The present invention claims the benefit of priority based on Korean Patent Application No. 2020-0011990 dated January 31, 2020 and Korean Patent Application No. 2021-0005334 dated January 14, 2021, and all The content is incorporated as part of this specification. [2] The present invention relates to a method for manufacturing a separator-integrated electrode including a multi-layered inorganic material layer and a separator-integrated electrode according thereto. Specifically, the unit electrode includes a first inorganic material layer containing first inorganic particles having a larger diameter than the pore size of the electrode active material layer and a second inorganic material layer containing second inorganic particles having a diameter smaller than the diameter of the first inorganic particles. It relates to a method for manufacturing a membrane combination electrode and a separation membrane combination electrode according thereto. background art [3] Among the components of the secondary battery, the separator separates the positive electrode and the negative electrode to prevent electrical short circuit between the two electrodes while allowing electrolyte and ions to pass through. The separator itself does not participate in the electrochemical reaction of the secondary battery, but has a great influence on the performance and safety of the secondary battery due to physical properties such as wettability to electrolyte, degree of porosity, and thermal shrinkage. [4] Polyolefin-based porous substrates are widely used as separators for secondary batteries. Since the porous substrate thermally contracts at a high temperature, it does not properly perform a role of separating the positive electrode and the negative electrode. Due to this, safety issues such as short-circuiting of the secondary battery or ignition or explosion of the battery have been continuously raised. [5] In order to compensate for the disadvantages of the porous substrate, a coating layer is added to one or both surfaces of the porous substrate, and various materials capable of supplementing the disadvantages of the porous substrate are added to the coating layer or the physical properties of the coating layer are changed. A metal oxide such as alumina (Al 2 O 3 ) or a metal hydroxide such as aluminum hydroxide (Al(OH) 3 ) is added as an inorganic substance to the coating layer to suppress thermal shrinkage of the separator or improve heat resistance. [6] A coating layer containing an inorganic material has a disadvantage in that adhesion to the electrode is weak. In addition, since the coating layer is added to one side or both sides of the porous substrate, there is a disadvantage in that the portion of the secondary battery that does not participate in the chemical reaction increases. [7] In order to improve the disadvantages of these separators, a separator-composite electrode has been proposed that serves as a conventional separator by forming an inorganic coating layer on the electrode active material layer. Electrode assemblies using membrane-integrated electrodes do not have a separate porous substrate, so there is no fear of heat shrinkage and consequent short circuit, and there is an advantage of minimizing the part of the secondary battery that does not participate in the chemical reaction. [8] 1 is a schematic diagram of a conventional membrane-integrated electrode. A conventional membrane combination electrode is formed by directly applying or coating an inorganic material on the electrode active material layer 20 or by bonding a pre-formed inorganic material layer 30 on the electrode active material layer 20 . An electrode active material layer 20 is coated on one surface of the current collector 10, and an inorganic material layer 30 is coated on the uppermost layer. [9] In many cases, the diameter of the particles of the inorganic material layer 30 of the conventional membrane-integrated electrode as shown in FIG. 1 is smaller than the pores of the electrode active material layer 20 formed on the electrode. Although small-sized inorganic particles are used for the role of the separator, the particles of the inorganic layer 30 may rather block the pores of the electrode active material layer 20 to increase the resistance of the battery. In addition, the binder for bonding the inorganic material layer may block pores of the electrode active material layer 20 formed on the electrode. When the resistance of the battery increases as described above, the battery capacity is rather reduced and the life of the battery is shortened. [10] Patent Document 1 has an inorganic particle layer composed of several layers, but this is a multilayer structure according to the role of the inorganic coating layer, and the structure for not blocking the pores of the electrode is not recognized. [11] Patent Document 2 also relates to an electrode provided with a current collector, an active material layer, and an inorganic material layer. Patent Document 2 uses ceramic fillers of various sizes and shapes in order to increase the ion conductivity of the ceramic separator itself by providing an inorganic material layer having two or more types of particle diameters, but this is to improve the performance of the separator itself. It is not recognized that the pores are clogged or the performance degradation of the battery due to this is not recognized. [12] In order to improve the safety of secondary batteries used closely in daily life and to develop secondary batteries that can meet the demand for high capacity and high density, it is necessary to provide a separator composite electrode that does not block the pores of the electrode and a secondary battery using the same there is [13] Republic of Korea Patent Publication No. 2016-0112266 (2016.09.28) ('Patent Document 1') [14] Republic of Korea Patent Publication No. 2008-0082289 (2008.09.11) ('Patent Document 2') DETAILED DESCRIPTION OF THE INVENTION technical challenge [15] The present invention is to solve the above problems, and in a separator composite electrode in which a multi-layered inorganic material layer serving as a separator is attached to one surface of the electrode without a separate separator, the pores of the electrode active material layer are not blocked, resulting in battery performance. It is an object of the present invention to provide a method for manufacturing a membrane-integrated electrode having low resistance as well as no degradation. In addition, an object of the present invention is to provide a separator composite electrode having excellent safety even at high temperatures, since there is no separate separator, and the inorganic material layer having a multilayer structure serving as the separator does not include a polymer substrate. means of solving the problem [16] In order to achieve this object, the method for manufacturing a membrane-integrated electrode provided by the present invention includes the steps of: S1) preparing a first inorganic layer slurry containing first inorganic particles and a first binder and having a viscosity of 5000 cP to 20000 cP; S2) Preparing a second inorganic material layer slurry including second inorganic particles and a second binder, S3) preparing a unit electrode having an electrode active material layer formed on at least one surface of an electrode current collector, and S4) unit of step S3) forming a first inorganic material layer composed of the first inorganic slurry on at least one surface of an electrode active material layer, and a second inorganic material layer composed of the second inorganic material slurry on the first inorganic material layer; The diameter of the inorganic particle is larger than the pore size of the electrode active material layer of the unit electrode, the diameter of the second inorganic particle is smaller than the diameter of the first inorganic particle, and the steps S1) to S3) proceed in any order. or two or more can be performed simultaneously. [17] The step S1) may include preparing a first inorganic solution by mixing the first inorganic particles and a first solvent; Preparing a first binder solution by mixing the first binder polymer and the first solvent; and preparing a first inorganic material layer slurry by mixing the first inorganic material solution and the first binder solution. [18] The step S2) may include preparing a second inorganic solution by mixing the second inorganic particles and a second solvent; Preparing a second binder solution by mixing the second binder polymer and the second solvent; and mixing the second inorganic material solution and the second binder solution to prepare a second inorganic material layer slurry. [19] The diameter of the first inorganic particle may be 500 nm to 3 μm, and the diameter of the second inorganic particle may be 20 nm to 300 nm. [20] A dispersant may be further included in the first inorganic material layer slurry of step S1) and/or the second inorganic material layer slurry of step S2). [21] The type of the dispersant is not limited as long as it is generally a material that can be used in a battery. For example, the dispersant may be a mixture of one or more selected from the group consisting of acrylic copolymers. In addition, the dispersing agent may be a mixture of one or more selected from the group consisting of acids. [22] The second inorganic particles may be a mixture of particles having different diameters. [23] The second inorganic particles may be prepared by adding a step of sequentially mixing them in order of smaller diameter in step S2). [24] When mixing the second inorganic particles, the method may further include mixing a dispersant between the mixing of the particles having a small particle size and the mixing of the particles having a large particle size. [25] The first inorganic material layer slurry may have a higher viscosity than the second inorganic material layer slurry. [26] The viscosity of the second inorganic material layer slurry may be 300 cP to 3000 cP. [27] In step S4), the first inorganic material layer slurry and the second inorganic material layer slurry may be simultaneously coated on at least one surface of the electrode active material layer of the unit electrode. [28] In the step S4), the first inorganic material layer slurry is coated on at least one surface of the electrode active material layer of the unit electrode to form the first inorganic material layer, and the second inorganic material layer slurry is coated on the first inorganic material layer. A second inorganic material layer may be formed. [29] A step of laminating each of the first inorganic material layer and/or the second inorganic material layer after formation may be further included. [30] The lamination may be performed at 50 °C to 200 °C. [31] The first inorganic particle and/or the second inorganic particle may include at least one of AlOOH, Al(OH) 3 , and Al 2O 3 . [32] The second inorganic particles may be surface-modified. [33] The first binder polymer and the second binder polymer are the same material, and may differ only in molecular weight or composition ratio of the copolymer. [34] The second binder polymer may have a different chemical component from that of the first binder polymer. [35] The molecular structure of the second binder polymer may be branched. [36] Each of the first inorganic material layer and/or the second inorganic material layer may have a thickness of 3 μm or more and less than 20 μm. Preferably, the thickness of the first inorganic material layer and/or the second inorganic material layer may be 3 μm or more and 10 μm or less. [37] A total thickness of the inorganic material layer, which is the sum of the thickness of the first inorganic material layer and the thickness of the second inorganic material layer, may be less than 30 μm. Preferably, the thickness of the entire inorganic material layer may be 20 μm or less. [38] The first inorganic material layer and the second inorganic material layer may have the same thickness. [39] The present invention may be a membrane-integrated electrode manufactured according to any one of the above-mentioned manufacturing methods. [40] The present invention also provides an electrode assembly including the membrane combination electrode. [41] The present invention also laminates at least one layer of the membrane combination electrode, More about this source textSource text required for additional translation information Send feedback Side panels History Saved Contribute 5,000 character limit. Use the arrows to translate more.It may include the step of manufacturing a unit cell by lamination. [42] The unit cell may be used by charging and discharging 20 times or more. [43] The present invention can be combined by selecting one or two or more of the configurations that do not conflict among the above configurations. Effects of the Invention [44] In the method for manufacturing a membrane-integrated electrode according to the present invention, a first inorganic material layer and a second inorganic material layer having a difference in the diameter and properties of inorganic particles and the properties of a slurry forming the inorganic material layer are formed, and the existing electrode is formed by the first inorganic material layer. It maintains the pores of the electrode, ensures that the pores of the electrode are uniformly formed by the second inorganic material layer, and serves to prevent electrical short circuit. [45] The membrane combination electrode according to the present invention has excellent safety even at high temperatures because it does not have a porous polymer substrate and uses an inorganic material that undergoes an endothermic reaction. In addition, since the electrode active material layer of the unit electrode can maintain the existing pores by the first inorganic material layer, it is possible to provide an electrode assembly with lower resistance than the conventional membrane-combined electrode. As the resistance of the electrode assembly is reduced, the capacity and lifespan of the battery are improved. [46] The present invention also has an excellent effect of preventing electrical short circuits compared to conventional membrane-composite electrodes by controlling the pore size of the second inorganic material layer. Theoretically, when the pores of the second inorganic material layer are reduced to an extent approaching the pore size of the conventional porous polymeric substrate, electrical short circuit is prevented similarly to the conventional porous polymeric substrate, and the durability of the second inorganic material layer and the separator composite electrode is improved. can have the effect of [47] In addition, since there is no separator substrate, the manufacturing method is simple compared to the conventional electrode assembly manufacturing method with a separator substrate, so the electrode assembly manufacturing method and lamination process can be simplified. Brief description of the drawing [48] 1 is a schematic diagram of a conventional membrane-integrated electrode. [49] 2 is a schematic diagram of a membrane-integrated electrode according to a first embodiment of the present invention. [50] 3 is a schematic diagram of a membrane-integrated electrode according to a second embodiment of the present invention. [51] 4 is a schematic diagram of an electrode assembly in which membrane-integrated electrodes are stacked according to the first embodiment of the present invention. [52] 5 is a schematic diagram of an electrode assembly in which membrane-integrated electrodes are stacked according to a third embodiment of the present invention. [53] 6 is a schematic diagram of an electrode assembly in which membrane-integrated electrodes are stacked according to a fourth embodiment of the present invention. [54] 7 is a graph of capacity retention rates after 45 charge/discharge cycles of Comparative Examples and Examples of the present invention. Mode for Carrying Out the Invention [55] Hereinafter, embodiments in which a person skilled in the art can easily practice the present invention will be described in detail. However, when it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention in describing the operating principle of the preferred embodiment of the present invention in detail, the detailed description will be omitted. [56] Throughout the specification, when a part is said to be connected to another part, this includes not only the case where it is directly connected, but also the case where it is indirectly connected with another element interposed therebetween. In addition, including a certain component does not exclude other components unless otherwise stated, but means that other components may be further included. [57] Hereinafter, although described with reference to the examples of the present invention, this is for easier understanding of the present invention, and the scope of the present invention is not limited thereto. [58] Hereinafter, the present invention will be described in more detail. [59] A method for manufacturing a separator-integrated electrode according to the present invention includes the steps of: S1) preparing a first inorganic layer slurry containing first inorganic particles and a first binder and having a viscosity of 5000 cP to 20000 cP; S2) second inorganic particles, preparing a second inorganic material layer slurry containing a binder; S3) preparing a unit electrode having an electrode active material layer formed on at least one surface of an electrode current collector; and S4) at least the unit electrode electrode active material layer of the step S3). forming a first inorganic material layer composed of the first inorganic slurry on one surface and a second inorganic material layer composed of the second inorganic material slurry on the first inorganic material layer, wherein the diameter of the first inorganic particle is The pore size of the unit electrode electrode active material layer is larger, the diameter of the second inorganic particle is smaller than the diameter of the first inorganic particle, and the steps S1) to S3) are performed in any order, or two or more It is characterized by being able to proceed simultaneously. [60] In the step S1), the slurry of the first inorganic material layer may be prepared by mixing the first inorganic particles and the first binder in a first solvent at once. In addition, preparing a first inorganic solution by mixing the first inorganic particles and the first solvent; Preparing a first binder solution by mixing the first binder polymer and the first solvent; and mixing the first inorganic material solution and the first binder solution to prepare a first inorganic material layer slurry. [61] After preparing the first inorganic solution as described above, if a step of preparing a separately prepared first binder solution is performed, there is an advantage in that the viscosity of the first inorganic layer slurry can be easily adjusted. [62] The above method may also be applied to forming the first inorganic material layer slurry. [63] 2 shows a schematic view of a first embodiment of a membrane-integrated electrode manufactured by the manufacturing method according to the present invention. [64] As shown in FIG. 2, the separator combination electrode according to the first embodiment of the present invention includes a unit electrode 250 including an electrode current collector 100 having an electrode active material layer 200 formed on one surface, and a unit electrode 250 The first inorganic material layer 300 and the first inorganic material layer ( 300) and may include a second inorganic material layer 400 including second inorganic particles having a smaller diameter than the first inorganic particles and a second binder polymer. [65] The unit electrode 250 is composed of an electrode current collector 100 and an electrode active material layer 200 formed on at least one surface thereof. Although FIG. 2 includes the electrode active material layer 200 formed on only one surface as an example, the electrode active material layer 200 may be formed on both sides. [66] Therefore, as a possible embodiment of the present invention, a unit electrode according to two combinations of electrode active material layers formed on one side or both sides of an electrode current collector and two combinations of inorganic material layers formed on one side or both sides of the electrode active material layer of the unit electrode are possible. A total of five combinations can be configured. Specifically, a combination of two layers according to the present invention formed on one side of the electrode current collector, a combination of two types of electrode active material layers formed on both sides of the electrode current collector and an inorganic layer formed on each side, and a combination of one inorganic layer formed on both sides of the electrode current collector A total of 5 combinations are possible. [67] The electrode current collector 100 may generally have a thickness of 3 μm to 500 μm. The electrode current collector 100 may form fine irregularities on its surface to increase the adhesion of electrode active materials, and may be used in various physical forms such as films, sheets, foils, nets, porous materials, foams, and nonwoven fabrics. A material used for the electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery. Both the positive electrode current collector and the negative electrode current collector can be used as the electrode current collector of the present invention. [68] The cathode current collector may use one selected from among stainless steel, aluminum, nickel, titanium, and aluminum or stainless steel surface-treated with carbon, nickel, titanium, or silver, preferably aluminum. there is. The negative current collector may be made of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel surface-treated with carbon, nickel, titanium, silver, or the like, or an aluminum-cadmium alloy. [69] The electrode active material layer 200 may be formed on one side or both sides of the electrode current collector 100 . The thickness of the electrode active material layer 200 may vary depending on the capacity of the battery and the type of active material. In general, the electrode active material layer 200 formed on one surface of the electrode current collector 100 may have a thickness of 3 μm to 500 μm. [70] In the case of using a positive electrode current collector in the electrode active material layer 200, the positive electrode active material that can be used is, for example, a layered compound such as lithium nickel oxide (LiNiO2) or a compound substituted with one or more transition metals; lithium manganese oxides such as Li 1+xMn 2-xO 4 (where x is 0 to 0.33), LiMnO 3 , LiMn 2O 3 , and LiMnO 2 ; lithium copper oxide (Li 2 CuO 2 ); Vanadium oxides, such as LiV 3O 8, LiV 3O 4, V 2O 5, and Cu 2V 2O 7; Ni site type lithium nickel oxide represented by the formula LiNi 1-xM xO 2 , where M = Co, Mn, Al, Cu, Fe, Mg, B or Ga, and x = 0.01 to 0.3; Formula LiMn 2-xM xO 2 where M = Co, Ni, Fe, Cr, Zn or Ta and x = 0.0 to 0.1 or Li 2Mn 3MO 8 where M = Fe, Co, Ni, Cu or a lithium manganese composite oxide represented by Zn); LiMn 2 O 4 in which Li part of the formula is substituted with an alkaline earth metal ion; disulfide compounds; It may be composed of Fe 2 (MoO 4) 3 and the like, but is not limited thereto. [71] In the case of using the negative electrode current collector, the negative electrode active material that can be used is, for example, carbon such as non-graphitizing carbon and graphite-based carbon; Li xFe 2O 3 (0≤x≤1), Li xWO 2 (0≤x≤1), Sn xMe 1-xMe' yO z (Me: Mn, Fe, Pb, Ge; Me': Al, B, P , Si, elements of groups 1, 2, and 3 of the periodic table, halogens; 0