll 20c are separated by the horizontal of the first conveyance sheet 11 and the second conveyance sheet 21. They are spaced apart so that they are not horizontal. By disposing the first conveying sheet recovery roll 10c and the second conveying sheet recovery roll 20c in this way, the first conveying sheet 11 and the second conveying sheet 21 are peeled off from the dried foam mixture, respectively, so that the heater The heat generated in (50) is more easily transferred to the dried foaming mixture, so that the bubbles that may be generated during foaming are easily discharged to the outside, thereby improving the foaming operation.

A pair of pretreatment ink sprayers 60 and 61 are disposed between the heater 50 and the electroless plating tank 70 to spray and apply the pretreatment ink to the upper or lower surface of the foamed urethane foam sheet to apply the pretreatment layer. (112). When the urethane foam sheet is guided by the auxiliary rollers 60a, 60b, and 60c and is disposed between a pair of pre-treatment ink ejectors 60 and 61 and the open-cell foamed metal recovery roll 80, copper ( The open cell foamed metal 111 is manufactured by plating a metal such as Cu) or aluminum (Al), and the open cell foamed metal 111 on which the metal plating is completed is an open cell disposed on the other side of the electroless plating tank 70 . It is recovered by being wound around a mold-type foamed metal recovery roll 80 .

Looking more specifically at the method of manufacturing the open-celled foamed metal using the above-described roll-to-roll process equipment, the step of applying the foamed mixture (S11) is a state in which the foamed mixture is applied on the upper portion of the first conveying sheet 11 The first transfer sheet 11 wound on the first transfer sheet take-up roll 10 is collected by the first transfer sheet recovery roll 10c, and the second transfer is carried out at an interval on the upper part of the first transfer sheet 11 . The thickness of the first transfer sheet 11 and the second transfer sheet 21 is uniform by collecting the second transfer sheet 21 wound on the sheet take-up roll 20 with the second transfer sheet collecting roll 20c. is spread out Here, the first transfer sheet 11 and the second transfer sheet 21 are each metal sheet (11a, 21a) and a heat conductive layer (11b, 21b) applied to the front surface of the metal sheet (11a, 21a) is applied, The material of the heat-conducting layers 11b and 21b is graphene, which transfers heat to the foam mixture through the first transfer sheet 11 and the second transfer sheet 21 . That is, the first transfer sheet 11 and the second transfer sheet 21 is applied between the coated and positioned foam mixture to easily transfer heat to reduce the process time such as drying or foaming time to improve work productivity do.

The step of drying the foamed mixture (S12) is to remove heat generated from a pair of heating blocks 41 and 42 respectively disposed in the upper and lower portions of the dryer 40 to the first transfer sheet 11 and the second transfer sheet. A pair of heating blocks 51 and 52 respectively disposed on the upper and lower sides of the heater 50 in the step (S13) of transferring the foam mixture to the foam mixture and drying the foam mixture, and forming a urethane foam sheet (S13) The heat generated from is transferred to the dried foam mixture through the first transfer sheet 11 and the second transfer sheet 21 to foam the foam mixture to form a urethane foam sheet. Here, the urethane foam sheet is heat-treated at 200 to 250 ° C. for 20 to 60 minutes of the dried foamed mixture, and has a thickness of 10 to 200 μm, and a plurality of foam sheet pores (not specified) are formed, so that the porosity is 85 to 98%, It is formed so that the average pore diameter is 0.5 to 0.1 mm. In the step (S14) of forming the open-celled foamed metal 111, the metal is applied to the entire surface of the urethane foam sheet using electroless plating to be used as a current collector of the electrode, and the open-celled foamed metal in which a plurality of pores 111a are formed. (111) is manufactured, and copper or aluminum is used as the material of the metal to be plated. The open-cell foamed metal 111 manufactured in this way has an inner side of a urethane foam sheet and an outer side is plated with metal to improve electrical conductivity while having ductility, so that it can be used while being lightweight.

A lithium ion secondary battery was prepared in order to confirm the electrical characteristics of the electrode manufactured using the electrode manufacturing method using the open-cell foamed metal of the present invention. In order to manufacture a lithium ion secondary battery, a negative electrode and a positive electrode were first prepared.

To prepare the negative electrode, an open-cell foamed metal 111 was first prepared, and polyol polycarbonate glycol was used as a polyurethane resin for foaming for the production of the open-celled foamed metal 111, and the diisocyanate compound was triphenyl methane. Triisocyanate was used, and the foaming agent was CO ₂ and chlorofluorocarbon to prepare a dried foamed mixture and then heat-treated the dried foamed mixture at 250° C. for 60 minutes to form a urethane foam sheet. After the urethane foam sheet was formed, copper (Cu) was plated using electroless plating to prepare an open cell foam metal 111 having a thickness of 200 μm, a porosity of 98%, and an average pore diameter of 0.1 mm. After the open-cell foamed metal 111 was prepared, a pretreatment layer 112 was formed on the entire surface of the open-celled foamed metal.

The pretreatment layer 112 was formed by applying pretreatment ink to the entire surface of the open-cell foamed metal 111, and the pretreatment ink was formed by adding 90 wt% of isopropyl alcohol and 20 wt% of pyromellitic acid to an additive at room temperature (25° C.) with a stirrer. was prepared by mixing at 500 RPM for 10 minutes, and the binder was mixed with 90 wt% of pure water and 10 wt% of maleic acid at 500 RPM at room temperature using a premixer for 10 minutes, and then 90 wt% of a mixture of pure water and maleic acid and conductivity The resin was prepared by mixing 10 wt% of carbon nanotubes at 2000 RPM using a premixer for 30 minutes, and mixing wt% of the additive and 85 wt% of the binder at 500 RPM at room temperature using a premixer for 10 minutes. After that, 5 wt% of acryl as a conductive resin and 5 wt% of the first electrode active material as a conductive resin were mixed in 90 wt% of a mixture of additives and binders at 1000 RPM at room temperature for 10 minutes using a premixer, and the first electrode active material was 90 wt% of activated carbon and A pretreatment ink was prepared by mixing 8 wt% of Super-P as a conductive agent and 2 wt% of PVDF as a binder. After the pretreatment layer 112 was formed, the electrode active material layer 113 was formed through the pretreatment layer 112 . The electrode active material layer 113 uses silicon (Si) powder as a second electrode active material to fill a plurality of pores 111a, respectively, to form a plurality of pore filling layers 113a, and then to cover the plurality of pore filling layers 113a. 1 A cover electrode layer 113a was formed using activated carbon as an active material electrode.

For the positive electrode manufacturing, first, polyol polycarbonate glycol was used as a polyurethane resin for foaming, triphenyl methane triisocyanate was used as the diisocyanate compound, and the blowing agent was CO ₂ and chlorofluorocarbon to prepare a dried foaming mixture. Then, the dried foam mixture was heat treated at 200° C. for 20 minutes to form a urethane foam sheet. After the urethane foam sheet was formed, aluminum (Al) was plated using electroless plating to prepare an open-cell foamed metal 111 having a thickness of 10 μm, a porosity of 85%, and an average pore diameter of 0.5 mm. After the open-cell foamed metal 111 was prepared, a pretreatment layer 112 was formed on the entire surface of the open-celled foamed metal.

The pretreatment layer 112 was formed by applying the pretreatment ink to the entire surface of the open-cell foamed metal 111, and the pretreatment ink was prepared by adding 80 wt% of isopropyl alcohol and 0 wt% of pyromellitic acid as an additive at room temperature (25° C.) with a stirrer. It was prepared by mixing at 350 RPM for 5 minutes using a binder, and the binder was mixed with 80 wt% of pure water and 20 wt% of maleic acid at 350 RPM at room temperature using a premixer for 5 minutes, and then 80 wt% of a mixture of pure water and maleic acid and a conductive resin 20 wt% of carbon nanotubes were prepared by mixing at 1500 RPM for 10 minutes using a premixer, and then 10 wt% of the additive and 90 wt% of the binder were mixed using a premixer at 350 RPM at room temperature for 5 minutes. To 80 wt% of the binder mixture, 10 wt% of acryl as a conductive resin and 10 wt% of the first electrode active material were mixed at 800 RPM at room temperature using a premixer for 5 minutes, and the first electrode active material was 80 wt% of activated carbon and superconducting agent. -Pretreatment ink was prepared by mixing 8 wt% of blood and 12 wt% of PVDF as a binder. After the pretreatment layer 112 was formed, the electrode active material layer 113 was formed through the pretreatment layer 112 . The electrode active material layer 113 was prepared by coating a known positive electrode active material used in a known lithium ion secondary battery to fill the plurality of pores 111a. When the negative electrode and the positive electrode thus prepared were prepared, the negative electrode and the positive electrode were manufactured in a cylindrical 18650 size lithium ion secondary battery, and then an electrical test was performed. As a result of an electrical test using a known test equipment, the energy density was measured to be 290 Wh/kg when the present invention was applied, and the conventional cylindrical lithium ion secondary battery of 18650 was measured to be 270 Wh/kg. Therefore, it can be seen that the energy density of the lithium secondary battery using the electrode using the open-cell foamed metal of the present invention is increased compared to that of the conventional lithium secondary battery.

As described above, in the electrode manufacturing method using the open-cell foamed metal of the present invention, the surface of the open-celled foamed metal 111, that is, the current collector, is pretreated with a pre-treatment ink to form an electrode between the current collector and the electrode active material when the electrode active material is applied. By improving adhesion, it is possible to prevent an increase in interfacial resistance due to peeling of the electrode active material, thereby improving output and lifespan characteristics, and by reducing the weight of the current collector as a whole, it is manufactured by the electrode manufacturing method using the open-cell foamed metal of the present invention. It is possible to reduce the weight of the electric double layer capacitor or the secondary battery using the electrode.

The electrode manufacturing method using the open-cell foamed metal of the present invention can be applied to manufacturing industries such as electric double-layer capacitors and secondary batteries.

10: first conveying sheet winding roll 20: second conveying sheet winding roll
30: foam mixture supply tank 40: dryer
50: heater 60, 61: pre-treatment ink ejector
70: electroless plating tank 80: open cell type foam metal recovery roll
110: electrode 111: open-cell foamed metal
112: pretreatment ink layer 113: electrode active material layer

Claims (5)

Preparing an open cell type foam metal in which a plurality of pores are formed;
forming a pretreatment layer by applying a pretreatment ink to the surface of the open cell foamed metal when the open cell foamed metal is prepared; and
When the pretreatment ink is applied to the surface of the open-cell foamed metal, applying an electrode active material to the open-celled foamed metal to form an electrode active material layer,
Forming the pretreatment layer includes preparing an additive by mixing isopropyl alcohol and pyromellitic acid, and preparing a binder by mixing pure water, maleic acid, and a conductive resin preparing a mixture of an additive and a binder by mixing the additive and the binder; and mixing a conductive resin and a first electrode active material in the mixture of the additive and the binder to form a pretreatment ink; Forming a pretreatment layer by applying a pretreatment ink to the surface of the open-cell foamed metal when the ink is formed,
The forming of the electrode active material layer includes forming a plurality of pore-buried layers by applying a second electrode active material through a pretreatment layer so that a plurality of pores are respectively filled, and on the surface of the upper or lower surface of the open-cell foamed metal. Forming a cover electrode layer by applying a first active material electrode so as to cover the plurality of pore buried layers in a state in which each is connected to the plurality of pore buried layers via the pretreatment layer,
Carbon or activated carbon is used as the first electrode active material, silicon (Si) powder is used as the second electrode active material, and the conductive resin is one of acrylic, nitrocellulose, and chitosan. A method for manufacturing an electrode using an open-cell foamed metal According to claim 1,
The step of preparing the open-cell foamed metal includes: applying a foamed mixture positioned between the first and second conveying sheets so that the thickness is regulated by the first and second conveying sheets;
transferring the first conveying sheet and the second conveying sheet to a dryer to dry the foamed mixture positioned between the first conveying sheet and the second conveying sheet;
Forming a urethane foam sheet by transferring the first conveying sheet and the second conveying sheet to a heater and positioned between the first conveying sheet and the second conveying sheet and heating the dried foam mixture; and
Transferring the urethane foam sheet to an electroless plating tank and plating the metal on the entire surface of the urethane foam sheet to form an open-cell foamed metal having a plurality of pores penetrating through the upper surface and the lower surface,
In the step of applying the foamed mixture, the foamed mixture is formed by mixing a foaming polyurethane resin and a foaming agent, and the foaming polyurethane resin includes a polyol and a diisocyanate compound, and the polyol is At least one of polyesterglycol, polyetherglycol, and polycarbonateglycol is used, and the diisocyanate compound is diisocyanate, methylene diphenyl diisocyanate, polymer Polymeric methylene diphenyl diisocyanate, tetra methylene diisocyanate, iso holon diisocyanate, naphthalene diisocyanate and triphenyl methane triisocyanate Two or more of them are used, and the blowing agent is CO ₂ , pure (H ₂ O), hydrochlorofluorocarbons, perfluorocarbons, and chlorofluorocarbons in which two or more are used. A method for manufacturing an electrode using a molded foam metal. According to claim 1,
The step of applying the foamed mixture, drying the foamed mixture, forming the urethane foam sheet, and applying the foamed mixture among the steps of forming the open-cell foamed metal is the first return of the foamed mixture In the state coated on the upper part of the sheet, the first transfer sheet wound on the first transfer sheet take-up roll is collected by the first transfer sheet recovery roll, and the first transfer sheet is wound on the second transfer sheet take-up roll at an interval on the upper part of the first transfer sheet. By collecting the second transfer sheet by the second transfer sheet recovery roll, the thickness of the first transfer sheet and the second transfer sheet is uniformly applied, and the first transfer sheet and the second transfer sheet are each a metal sheet and the metal sheet A heat-conducting layer applied to the front surface of the is applied, and the material of the heat-conducting layer is graphene to transfer heat to the foam mixture through the first and second transfer sheets,
In the step of drying the foamed mixture, heat generated from a pair of heating blocks disposed on the upper and lower portions of the dryer is transferred to the foamed mixture through the first and second transfer sheets to dry the foamed mixture,
In the step of forming the urethane foam sheet, heat generated from a pair of heating blocks disposed above and below the heater is transferred to the dried foam mixture through the first conveying sheet and the second conveying sheet to foam the foamed mixture. It forms a urethane foam sheet,
The step of forming the open-cell foamed metal is an electrode manufacturing method using an open-celled foamed metal using copper as the material of the metal. 4. The method of claim 3,
The urethane foam sheet is heat-treated for 20 to 60 minutes at 200 to 250° C. of the dried foamed mixture to have a thickness of 10 to 200 μm, a porosity of 85 to 98%, and an average pore diameter of 0.5 to 0.1 mm. A method for manufacturing an electrode using a molded foam metal. According to claim 1,
Preparing an additive by mixing the isopropyl alcohol and pyromellitic acid, preparing a binder by mixing the pure water, maleic acid, and a conductive resin, and mixing the additive and the binder to prepare a mixture of the additive and the binder and mixing the conductive resin and the first electrode active material with the mixture of the additive and the binder to form the pretreatment ink, in the step of preparing the additive by mixing the isopropyl alcohol and pyromellitic acid, the additive is isopropyl 80 to 90 wt% of alcohol and 10 to 20 wt% of pyromellitic acid are mixed at room temperature (25° C.) at 350 to 500 RPM (revolutions per minute) for 5 to 10 minutes using a stirrer, and the pure water and maleic acid are conductive In the step of preparing the binder by mixing the resin, the binder is prepared by mixing pure water and maleic acid to prepare a mixture of pure water and maleic acid, and then mixing the conductive resin with the mixture of pure water and maleic acid to prepare a conductive resin mixture, The mixture of pure water and maleic acid is mixed with 80 to 90 wt% of pure water and 10 to 20 wt% of maleic acid at 350 to 500 RPM at room temperature using a pre-mixer for 5 to 10 minutes, and the mixture of the conductive resin Silver is prepared by mixing 80 to 90 wt% of a mixture of pure water and maleic acid and 10 to 20 wt% of a conductive resin at 1500 to 2000 RPM for 10 to 30 minutes using a pre-mixer, At least one of graphene and carbon nanotubes is used as the conductive resin mixed into the mixture, and in the step of preparing a mixture of the additive and the binder by mixing the additive and the binder, the mixture of the additive and the binder is additives 10 to 15 It is prepared by mixing wt% and 85 to 90 wt% of the binder at 350 to 500 RPM at room temperature using a pre mixer for 5 to 10 minutes, and the conductive resin and the first electrode active in the mixture of the additive and the binder. In the step of mixing the materials, the conductive resin and the first electrode active material are prepared by adding 5 to 10 wt% of the conductive resin and 5 to 10 wt% of the first electrode active material to 80 to 90 wt% of the mixture of the additive and the binder, respectively. ) at room temperature at 800 to 1000 RPM for 5 to 10 minutes, and the conductive resin mixed in the mixture of the additive and the binder is one of acrylic, nitrocellulose and chitosan. and the first electrode active material consists of 80 to 90 wt% of activated carbon, 8 to 15 wt% of a conductive agent, and 5 to 12 wt% of a binder, and the conductive agent includes Super-P, ketjen black, and One of carbon black is used, and as the binder, one of polyvinylidene difluoride (PVDF), polytetrafluoroethylene (PTFE), styrene butadiene rubber (SBR), and carboxymethylcellulose (CMC) is used. Way.

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