Electrode and battery

Abstract

An electrode and a battery of the present invention comprise: an electrode current collector; an electrolyte layer disposed on one surface or both surfaces of the electrode current collector; an electrode active material layer disposed between the electrode current collector and the electrolyte layer; and a support layer disposed between the electrode active material layer and the electrolyte layer and including first inorganic particles and second inorganic particles, wherein the true density of the first inorganic particles may be less than or equal to the true density of the second inorganic particles.

Description

Electrode and battery

[0001] This document claims the benefit of the priority date of Application No. 10-2024-0123138 filed with the Korean Intellectual Property Office on September 10, 2024, and incorporates the entire contents thereof by reference.

[0002] The present invention relates to an electrode.

[0003] The present invention relates to a battery.

[0004] The inorganic separator may include a substrate layer comprising an inorganic material as the main component. The substrate layer of the inorganic separator may be placed directly on the electrode active material layer. The inorganic separator may be integrated with the electrode. The inorganic separator may not easily generate high-temperature thermal shrinkage. When abnormal behavior (abuse), such as mechanical, electrical, and chemical behavior, occurs in the battery, only localized heat generation may occur in the inorganic separator.

[0005] If a battery using an inorganic separator reduces the amount of residual electrolyte, the incidence of heat propagation or runaway can be reduced. Using a gel polymer electrolyte with controlled crystallinity as the electrolyte for this battery can increase the ionic conductivity of the inorganic separator.

[0006] The present invention aims to provide an electrode exhibiting excellent mechanical properties, thermal properties, and ion conductivity.

[0007] The present invention aims to provide a battery exhibiting improved safety.

[0008] An embodiment of the present invention comprises: an electrode current collector; an electrolyte layer disposed on one or both sides of the electrode current collector and comprising a first composition; an electrode active material layer disposed between the electrode current collector and the electrolyte layer; and a support layer disposed between the electrode active material layer and the electrolyte layer and comprising a second composition; wherein the first composition comprises a binder, a crosslinking agent, an initiator, and an electrolyte, and the second composition comprises a first inorganic particle and a second inorganic particle, and the true density of the first inorganic particle is less than or equal to the true density of the second inorganic particle.

[0009] The green density of the first inorganic particle may be greater than the green density of the second inorganic particle.

[0010] The content of the first inorganic particles and the second inorganic particles of the second composition may be greater than the binder content of the first composition.

[0011] The content of the second inorganic particle of the second composition may be 5% by weight or more of the total content of the first inorganic particle and the second inorganic particle of the second composition.

[0012] The active layer may comprise a cured product of the first composition, and the support layer may comprise a dried product of the second composition.

[0013] The average size of the first inorganic particle may be in the range of 100 nm to 500 nm, the average longitudinal length of the second inorganic particle may be in the range of 100 nm to 200 nm, and the average transverse length of the second inorganic particle may be in the range of 25 nm to 50 nm.

[0014] The first inorganic particle and the second inorganic particle may each independently comprise a lithium-containing metal oxide, a lithium-non-containing metal oxide, or a combination thereof.

[0015] The above binder comprises a fluorine-based binder, wherein the fluorine-based binder comprises a first unit derived from vinylidene fluoride and a second unit derived from a fluorine-containing alkyl vinyl compound, wherein the content of the second unit of the fluorine-based binder is in the range of 10% to 50% by weight, and the weight average molecular weight of the fluorine-based binder may be in the range of 300,000 g / mol to 1,000,000 g / mol.

[0016] The above crosslinking agent includes a first polyfunctional crosslinking agent and a second polyfunctional crosslinking agent, and the number of functional groups of the first polyfunctional crosslinking agent may be greater than the number of functional groups of the second polyfunctional crosslinking agent.

[0017] The above initiator may include a photopolymerization initiator.

[0018] The above electrolyte comprises a non-aqueous solvent, a lithium salt, and an electrolyte additive, wherein the non-aqueous solvent comprises ethylene carbonate and ethyl methyl carbonate, the lithium salt comprises LiN(CF3SO2)2, and the electrolyte additive may comprise vinylene carbonate.

[0019] Another embodiment of the present invention comprises: an electrode current collector; an electrolyte layer disposed on one or both sides of the electrode current collector; an electrode active material layer disposed between the electrode current collector and the electrolyte layer; and a support layer disposed between the electrode active material layer and the electrolyte layer; wherein the electrolyte layer comprises a polymeric cross-linked structure and an electrolyte impregnated in the polymeric cross-linked structure, and the support layer comprises a first inorganic particle and a second inorganic particle, and the true density of the first inorganic particle is less than or equal to the true density of the second inorganic particle.

[0020] The electrode active material layer and the support layer can come into contact with each other.

[0021] The first inorganic particle and the second inorganic particle may include boehmite (AlO(OH)).

[0022] The first inorganic particle is a polygonal inorganic particle, and the second inorganic particle may be a plate-shaped inorganic particle or a needle-shaped inorganic particle.

[0023] The thickness per layer of the electrolyte layer is greater than the thickness of the electrode current collector, the thickness per layer of the electrolyte layer is greater than the thickness per layer of the inorganic layer, and the thickness per layer of the inorganic layer may be greater than the thickness of the electrode current collector.

[0024] Another embodiment of the present invention comprises a positive electrode and a negative electrode, wherein at least one of the positive electrode and the negative electrode comprises: an electrode current collector; an electrolyte layer disposed on one or both sides of the electrode current collector; an electrode active material layer disposed between the electrode current collector and the electrolyte layer; and a support layer disposed between the electrode active material layer and the electrolyte layer; wherein the electrolyte layer comprises a polymeric cross-linked structure and an electrolyte impregnated in the polymeric cross-linked structure, and the support layer comprises a first inorganic particle and a second inorganic particle, and the true density of the first inorganic particle is less than or equal to the true density of the second inorganic particle.

[0025] The above positive electrode comprises a positive current collector and a positive active material layer disposed on one or both sides of the positive current collector, and the above negative electrode comprises a negative current collector; a negative electrolyte layer disposed on one or both sides of the negative current collector; a negative active material layer disposed between the negative current collector and the negative electrolyte layer; and a negative support layer disposed between the negative active material layer and the negative electrolyte layer; wherein the negative electrolyte layer comprises a first polymeric crosslinking structure and a first electrolyte impregnated in the first polymeric crosslinking structure, and the negative support layer comprises a first inorganic particle and a second inorganic particle, and the true density of the first inorganic particle may be less than or equal to the true density of the second inorganic particle.

[0026] The above anode further comprises an anode electrolyte layer, the anode active material layer is disposed between the anode current collector and the anode electrolyte layer, and the anode electrolyte layer may comprise a second polymeric crosslinking structure and a second electrolyte impregnated in the second polymeric crosslinking structure.

[0027] Another embodiment of the present invention comprises a first electrode and a second electrode, wherein the first electrode comprises a first electrode current collector, a negative electrolyte layer disposed on one side of the first electrode current collector, a positive active material layer disposed on the other side of the first electrode current collector, a negative active material layer disposed between the first electrode current collector and the negative electrolyte layer, and a negative support layer disposed between the negative electrolyte layer and the negative active material layer, and the second electrode comprises a second electrode current collector, a negative electrolyte layer disposed on one side of the second electrode current collector, a positive active material layer disposed on the other side of the second electrode current collector, a negative active material layer disposed between the second electrode current collector and the negative electrolyte layer, and a negative support layer disposed between the negative electrolyte layer and the negative active material layer, wherein the negative electrolyte layer comprises a first polymeric crosslinking structure and a first electrolyte impregnated in the first polymeric crosslinking structure, and the negative support layer comprises a first inorganic particle and a second inorganic It is a battery containing particles, wherein the true density of the first inorganic particle is less than or equal to the true density of the second inorganic particle.

[0028] The first electrode and the second electrode further comprise an anode electrolyte layer, and the anode active material layer is disposed between the first electrode current collector and the anode electrolyte layer and between the second electrode current collector and the anode electrolyte layer, and the anode electrolyte layer may comprise a second polymeric crosslinking structure and a second electrolyte impregnated in the second polymeric crosslinking structure.

[0029] The electrode of the present invention can exhibit excellent mechanical properties, thermal properties, and ionic conductivity.

[0030] The battery of the present invention can exhibit improved safety.

[0031] Figure 1 is a schematic diagram of the electrode of the present invention.

[0032] FIG. 2 is a schematic diagram of an exemplary battery of the present invention.

[0033] FIG. 3 is a schematic diagram of another exemplary battery of the present invention.

[0034] FIG. 4 is a schematic diagram of another exemplary battery of the present invention.

[0035] FIG. 5 is a schematic diagram of another exemplary battery of the present invention.

[0036] Figure 6 is an SEM image of the first inorganic particle used in an embodiment of the present invention.

[0037] Figure 7 is an SEM image of the second inorganic particle used in an embodiment of the present invention.

[0038] Figure 8 is an SEM image of another second inorganic particle used in an embodiment of the present invention.

[0039] This document may use ordinal numbers such as “first” and “second” when referring to multiple components. There is no priority among the components.

[0040] In this document, if a specific commercially available product is used as an ingredient, the characteristics of that ingredient may refer to the characteristics listed in the product's Technical Data Sheet (TDS) or Certification of Analysis (COA).

[0041] In this document, if the physical properties of a specific material vary depending on temperature and pressure, the measurement criteria for those physical properties may be 25 ℃ and 101.325 kPa.

[0042] In this document, the numerical range “A to B” means “A or greater and B or less.”

[0043] The numbers mentioned in this document are rounded values. For example, 1.5 is a number within the range of 1.45 to 1.54.

[0044] The present document describes the invention in more detail below.

[0045] One embodiment (Embodiment) of the present invention is an electrode.

[0046] The electrode of the present invention can be integrated with a separator. The electrode can be integrated with a separator and an electrolyte. Therefore, a battery comprising the electrode integrated with the separator and electrolyte of the present invention may differ from a conventional battery in that it does not require a separate separator and an electrolyte.

[0047] In an electrode integrated with a separator, the integrated structure of the electrode and the separator can be treated as a single unit. That is, the electrode of the present invention does not treat the separator as a separate component from the electrode.

[0048] Figure 1 is a schematic diagram of the electrode of the present invention.

[0049] Referring to FIG. 1, the electrode (ETD) may include an electrode current collector (EC), an electrolyte layer (EL) disposed on one or both sides of the electrode current collector (EC), an electrode active material layer (AM) disposed between the electrode current collector (EC) and the electrolyte layer (EL), and a support layer (SP) disposed between the electrode active material layer (AM) and the electrolyte layer (EL).

[0050] The above support layer can support the electrolyte layer by including inorganic particles.

[0051] The electrolyte layer may be disposed at the outermost edge of the electrode. The electrolyte layer may be disposed at the top, bottom, or both of the top and bottom of the electrode.

[0052] The above electrode current collector is a member that supports the electrode. The components included in the above electrode current collector may vary depending on the polarity exhibited by the electrode.

[0053] If the above electrode is a negative electrode, the electrode current collector may include one or more materials selected from the group consisting of copper, gold, and nickel. Preferably, the electrode current collector may include a copper film.

[0054] If the electrode is a positive electrode, the electrode current collector may include one or more materials selected from the group consisting of aluminum and nickel. Preferably, the electrode current collector may include an aluminum film.

[0055] The electrode active material layer may be disposed between the electrode current collector and the electrolyte layer. The components constituting the electrode active material layer may vary depending on the polarity of the electrode.

[0056] If the above electrode is a negative electrode, the electrode active material layer may include a lithium intercalation material. The lithium intercalation material may include one or more selected from the group consisting of lithium-based metals and carbon-based compounds.

[0057] The above lithium-based metal may include one or more selected from the group consisting of lithium metal and lithium alloy.

[0058] The above carbon-based compound may include one or more selected from the group consisting of carbon, petroleum coke, activated carbon, and graphite.

[0059] If the electrode is a positive electrode, the electrode active material layer may include a lithium adsorption material. The lithium adsorption material may include a lithium transition metal oxide. The lithium transition metal oxide may include one or more selected from the group consisting of lithium manganese oxide, lithium cobalt oxide, lithium nickel oxide and lithium iron oxide, lithium nickel-manganese oxide, lithium nickel-cobalt oxide, and lithium nickel-manganese-cobalt oxide.

[0060] The electrolyte layer may be disposed on one or both sides of the electrode current collector. The electrode current collector may include a first surface and a second surface facing the first surface. The electrolyte layer may be disposed on the first surface, the second surface, or both the first surface and the second surface of the electrode current collector. The support layer may be disposed between the electrode current collector and the electrolyte layer.

[0061] The electrolyte layer and the support layer can prevent physical contact between the positive and negative electrodes in the battery. The electrolyte layer can move the charge medium (e.g., lithium ions) of the battery between the electrodes.

[0062] The above electrolyte layer may include a polymer component and an electrolyte. The electrolyte may be impregnated into the polymer component. The electrolyte may swell the polymer component. The polymer component may swell to exhibit a gel phase.

[0063] The above electrolyte layer may include a curable composition. Specifically, the electrolyte layer may be formed by curing the curable composition. This curable composition may be distinguished from the composition forming the support layer described below, which is referred to as the first composition. The method of curing may include, for example, thermal curing, photocuring, and thermal-photo dual curing. Preferably, the method of curing may be photocuring.

[0064] A cured product of a composition may refer to a composition that has undergone a chemical process in which it hardens or solidifies as the structure of the components contained in the composition changes due to chemical reactions between those components. This curing may differ from drying, which is a physical process in which a portion of the composition dries or hardens as some of the components contained in the composition (e.g., solvents such as water, volatile components) evaporate.

[0065] The first composition may include a binder and an electrolyte. When the first composition is cured, the binder may form a polymer component. The electrolyte may be impregnated into the polymer component. The polymer component may be a polymeric cross-linked structure.

[0066] The first composition may further include a crosslinking agent and an initiator. When the first composition is cured, the crosslinking agent may form a polymeric crosslinked structure by connecting the crosslinking agents, the binders, and between the crosslinking agent and the binder. When an external force (heat, light, or heat and light) is applied for curing the first composition, the initiator may start a crosslinking reaction between the binder and the crosslinking agent.

[0067] The electrode of the present invention may include a plurality of inorganic particles having different characteristics. The electrode may include the plurality of inorganic particles as a separate layer (the support layer) from the electrolyte layer. The support layer may be disposed between the electrode current collector and the electrolyte layer. The support layer may include the plurality of inorganic particles. Specifically, the support layer may be formed by drying a composition containing a plurality of inorganic particles. This composition may be referred to as a second composition to distinguish it from the first composition described above. The support layer may include a dried product of the second composition. The support layer supports the electrolyte layer and can protect the electrode current collector and the electrode active material layer from external physical stimuli. As a result, the dielectric breakdown voltage of the support layer may increase while maintaining the ion conductivity of the electrode.

[0068] The dried product of a composition may refer to a physical process in which a portion of the composition dries or hardens as some of the components contained in the composition (e.g., solvents such as water, volatile components) evaporate. The above-mentioned curing may differ from drying, which is a chemical process in which the composition hardens or solidifies as the structure of the components contained in the composition changes due to chemical reactions between those components.

[0069]

[0070] The second composition may include a first inorganic particle and a second inorganic particle. The first inorganic particle and the second inorganic particle may differ in particle size, particle shape, density, etc. The true density of the first inorganic particle may be equal to or different from the true density of the second inorganic particle. The true density of the first inorganic particle may be less than or equal to the true density of the second inorganic particle.

[0071] In this way, when the support layer contains different inorganic particles and the electrolyte layer contains a polymer component impregnated with an electrolyte, and the support layer and the electrolyte layer are composed of separate layers, the uniformity of the cross-linking structure within the electrolyte layer, specifically the pore structure within the electrolyte layer, can be improved. In addition, damage to the electrode current collector and the electrode active material layer caused by lithium dendrites can be reduced.

[0072] In this document, a uniform pore structure may refer to a structure in which the average size, shape, and density of the pores are nearly constant regardless of the position within the layer, thereby maintaining a constant material transport path within the layer. A uniform pore structure may refer to a state in which the variation in the size and spatial distribution of the pores is small throughout the entire layer containing the pores, the pores are continuously connected to one another, and the pores are not localized in a specific direction or position.

[0073] Although the detailed mechanism is not certain, the following is speculated. When the polymer component impregnated with the electrolyte and the inorganic particles are composed of an electrolyte layer and a support layer, respectively, scattering by the inorganic particles during UV irradiation in the electrolyte layer can be suppressed. Accordingly, the rate of the cross-linking reaction of the polymer component can be maintained uniformly regardless of the location within the electrolyte layer. In addition, inorganic particles of different true densities can form a dense structure in the support layer. Accordingly, the current density applied to the electrode can be maintained uniformly regardless of the application surface.

[0074] In this document, the true density of a particle may refer to the density calculated solely from the mass and volume of the particle itself, excluding voids within the particle. The true density of the inorganic particle may be a known value for the inorganic particle or a value measured according to known methods. The true density of the inorganic particle may be determined by the chemical composition of the inorganic particle.

[0075] True density of the first inorganic particle and the second inorganic particle [g / cm²] 3 ] may each independently be within the range of 2 to 5. Preferably, the true density [g / cm²] of the first inorganic particle and the second inorganic particle is 3 Each of these can independently range from 3 to 4.

[0076] The characteristics of the first inorganic particle and the second inorganic particle can be further controlled to form a more uniform pore structure of the electrolyte layer.

[0077] The green density of the first inorganic particle may be greater than the green density of the second inorganic particle.

[0078] In this document, the green density of the particles (compact density) may refer to the density of the particles in a state where they have been processed into a compact of a predetermined shape. The green density is a density that reflects not only the density of the particles themselves but also the voids between the particles. The method for measuring the green density of the inorganic particles is described in detail in the examples.

[0079] That is, in the second composition, the second inorganic particles may be arranged less densely, and the first inorganic particles may be arranged more densely. As a result, a structure in which the first inorganic particles fill the pores formed by the second inorganic particles may be formed in the support layer. When pores of uniform distribution are formed in the support layer, the ion conduction path becomes uniform, which can reduce the electrical resistance of the electrode, reduce the variation in local current density, which can reduce the amount of lithium dendrites in the battery, and maintain the mechanical properties of the electrode evenly.

[0080] Green density of the above first inorganic particle [g / cm²] 3 ] may be in the range of 1 to 3. Preferably, the green density [g / cm³] of the first inorganic particle is green. 3 ] may be in the range of 1.2 to 2.5. More preferably, the green density [g / cm³] of the first inorganic particle is more preferably. 3 ] can be in the range of 1.3 to 1.5.

[0081] Green density of the above second inorganic particle [g / cm²] 3 ] may be in the range of 0.5 to 2.5. Preferably, the green density [g / cm³] of the second inorganic particle is 3 ] may be in the range of 0.7 to 1.5. More preferably, the green density [g / cm³] of the second inorganic particle is 3 ] can be in the range of 0.9 to 1.0.

[0082] The BET specific surface area of ​​the first inorganic particle may differ from the BET specific surface area of ​​the second inorganic particle. Preferably, the BET specific surface area of ​​the first inorganic particle may be smaller than the BET specific surface area of ​​the second inorganic particle.

[0083] The above support layer includes inorganic particles with different BET specific surface areas to increase the electrolyte impregnation amount and simultaneously maintain a stable pore structure, thereby optimally maintaining the ion conduction pathway. As a result, a battery including the electrode can mitigate electrolyte consumption or concentration variations, thereby improving its lifespan.

[0084] BET specific surface area of ​​the first inorganic particle [m² 2 [ / g] may be in the range of 50 to 100. Preferably, the BET specific surface area [m²] of the first inorganic particle 2 [ / g] may be in the range of 55 to 85. More preferably, the BET specific surface area [m²] of the first inorganic particle 2 [ / g] can be in the range of 60 to 70.

[0085] BET specific surface area of ​​the above second inorganic particle [m² 2 [ / g] may be in the range of 70 to 150. Preferably, the BET specific surface area [m²] of the second inorganic particle 2 [ / g] may be in the range of 85 to 130. More preferably, the BET specific surface area [m²] of the second inorganic particle 2 [ / g] can be in the range of 95 to 105.

[0086] The content relationship of the inorganic particles and binder in the electrode, specifically the first composition and the second composition, can be appropriately controlled.

[0087] The content of the binder included in the first composition may be greater than the total content of the inorganic particles included in the second composition. Among the remaining components excluding the electrolyte in the first and second compositions, the content of the binder may be greater than the content of the inorganic particles. In this case, the binder may form a more uniform polymeric cross-linked structure in the electrolyte layer.

[0088] In this document, the statement that the polymeric crosslinked structure is uniform may mean that the positional variation of physical properties such as crosslinking density and gel fraction is small throughout the electrolyte layer, and that electrochemical properties such as mechanical properties or ion conductivity do not change locally (within the margin of error).

[0089] Among the remaining components excluding the electrolyte in the first composition and the second composition, the content of inorganic particles may be greater than the content of the binder. The total content of the first inorganic particles and the second inorganic particles in the second composition may be greater than the content of the binder in the first composition. In this case, the inorganic particles can suppress dendrite growth by making the distribution of the current applied to the support layer uniform, thereby reducing damage to the electrode current collector and the electrode active material layer. As a result, physical properties such as heat resistance and impact resistance of the electrode can also be improved.

[0090] The content ratio between the first inorganic particle and the second inorganic particle in the second composition can also be adjusted.

[0091] The content of the second inorganic particle of the second composition may be 5% by weight or more of the total content of the first inorganic particle and the second inorganic particle of the second composition. The content of the second inorganic particle may be 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, or 30% by weight or more. The content of the second inorganic particle may be 50% by weight or less, 45% by weight or less, 40% by weight or less, 35% by weight or less, or 30% by weight or less.

[0092] The first inorganic particle and the second inorganic particle may be dispersed in the support layer. The first inorganic particle and the second inorganic particle may be arranged in a dispersed state in a separate layer distinguished from the electrolyte layer. The inorganic particles dispersed in this way can form a uniform pore structure in the support layer due to the aforementioned relationship of true density, etc. The uniform pore structure of the support layer can enhance the ion transport performance of the electrode.

[0093] The relationship of true density between the first inorganic particle and the second inorganic particle can be determined according to the chemical composition of the compounds constituting the first inorganic particle and the second inorganic particle. The chemical composition of the compounds constituting the first inorganic particle and the second inorganic particle may vary depending on whether they are involved in the transport of lithium ions in the battery.

[0094] The first inorganic particle and the second inorganic particle may each independently participate in the transport of lithium ions, not participate in the transport of lithium ions, or partially participate and partially not participate. The first inorganic particle and the second inorganic particle may each independently include a lithium-containing metal oxide, a lithium-non-containing metal oxide, or a combination thereof.

[0095] The above lithium-containing metal oxide may include one or more selected from the group consisting of lithium aluminum germanium phosphate (LAGP)-based compounds, lithium lanthanum zirconium oxide (LLZO)-based compounds, lithium aluminum titanium phosphate (LATP)-based compounds, lithium lanthanum zirconium tantalum oxide (LLZTO)-based compounds, lithium silicon titanium phosphate (LSTP)-based compounds, and lithium oxide.

[0096] The above lithium-free metal oxide may include one or more selected from the group consisting of zinc oxide (ZnO), calcium carbonate (CaCO3), silicon dioxide (SiO2), alumina (Al2O3), boehmite (Al(O)OH), barium titanate (BaTiO3), barium sulfate (BaSO4), and titanium dioxide (TiO2).

[0097] Preferably, the first inorganic particle and the second inorganic particle may include boehmite.

[0098] The green density relationship between the first inorganic particle and the second inorganic particle can be determined according to the shape and size of each of the first inorganic particle and the second inorganic particle. As previously mentioned, the shape of the first inorganic particle may differ from the shape of the second inorganic particle.

[0099] The first inorganic particle mentioned above may be a polygonal inorganic particle.

[0100] The second inorganic particle may be a polygonal inorganic particle, an acicular inorganic particle, or a plate-shaped inorganic particle. Preferably, the second inorganic particle may be an acicular inorganic particle or a plate-shaped inorganic particle. More preferably, the second inorganic particle may be an acicular inorganic particle.

[0101] In this document, a polygonal particle may refer to a polyhedral particle whose outer edge is composed of several straight lines. When the maximum length, maximum width, and maximum thickness of the polygonal particle are L, W, and T, respectively, L / W and W / T may each be within the range of 1 to 3. The shape of the polyhedron constituting the polygonal particle is not particularly limited. The polygonal particle may be a particle having a polyhedral shape that satisfies the conditions of L, W, and T described above.

[0102] In this document, needle-shaped particles may refer to particles that are long and thin like needles or fibers, with a length that is very long compared to their thickness or width. When the maximum length, maximum width, and maximum thickness of the needle-shaped particles are L, W, and T, respectively, L / W or L / T may be 3 or greater.

[0103] In this document, plate-shaped particles may refer to particles that are flat like a plate because their thickness is very thin compared to their length or width. When the maximum length, maximum width, and maximum thickness of the plate-shaped particles are L, W, and T, respectively, L / T or W / T may be 3 or greater.

[0104] The size of each of the first inorganic particle and the second inorganic particle can also be adjusted by considering the relationship between the true density and green density of each inorganic particle.

[0105] The average size of the first inorganic particle may be in the range of 100 nm to 500 nm. Preferably, the average size of the first inorganic particle may be in the range of 150 nm to 450 nm. More preferably, the average size of the first inorganic particle may be in the range of 200 nm to 400 nm. Most preferably, the average size of the first inorganic particle may be in the range of 250 nm to 350 nm.

[0106] Preferably, the second inorganic particle is a needle-shaped particle, and the transverse length and longitudinal length of the second inorganic particle can each be adjusted. The longitudinal length of the second inorganic particle may be longer than the transverse length of the second inorganic particle.

[0107] The average longitudinal length of the second inorganic particle may be in the range of 100 nm to 200 nm. Preferably, the average longitudinal length of the second inorganic particle may be in the range of 130 nm to 170 nm. More preferably, the average longitudinal length of the second inorganic particle may be in the range of 150 nm to 160 nm.

[0108] The average transverse length of the second inorganic particle may be in the range of 25 nm to 50 nm. Preferably, the average transverse length of the second inorganic particle may be in the range of 30 nm to 45 nm. More preferably, the average transverse length of the second inorganic particle may be in the range of 35 nm to 40 nm.

[0109] The longitudinal length of the second inorganic particle may refer to the maximum length of the second inorganic particle. The transverse length of the second inorganic particle may refer to the longer length among the dimensions measured in a direction orthogonal to the longitudinal direction.

[0110] The average longitudinal length of the second inorganic particle can be measured using an electron microscope image of the second inorganic particle. The average of the number of inorganic particles with the maximum length of each second inorganic particle identified in the electron microscope image may be the average longitudinal length of the second inorganic particle. Additionally, the average of the number of inorganic particles with a length perpendicular to the maximum length of each second inorganic particle measured in the electron microscope image may be the average transverse length of the second inorganic particle.

[0111] The binder can form a framework in the electrolyte layer formed by the first composition. The binder may have appropriate crystallinity and polarity to enable the composite electrolyte to exhibit appropriate ionic conductivity. In particular, the polar portion of the binder may combine with a crosslinking agent described later. In this case, the binder may form a crosslinked structure in the electrolyte layer.

[0112] The above binder may include a fluorine-based binder. The above fluorine-based binder may refer to a binder whose constituent unit contains fluorine as part or all. The above fluorine-based binder may include a PVDF-based binder.

[0113] The above PVDF-based binder may be a homopolymer or copolymer comprising a polymerization unit derived from vinylidene fluoride. The above fluorine-based binder may comprise a first unit derived from vinylidene fluoride and a second unit derived from a fluorine-containing alkyl vinyl compound. The above PVDF-based binder may be a block copolymer or a random copolymer comprising the first unit and the second unit. Preferably, the above PVDF-based binder may be a random copolymer comprising the first unit and the second unit.

[0114] The above fluorine-containing alkyl vinyl compound is C n H (2n+1-y) F y It may mean a compound in which at least one fluorine-containing alkyl group represented by is bonded to a vinyl group. However, vinylidene fluoride is excluded.

[0115] The fluorine-containing alkyl vinyl compound may include one or more selected from the group consisting of vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, and hexafluoropropylene. Preferably, the fluorine-containing alkyl vinyl compound may include one or more selected from the group consisting of hexafluoropropylene, tetrafluoroethylene, and chlorotrifluoroethylene. More preferably, the fluorine-containing alkyl vinyl compound may include hexafluoropropylene.

[0116] The second unit content of the above-mentioned fluorine-based binder can be adjusted. The second unit content of the above-mentioned fluorine-based binder can affect the crystallinity of the above-mentioned fluorine-based binder, the ionic conductivity of the above-mentioned battery, and the mechanical strength.

[0117] The second unit content of the fluorine-based binder may be in the range of 10% to 50% by weight. Preferably, the second unit content of the fluorine-based binder may be in the range of 20% to 45% by weight. More preferably, the second unit content of the fluorine-based binder may be in the range of 25% to 40% by weight. Even more preferably, the second unit content of the fluorine-based binder may be in the range of 30% to 35% by weight.

[0118] The first and second unit contents of the above fluorine-based binder are relative to the above fluorine-based binder 19 It can be measured by F-NMR analysis.

[0119] The weight-average molecular weight of the fluorine-based binder can also be controlled. The weight-average molecular weight of the fluorine-based binder may be in the range of 300,000 g / mol to 1,000,000 g / mol. Preferably, the weight-average molecular weight of the fluorine-based binder may be in the range of 350,000 g / mol to 800,000 g / mol. More preferably, the weight-average molecular weight of the fluorine-based binder may be in the range of 450,000 g / mol to 600,000 g / mol. Even more preferably, the weight-average molecular weight of the fluorine-based binder may be in the range of 500,000 g / mol to 550,000 g / mol.

[0120] The weight average molecular weight of the above fluorine-based binder can be measured by gel permeation chromatography.

[0121] The melting point of the above fluorine-based binder can also be controlled. The melting point of the above fluorine-based binder may be in the range of 100 ℃ to 140 ℃. Preferably, the melting point of the above fluorine-based binder may be in the range of 105 ℃ to 135 ℃. More preferably, the melting point of the above fluorine-based binder may be in the range of 110 ℃ to 130 ℃. Even more preferably, the melting point of the above fluorine-based binder may be in the range of 115 ℃ to 125 ℃.

[0122] The melting point of the above fluorine-based binder can be measured by differential scanning calorimetry (DSC).

[0123] The above-mentioned crosslinking agent can form a crosslinking structure either by itself or together with the above-mentioned binder.

[0124] The above cross-linked structure may be formed by a bond between a functional group having the binder and a functional group having the cross-linking agent. The cross-linking agent may have a photoreactive functional group. The cross-linked structure formed by the binder may be formed by a bond between a functional group having the binder and a photoreactive functional group. The cross-linked structure formed by the binder may be formed by applying an external force to the first composition. Specifically, the cross-linked structure may be formed by applying heat or light to the first composition. More specifically, the cross-linked structure may be formed by applying light to the first composition.

[0125] The above-mentioned crosslinking structure may be formed by at least two binders being bonded via a crosslinking agent, or by crosslinking agents being bonded to each other. Since the crosslinking agent acts as a medium, the crosslinking agent may include a polyfunctional crosslinking agent. The crosslinking agent may include two or more crosslinking functional groups. The crosslinking functional groups may be functional groups involved in the above-mentioned crosslinking structure.

[0126] The crosslinking agent may include two or more photoreactive functional groups. The crosslinking agent may include a (meth)acrylate group as the photoreactive functional group. The crosslinking agent may include a polyfunctional (meth)acrylate. The crosslinking agent may include a compound comprising at least two (meth)acrylate groups.

[0127] The above (meth)acrylate group may mean an acrylate group or a methacrylate group. The above (meth)acrylate group may mean a monovalent functional group derived from an ester of (meth)acrylic acid.

[0128] The above crosslinking agent may include polyfunctional crosslinking agents having different numbers of functional groups. The crosslinking agent includes a first polyfunctional crosslinking agent and a second polyfunctional crosslinking agent, and the number of functional groups of the first polyfunctional crosslinking agent may be greater than the number of functional groups of the second polyfunctional crosslinking agent.

[0129] In this document, the number of crosslinkable functional groups for each crosslinking agent may refer to the number of crosslinkable functional groups per molecule of each crosslinking agent.

[0130] The number of functional groups of the first polyfunctional crosslinking agent may be 3 or more. The number of functional groups of the second polyfunctional crosslinking agent may be 2 or more.

[0131] The first polyfunctional crosslinking agent may be a monomeric crosslinking agent. The second polyfunctional crosslinking agent may be a polymeric crosslinking agent.

[0132] The above-mentioned monomeric crosslinking agent may mean that the remaining moiety, excluding the crosslinking functional group, originates from the monomer. The above-mentioned polymeric crosslinking agent may mean that the remaining moiety, excluding the crosslinking functional group, originates from the polymer.

[0133] The first multifunctional crosslinking agent may include one or more selected from the group consisting of trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), pentaerythritol triacrylate (PETA), and pentaerythritol trimethacrylate (PETMA). Preferably, the first multifunctional crosslinking agent may include trimethylolpropane triacrylate (TMPTA).

[0134] The second multifunctional crosslinking agent may include one or more selected from the group consisting of polyethylene glycol diacrylate (PEGDA), polyethylene glycol dimethacrylate (PEGDMA), polyurethane diacrylate (PUDA), and polyurethane dimethacrylate (PUDMA). Preferably, the second multifunctional crosslinking agent may include polyurethane diacrylate.

[0135] If the second multifunctional crosslinking agent is a polymeric crosslinking agent, the molecular weight of the second multifunctional crosslinking agent can also be controlled. The second multifunctional crosslinking agent may include one or more selected from the group consisting of polyethylene glycol diacrylate with a molecular weight in the range of 400 Da to 700 Da and polyurethane diacrylate with a molecular weight in the range of 1400 Da to 2100 Da.

[0136] An initiator (thermal polymerization initiator or photopolymerization initiator) can form a cross-linked structure of a polymer component derived from the binder. Preferably, the first composition may include a photopolymerization initiator.

[0137] The above photopolymerization initiator may include one or more selected from the group consisting of short-wavelength photopolymerization initiators and long-wavelength photopolymerization initiators.

[0138] The above short-wavelength photopolymerization initiator may include one or more selected from the group consisting of IRGACURE 127 (1,1'-(Methylene-di-4,1-phenylene)bis[2-hydroxy-2-methyl-1-propanone]), IRGACURE 1173 (2-Hydroxy-2-methylpropiophenone, HMPP), DMPA (2,2-dimethoxy-2-phenylacetonephenone), HOMPP (2-hydroxy-2-methylpropipphenone), and LAP (Lithium phenyl-2,4,6-trimethylbenzoylphosphinate).

[0139] The above long-wavelength photopolymerization initiator may include one or more selected from the group consisting of Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide and Ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate.

[0140] The above electrolyte may be impregnated into the binder, specifically a polymer component, and more specifically, a polymeric cross-linked structure formed by the binder. The above electrolyte may include a non-aqueous solvent, a lithium salt, and an electrolyte additive. The lithium salt may be dissolved in the non-aqueous solvent.

[0141] The above-mentioned non-aqueous solvent may refer to an organic solvent that does not contain water or, even if water is included, contains only trace amounts. The above-mentioned non-aqueous solvent may include one or more selected from the group consisting of propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), dimethyl sulfoxide, acetonitrile, dimethoxyethane, diethoxyethane, tetrahydrofuran, N-methyl-2-pyrrolidone (NMP), ethylmethyl carbonate (EMC), and gamma-butyrolactone (γ-butyrolactone).

[0142] A carbonate-based solvent can be used as the solvent for the electrolyte of a lithium secondary battery. The above-mentioned non-aqueous solvent may include one or more selected from the group consisting of propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and dipropyl carbonate (DPC).

[0143] Preferably, the non-aqueous solvent may include ethylene carbonate and ethyl methyl carbonate. More preferably, the non-aqueous solvent may include ethylene carbonate and ethyl methyl carbonate, and the non-aqueous solvent may include more ethyl methyl carbonate than ethylene carbonate.

[0144] The above lithium salt may refer to a material that decomposes into lithium cations and anions upon dissociation. The above lithium salt may include one or more selected from the group consisting of LiPF6, LiBF4, LiCl, LiBr, LiI, LiClO4, LiAsF6, LiCH3CO2, LiCF3SO3, LiN(CF3SO2)2, LiN(FSO2)2, and LiC(CF2SO2)3. Preferably, the lithium salt comprises LiN(CF3SO2)2 It can be included.

[0145] The above electrolyte additive may refer to a substance applied in small amounts to the electrolyte for the purpose of stabilizing the electrode interface, improving electrochemical stability, controlling conductivity characteristics, improving temperature characteristics, suppressing gas generation, etc. The above electrolyte additive may include one or more selected from the group consisting of vinylene carbonate, 1,3-propane sultone, 1,3-propene sultone, lithium difluorophosphate, lithium tetrafluoro(oxalate)phosphate, lithium bis(fluorosulfonyl)imide, fluoroethylene carbonate, and vinyl ethylene carbonate. Preferably, the above electrolyte additive may include vinylene carbonate.

[0146] The second composition may further include a binding binder. The binding binder may bind the inorganic particles or the inorganic particles to the support layer.

[0147] The above binding binder is polymethylmethacrylate, polybutylacrylate, polybutylmethacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate, polyethylene-co-vinyl acetate copolymer, polyethylene oxide, polyarylate, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, It may include one or more selected from the group consisting of pullulan and carboxyl methyl cellulose.Preferably, the binding binder may include one or more selected from the group consisting of polymethylmethacrylate, polybutylacrylate, polybutylmethacrylate, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and carboxyl methyl cellulose.

[0148] Since the electrolyte is impregnated into the binder or the cross-linked structure formed by the binder in the electrolyte layer, the thickness of the electrolyte layer may generally be thick. Specifically, the electrolyte layer may be thicker than the support layer and the electrode current collector. In this case, the thickness of the electrolyte layer refers to the thickness per layer.

[0149] The above-mentioned inorganic particles may also be arranged in the support layer with an appropriate density relationship to form a predetermined layered structure. In this case, the thickness of the support layer may be greater than the thickness of the electrode current collector. The thickness of the support layer may be smaller than the thickness of the electrolyte layer.

[0150] The drying of the second composition and the UV curing of the first composition may be applied in a manner that forms the support layer and the electrolyte layer of the substrate layer. Drying of the composition is a process of volatilizing or evaporating the liquid within the composition by leaving the composition at room temperature or heating it to an appropriate temperature. UV curing can form cross-linked structures between binders within the composition, between binders and crosslinking agents, and between crosslinking agents using external force.

[0151] In the electrode of the present invention, the process of forming a support layer by drying the second composition and the process of forming an electrolyte layer by UV curing the first composition may proceed sequentially. The above process may include the following steps. The number of each step does not indicate the order of each step:

[0152] (1) Prepare a second composition comprising a first inorganic particle, a second inorganic particle, a dispersion medium, and a binding binder;

[0153] (2) Prepare a first composition comprising a binder, a crosslinking agent, a photopolymerization initiator, and an electrolyte;

[0154] (3) Applying and drying the second composition on one or both sides of an electrode (including an electrode current collector and an electrode active material layer on one or both sides thereof) to form a support layer;

[0155] (4) Applying the first composition onto the support layer;

[0156] (5) Irradiate the above-mentioned first composition with UV light.

[0157] In the above (1) and (2) processes, the preparation of the composition may include directly manufacturing the composition or applying a previously manufactured composition.

[0158] Conditions such as the application method and thickness of each composition are not particularly limited.

[0159] The conditions of UV irradiation applied to the first composition above are not particularly limited.

[0160] Another embodiment of the present invention is also an electrode.

[0161] In the description of the electrode in the present embodiment, any description that overlaps with the description of the electrode in the aforementioned embodiment may be omitted.

[0162] The electrode of the present embodiment may include an electrode current collector, an electrolyte layer, an electrode active material layer, and a support layer.

[0163] The electrolyte layer may be disposed on one or both sides of the electrode current collector. The electrode active material layer may be disposed between the electrode current collector and the electrolyte layer. The support layer may be disposed between the electrode active material layer and the electrolyte layer.

[0164] The electrode of the aforementioned embodiment may primarily consist of the first composition used to form the electrolyte layer and the second composition used to form the support layer, respectively. The electrode of the present embodiment may primarily consist of the electrolyte layer and the heat-resistant layer, respectively.

[0165] In the electrode of the present embodiment, the electrolyte layer may comprise a polymeric cross-linked structure and an electrolyte. The electrolyte may be impregnated into the polymeric cross-linked structure.

[0166] The above polymeric crosslinked structure may be formed by a crosslinking reaction of the binder, crosslinking agent, and initiator of the first composition described above. The above polymeric crosslinked structure may include components derived from each of the binder, the crosslinking agent, and the initiator. The description of the binder, the crosslinking agent, and the initiator is the same as that described for the electrode of the aforementioned specific example.

[0167] In this document, components derived from a specific substance may include the component itself or derivatives thereof.

[0168] The above electrolyte can be impregnated into the above polymeric cross-linked structure.

[0169] The above support layer may include inorganic particles. The inorganic particles may include a plurality of different inorganic particles. The inorganic particles may include a first inorganic particle and a second inorganic particle. The first inorganic particle may be different from the second inorganic particle. The description of the two different inorganic particles is the same as that described in the electrode of the aforementioned specific example.

[0170] In the electrode of the present embodiment, the true density of the first inorganic particle may be less than or equal to the true density of the second inorganic particle, just like the electrode of the aforementioned embodiment.

[0171] The electrode of the present embodiment differs from conventional electrodes in that it does not include a polymer substrate layer. Typically, a polymer substrate layer can be disposed between an electrode active material layer and an inorganic coating layer. In the electrode of the present embodiment, a separate layer may not be disposed between the electrode active material layer and the support layer (containing inorganic material). The electrode active material layer and the support layer may come into contact with each other.

[0172] The chemical composition of the first inorganic particle and the second inorganic particle is also the same as that mentioned in the electrode of the aforementioned specific example.

[0173] Preferably, the first inorganic particle and the second inorganic particle may each independently comprise alumina (Al2O3) or boehmite (AlO(OH)). More preferably, the first inorganic particle and the second inorganic particle may comprise boehmite (AlO(OH)).

[0174] The shapes of the first inorganic particle and the second inorganic particle are also the same as those mentioned in the electrode of the aforementioned specific example.

[0175] The first inorganic particle mentioned above may be a polygonal inorganic particle.

[0176] The second inorganic particle may be a polygonal inorganic particle, an acicular inorganic particle, or a plate-shaped inorganic particle. Preferably, the second inorganic particle may be an acicular inorganic particle or a plate-shaped inorganic particle.

[0177] As described above, since the electrolyte is impregnated into the polymeric cross-linked structure in the electrolyte layer, the thickness of the electrolyte layer may generally be thick. Specifically, the electrolyte layer may be thicker than the electrode current collector and the support layer. The thickness of the electrolyte layer refers to the thickness per layer.

[0178] In addition, all remaining layers of the electrode excluding the electrode current collector may be thicker than the electrode current collector. The sum of the thickness per layer of the electrolyte layer and the thickness per layer of the support layer may be greater than the thickness of the electrode current collector layer.

[0179] The present invention is a battery in another embodiment.

[0180] The above battery may refer to a lithium secondary battery. The above lithium secondary battery may refer to a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery, etc. More specifically, the above battery may be a lithium ion secondary battery.

[0181] The above battery may include a first electrode and a second electrode. The polarity of the first electrode may be opposite to the polarity of the second electrode. That is, if the first electrode is a positive electrode (negative electrode), the second electrode may be a negative electrode (positive electrode). Only the first electrode, only the second electrode, or both the first electrode and the second electrode may include the electrodes of the present invention.

[0182] Accordingly, another embodiment of the present invention comprises a positive electrode and a negative electrode, wherein at least one of the positive electrode and the negative electrode comprises: an electrode current collector; an electrolyte layer disposed on one or both sides of the electrode current collector; an electrode active material layer disposed between the electrode current collector and the electrolyte layer; and a support layer disposed between the electrode active material layer and the electrolyte layer; wherein the electrolyte layer comprises a polymeric cross-linked structure and an electrolyte impregnated in the polymeric cross-linked structure, and the support layer comprises a first inorganic particle and a second inorganic particle, and the true density of the first inorganic particle is less than or equal to the true density of the second inorganic particle. The positive electrode may be an electrode that undergoes a reduction reaction during discharge. The negative electrode may be an electrode that undergoes an oxidation reaction during discharge.

[0183] In the battery of the present invention, a separate polymer substrate layer is not disposed between the positive electrode and the negative electrode. Here, the polymer substrate layer may refer to a polyolefin-based film used as a polymer substrate layer of a conventional separator. Accordingly, the support layer may be disposed between the electrolyte layer and the positive electrode active material layer and / or between the electrolyte layer and the negative electrode active material layer.

[0184]

[0185] In a battery, the area of ​​the system formed by the separator and the electrolyte can be larger than the area of ​​the negative electrode. Additionally, the area of ​​the negative electrode can be larger than the area of ​​the positive electrode. That is, since the area of ​​the negative electrode is larger than the area of ​​the positive electrode, the probability of a short circuit within the battery can be reduced if the negative electrode is the electrode of the present invention. Therefore, in the battery of the present invention, only the negative electrode may include the electrode of the present invention. FIG. 2 is a schematic diagram of the battery of the present invention at this time.

[0186] Referring to FIG. 2, the first electrode may be a positive electrode and the second electrode may be a negative electrode. The positive electrode may include a positive current collector (PEC) and a positive active material layer (PAM) disposed on one or both sides of the positive current collector (PEC).

[0187] Referring to FIG. 2, the cathode may include a cathode current collector (NEC); a cathode electrolyte layer (NEL) disposed on one or both sides of the cathode current collector (NEC); a cathode active material layer (NAM) disposed between the cathode current collector (NEC) and the cathode electrolyte layer (NEL); and a cathode support layer (NSP) disposed between the cathode active material layer (NAM) and the cathode electrolyte layer (NEL).

[0188] The above positive active material layer (PAM) may include a positive active material. The above negative active material layer (NAM) may include a negative active material.

[0189] The description of the above-mentioned cathode electrolyte layer (NEL) is the same as the description of the electrolyte layer of the electrode of the aforementioned specific example. The above-mentioned cathode electrolyte layer (NEL) may include a first polymeric crosslinked structure and a first electrolyte impregnated in the first polymeric crosslinked structure.

[0190] The description of each of the first polymeric crosslinking structure and the first electrolyte is the same as the description of each of the polymeric crosslinking structure and the electrolyte of the electrode of the aforementioned specific example.

[0191] The description of the above cathode support layer (NSP) may be the same as the description of the electrode support layer of the aforementioned specific example. The above cathode support layer (NSP) may include a first inorganic particle and a second inorganic particle. The true density of the first inorganic particle may be less than or equal to the true density of the second inorganic particle.

[0192] Referring to FIG. 2, the positive active material layer (PAM) and the negative electrolyte layer (NEL) may face each other. Specifically, the positive active material layer (PAM) and the negative electrolyte layer (NEL) may come into contact with each other.

[0193] FIG. 3 is a schematic diagram of another exemplary battery (BAT) of the present invention. The positive electrode may be combined with a gel electrolyte. The negative electrode may include an electrode of a specific embodiment of the present invention.

[0194] Referring to FIG. 3, the anode may further include an anode electrolyte layer (PEL) in addition to the anode current collector (PEC) and the anode active material layer (PAM). The anode active material layer (PAM) may be disposed between the anode current collector (PEC) and the anode electrolyte layer (PEL). The anode electrolyte layer (PEL) may include a second polymeric crosslinking structure and a second electrolyte impregnated in the second polymeric crosslinking structure.

[0195] The compositions of the first polymeric crosslinked structure and the second polymeric crosslinked structure may be the same or different from each other. Preferably, the compositions of the first polymeric crosslinked structure and the second polymeric crosslinked structure may be different. More preferably, the first polymeric crosslinked structure may include components derived from a binder, a crosslinking agent, and an initiator, and the second polymeric crosslinked structure may include components derived from a crosslinking agent and an initiator.

[0196] The description of each of the above binder, the above crosslinking agent, and the above initiator is the same as the description of each of the binder, the crosslinking agent, and the initiator of the composite electrolyte of the aforementioned specific example.

[0197] The compositions of the first electrolyte and the second electrolyte may be the same or different from each other. Preferably, the compositions of the first electrolyte and the second electrolyte may be the same.

[0198] Referring to FIG. 3, the positive electrolyte layer (PEL) and the negative electrolyte layer (NEL) may face each other. Specifically, the positive electrolyte layer (PEL) and the negative electrolyte layer (NEL) may come into contact with each other.

[0199] Referring to FIG. 3, the positive active material layer (PAM) and the negative active material layer (NAM) may each independently further include the second polymeric crosslinked structure and the second electrolyte impregnated in the second polymeric crosslinked structure.

[0200] The above battery (BAT) may be a bipolar battery. In a bipolar battery, the bipolar electrode may include a positive electrode (negative electrode) on one side of a current collector and a negative electrode (positive electrode) on the other side. The bipolar battery may include a separator disposed between sequentially stacked bipolar electrodes. The battery of the present invention may adopt a configuration similar to the electrode of the aforementioned specific example by combining this separator with any one of the electrodes. FIG. 4 is a schematic diagram of the battery.

[0201] Referring to FIG. 4, the battery of the present invention may include a first electrode and a second electrode facing each other.

[0202] Referring to FIG. 4, the first electrode may include a first electrode current collector, a negative electrolyte layer disposed on one side of the first electrode current collector, a positive active material layer disposed on the other side of the first electrode current collector, a negative active material layer disposed between the first electrode current collector and the negative electrolyte layer, and a negative support layer disposed between the negative electrolyte layer and the negative active material layer.

[0203] Referring to FIG. 4, the second electrode may include a second electrode current collector, a negative electrolyte layer disposed on one side of the second electrode current collector, a positive active material layer disposed on the other side of the second electrode current collector, a negative active material layer disposed between the second electrode current collector and the negative electrolyte layer, and a negative support layer disposed between the negative electrolyte layer and the negative active material layer.

[0204] The above positive active material layer (PAM) may include a positive active material. The above negative active material layer (NAM) may include a negative active material.

[0205] The above-mentioned cathode electrolyte layer and the above-mentioned cathode support layer may be identical to the electrolyte layer and support layer mentioned in the electrode of the aforementioned specific example.

[0206] The above cathode electrolyte layer may include a first polymeric crosslinked structure and a first electrolyte impregnated in the first polymeric crosslinked structure. The cathode support layer includes a first inorganic particle and a second inorganic particle, and the true density of the first inorganic particle may be less than or equal to the true density of the second inorganic particle.

[0207] Referring to FIG. 4, the positive active material layer (PAM) and the negative electrolyte layer (NEL) may face each other. Specifically, the positive active material layer (PAM) and the negative electrolyte layer (NEL) may come into contact with each other.

[0208] The positive portion of each of the first electrode and the second electrode may be combined with a gel electrolyte. The negative portion of each of the first electrode and the second electrode may have a structure similar to the electrode of a specific embodiment of the present invention. FIG. 5 is a schematic diagram of a battery at this time.

[0209] Referring to FIG. 5, the first electrode and the second electrode may further include a positive electrolyte layer (PEL) in addition to the positive current collector (PEC) and the positive active material layer (PAM). The positive active material layer (PAM) may be disposed between the positive current collector (PEC) and the positive electrolyte layer (PEL). The positive electrolyte layer (PEL) may include a second polymeric crosslinked structure and a second electrolyte impregnated in the second polymeric crosslinked structure.

[0210] Referring to FIG. 5, the positive electrolyte layer (PEL) and the negative electrolyte layer (NEL) may face each other. Specifically, the positive electrolyte layer (PEL) and the negative electrolyte layer (NEL) may come into contact with each other.

[0211] The positive active material layer (PAM) and the negative active material layer (NAM) may each independently further include the second polymeric crosslinking structure and the second electrolyte impregnated in the second polymeric crosslinking structure. The description of the second polymeric crosslinking structure and the second electrolyte is the same as that described above.

[0212] Hereinafter, the present invention is described in more detail through examples and comparative examples. However, the present invention is not limited to the examples.

[0213] [Test Method]

[0214] 1. SEM imaging of inorganic particles

[0215] The shape and size of the inorganic particles used in the preparation of the composite electrolytes of the examples and comparative examples were confirmed by SEM images. The capture of the SEM images was carried out through the following process.

[0216] (1) A dispersion is prepared in which inorganic particles at a concentration of 5 wt% are dispersed in ethanol by ultrasonic treatment (using Lab Companion’s UCP-10, 300 W, 40 kHz, 10 min, 25 ℃).

[0217] (2) 1 mL of dispersion is applied onto a substrate film (36 μm PET) with a dropper and dried in a convection oven (no nitrogen or vacuum treatment, 80 ℃, 10 min).

[0218] (3) The dried film is attached to the holder of the SEM equipment (FESEM-JSM7610F-plus, JEOL) via carbon tape (T01-215-015 of NISSHIN EM Co., Ltd).

[0219] (4) A photograph is taken with a SEM device (acceleration voltage: 5 kV, working distance: 8.3~8.5 mm, SEM mode, magnification: 30,000 or 50,000).

[0220] (5) The shape of the inorganic particles identified in the acquired SEM images is determined in the following way. IMAGE J software is used. 50 inorganic particles are selected per SEM image.

[0221] 1) Acicular particles: Those where L / W or L / T is 3 or greater, given that the maximum length, maximum width, and maximum thickness are L, W, and T, respectively.

[0222] 2) Plate-shaped particles: When the maximum length, maximum width, and maximum thickness of the particles are L, W, and T, respectively, L / T or W / T is 3 or greater.

[0223] 3) Polygonal particle: When the maximum length, maximum width, and maximum thickness are L, W, and T, respectively, L / W and W / T are each within the range of 1 to 3.

[0224] (6) The size of inorganic particles identified in the acquired SEM images is measured in the following way. IMAGE J software is used. 50 inorganic particles are selected per SEM image.

[0225] 1) Needle-shaped or plate-shaped particles: The average longitudinal length is determined by the average of the number of inorganic particles with the maximum length of each inorganic particle. The average transverse length is determined by the average of the number of inorganic particles with the length in the direction perpendicular to the maximum length of each inorganic particle.

[0226] 2) Polygonal particles: The average size is determined by the average of the number of inorganic particles with the maximum length of each inorganic particle.

[0227] 2. Measurement of Green Density of Inorganic Particles

[0228] The green density of inorganic particles was measured according to the following process.

[0229] (1) Inorganic particles are pretreated by vacuum drying (80°C, 6 hours) and subsequent aging (25°C, 7 days).

[0230] (2) 1 g of pre-treated inorganic particles is placed into a cylindrical mold with a diameter of 16 mm.

[0231] (3) Next, 1 ton / cm 2 Pressure is applied to the above-mentioned cylindrical mold to produce a specimen in the form of a powder pellet (Green pellet). The pressure application conditions are as follows.

[0232] Pressure application equipment: Carver hydraulic press 4386,

[0233] Applying load holding time: 30 seconds

[0234] Compression count: 1 time

[0235] (4) The thickness of the center of the above specimen is measured three times with Mitutoyo’s CD-15APX to calculate the volume of the above specimen.

[0236] (5) The green density of the inorganic particles is calculated using the volume of the specimen and the weight (1 g) of the specimen measured in (4) above.

[0237] 3. Measurement of the specific surface area of ​​inorganic particles

[0238] The Bruner-Emit-Teller (BET) specific surface area of ​​nitrogen adsorption / desorption of inorganic particles was measured according to the following process.

[0239] (1) 1.3 mg of inorganic particle sample is pretreated (vacuum, 105 ℃, 6 hours).

[0240] (2) The sample pretreated in (1) is introduced into a sample cell (MICROTRAC, BET MAX STD Sample cell).

[0241] (3) The BET specific surface area of ​​the particles in the sample cell was measured using a specific surface area analyzer (BEL Japan Inc., BELSORP-max). An air oven was installed in the analyzer and its temperature was maintained at 40 ℃.

[0242] 4. Measurement of insulation breakdown voltage of the support layer

[0243] (1) A voltage with a step-up rate of 100 V / sec is applied to the cathode semi-finished product (laminated structure of cathode current collector / active material layer / support layer) obtained in the example and comparative example using a Hi-pot meter (Chroma 19055).

[0244] (2) The maximum allowable voltage is measured before insulation breakdown occurs.

[0245] (3) The dielectric breakdown voltage of the support layer (kV / mil) is calculated by dividing the measured maximum voltage by the thickness of the inorganic layer.

[0246] 5. Ionic conductivity of the inorganic layer

[0247] The ionic conductivity of the support layer of the examples and comparative examples was calculated by measuring the electrical resistance of the cathodes of the examples and comparative examples using electrochemical impedance spectroscopy (EIS) and by conversion through the Nyquist plot method. The specimen is a 2016 coin cell fabricated by punching the cathode to a size of 19 pi. The electrical resistance measurement was performed under AC voltage conditions of an amplitude of 10 mV and a frequency of 1,000,000 to 1,000 Hz. The ionic conductivity value was determined as the average of the measurements for each of the five samples by substituting the thickness and area of ​​the inorganic layer.

[0248] 6. Battery Capacity and Cycle Performance

[0249] (1) Cycling of the batteries of the examples and comparative examples was performed. Cycling was performed at room temperature and at 2.2 to 3.8 V at a rate of 0.1 C-rate.

[0250] (2) Then, the cycling was repeated 10 times, and the charge capacity, discharge capacity, and discharge capacity retention rate were measured using the capacity retention rate measured at this time.

[0251] [Manufacture of Electrodes and Batteries]

[0252] Example 1. Electrode and battery

[0253] (1) Cathode

[0254] 1) A cathode material composition is prepared in which a component comprising 95.6% by weight of a material consisting of 100% by weight of a graphite-based material in which artificial graphite and natural graphite are mixed in a weight ratio of 5:5 as a cathode active material; 1% by weight of acetylene black as a conductive material; 1.1% by weight of carboxymethyl cellulose (CMC) as a first binder; and 2.3% by weight of styrene butadiene rubber (SBR) as a second binder is mixed with water.

[0255] 2) The above cathode material composition is applied to one side of a copper current collector with a thickness of 10 μm using a comma coater, and then dried and rolled at 130°C to prepare a cathode plate with a stacked cathode active material layer. The porosity and thickness of the cathode active material layer were 28% and 78 μm, respectively.

[0256] 3) First inorganic particle: polygonal boehmite (Sasol's Disperal 60; AlO(OH); true density: 3.03 g / cm³ 3 Green density: 1.35 g / cm³ 3 ; BET specific surface area due to nitrogen adsorption / desorption: 63 m 2 / g; average size: 350 nm) and second inorganic particles, acicular boehmite (LM37 of Tianjin Bihailantian Waterbased Polymer Materials Co., Ltd; AlO(OH); density: 3.03 g / cm³ 3 Green density: 0.99 g / cm³ 3 ; BET specific surface area due to nitrogen adsorption / desorption: 101 m 2 / g; average transverse length: 35 nm; average longitudinal length: 155 nm) is prepared.

[0257] 4) A dispersion is prepared in which a mixture of 9.0 g of the first inorganic particle and 1.0 g of the second inorganic particle is dispersed in 10 g of N-methyl-pyrrolidone (NMP).

[0258] 5) PVDF-HFP (Arkema’s Kynar LBG, weight-average molecular weight: 700,000 g / mol, substitution rate: 5%) is added to the dispersion as a binding binder and stirred with a homogenizer to prepare a second composition.

[0259] 6) The second composition is applied onto the cathode active material layer using a dual slot die, and then the slurry is vaporized at a temperature of 100°C. A support layer with a thickness of 17 μm is formed. The inorganic layer consists of 90 wt% inorganic particles and 10 wt% binding binder.

[0260] 7) A slurry is prepared by adding 1.4 g of PVDF-HFP (Arkema’s Kynar 2501-20, weight-average molecular weight: 300,000 g / mol, substitution rate: 17%) as a binder, 2.8 g of TMPTA as a first crosslinking agent, and 0.8 g of polyurethane diacrylate (Miwon Specialty Chemical’s Miramer PU2100, weight-average molecular weight: 1400 g / mol) as a second crosslinking agent to 95 g of electrolyte.

[0261] 8) The above slurry is stirred with a homogenizer, and 2% of the photopolymerization initiator Omnirad TPO-L is added to it relative to the total amount of the crosslinking agent to prepare the first composition.

[0262] 9) The above electrolyte is prepared by dissolving 1M LiPF6 and 2 wt% vinylene carbonate in a mixed solvent in which ethylene carbonate and ethyl methyl carbonate are mixed in a volume ratio of 3:7.

[0263] 10) The first composition is applied to the upper surface of the support layer using a dual slot die. Then, UV light is irradiated thereon to obtain an electrolyte layer with a thickness of 50 μm.

[0264] 11) The cathode plate on which the support layer and the electrolyte layer are formed is stamped to a size of 31 mm x 43 mm.

[0265] (2) bipolar

[0266] 1) A mixture is prepared consisting of 495 wt% LiFePO4 as the positive active material, 2 wt% conductive carbon black (Super P; IMERYS Graphite & Carbon) as the conductive material, and 3 wt% PVdF with a weight-average molecular weight of about 800,000 as the binder. A slurry is obtained in which the above mixture is uniformly dispersed in NMP.

[0267] 2) The above slurry is applied to one side of an aluminum current collector with a thickness of 20 μm, and then dried and rolled to prepare an anode plate with a laminated anode active material layer.

[0268] 3) The porosity and thickness of the positive active material layer are 30% and 101.4 μm, respectively.

[0269] 4) The above positive plate is stamped to a size of 30 mm x 42 mm.

[0270] (3) Battery assembly

[0271] An electrode assembly is fabricated in which the positive active material layer of the positive plate and the electrolyte layer of the negative plate are arranged to face each other. This electrode assembly is housed in a pouch to complete the battery. Five samples of this battery are fabricated. The performance of the battery is the arithmetic mean of the five samples.

[0272] Example 2. Electrode and battery

[0273] In step 7) of the cathode manufacturing process, the process of Example 1 is repeated except that the input amounts of the binder and the first crosslinking agent are changed to 2.8 g and 1.4 g, respectively. An electrode and a battery are obtained.

[0274] Example 3. Electrode and battery

[0275] In the 7) process of manufacturing the cathode, the process of Example 1 is repeated except that the input amounts of the binder, the first crosslinking agent, and the second crosslinking agent are changed to 2.1 g, 4.2 g, and 0.8 g, respectively. An electrode and a battery are obtained.

[0276] Example 4. Electrode and battery

[0277] In step 4) of cathode manufacturing, the same process as in Example 1 is repeated, except that the input amounts of the first inorganic particle and the second inorganic particle are changed to 8.0 g and 2.0 g, respectively. An electrode and a battery are obtained.

[0278] Example 5. Electrode and battery

[0279] In step 3) of cathode manufacturing, polygonal alumina (Sumitomo's AES-11, true density: 3.95 g / cm³) is used as the second inorganic particle. 3Green density: 2.06 g / cm³ 3 ; BET specific surface area due to nitrogen adsorption / desorption: 6.4 m 2 The process of Example 1 is repeated, except that an electrode and a cell are prepared (average size: 436 nm).

[0280] Comparative Example 1. Electrode and battery

[0281] The same process as in Example 1 is repeated, except that in the process of manufacturing the cathode 4), a dispersion is prepared in which 10.0 g of the first inorganic particle is dispersed in 10 g of N-methyl-pyrrolidone (NMP). An electrode and a battery are obtained.

[0282] Comparative Example 2. Electrode and battery

[0283] The same process as in Example 1 is repeated, except that in the process of manufacturing the cathode 4), a dispersion is prepared in which 10.0 g of the second inorganic particle is dispersed in 10 g of N-methyl-pyrrolidone (NMP). An electrode and a battery are obtained.

[0284] Comparative Example 3. Electrode and battery

[0285] In process 4) of cathode manufacturing, polygonal alumina (Sumitomo's AES-11, true density: 3.95 g / cm³) 3 Green density: 2.06 g / cm³ 3 ; BET specific surface area due to nitrogen adsorption / desorption: 6.4 m 2 The same process as in Example 1 is repeated, except that a dispersion is prepared in which 10.0 g of (average size: 436 nm) is dispersed in 10 g of N-methyl-pyrrolidone (NMP). An electrode and a cell are obtained.

[0286] [Results and Discussion]

[0287] 1. SEM image of inorganic particles

[0288] FIG. 4 is an SEM image of a first inorganic particle used in an embodiment of the present invention. Referring to FIG. 4, it is confirmed that the first inorganic particle is polygonal and that its average size is about 350 nm.

[0289] FIG. 5 is an SEM image of a second inorganic particle used in an embodiment of the present invention. Referring to FIG. 5, it is confirmed that the second inorganic particle is needle-shaped, and that its average longitudinal length is about 155 nm and its average transverse length is about 35 nm.

[0290] Figure 6 is an SEM image of another second inorganic particle used in an embodiment of the present invention. Referring to Figure 6, it is confirmed that this second inorganic particle is polygonal and has an average size of 436 nm. 2. Measurement of Green Density of Inorganic Particles

[0291] The green density of the first inorganic particle is 1.35 g / cm³ 3 It was measured as. The green density of the second inorganic particle was 0.99 g / cm³. 3 It was measured as follows. The green density of the inorganic particles used in Example 5 and Comparative Example 3 was 2.06 g / cm³. 3 It was measured as.

[0292] 3. Measurement of the specific surface area of ​​inorganic particles

[0293] The specific surface area of ​​the first inorganic particle is 63 m² 2 It was measured as / g. The specific surface area of ​​the second inorganic particle is 101 m² 2 It was measured as / g. The specific surface area of ​​the inorganic particles used in Example 5 and Comparative Example 3 was 6.4 m² 2 It was measured as / g.

[0294] 4. Dielectric breakdown voltage and ion conductivity of the support layer

[0295] Table 1 below shows the measurement results of the dielectric breakdown voltage and ion conductivity of the supporting layers of the examples and comparative examples.

[0296] Dielectric breakdown voltage Ionic conductivity kV / milm S / cm Example 1 1.33 1.64 2 1.33 1.57 3 1.33 1.55 4 1.53 1.69 5 0.69 1.17 Comparative Example 10.74 1.12 2 1.46 0.83 3 0.59 1.26

[0297] Referring to Table 1, it can be seen that the dielectric breakdown voltage and ion conductivity of the examples are generally higher than those of the comparative examples. In particular, it is confirmed that Examples 1 to 4 simultaneously exhibit superior dielectric breakdown voltage and ion conductivity compared to the comparative examples.

[0298] 5. Battery Capacity and Cycle Performance

[0299] Table 2 below shows the measurement results of battery capacity and cycle performance of the examples and comparative examples.

[0300] 1st Cycle 10th Cycle 10 Cycle Retention Discharge Capacity Charge Capacity Discharge Capacity Charge Capacity Discharge Capacity Retention Rate mAh / gmAh / gmAh / gmAh / g% Example 1 41.3 43.3 40.7 43.1 98.5 52 41.1 44.1 39.8 42.1 96.8 43 41.3 43.8 40.1 43.3 97.0 9 44 2 42.9 41.2 42.9 98.1 539.6 43.6 34.5 39.5 87.1 3 Comparative Example 1 40.5 43.6 36.2 39.7 89.3 82 38.3 41.9 31.1 37.3 81.2 339.2 42.7 30.3 39.1 77.3 0

[0301] Referring to Table 3, it is confirmed that the batteries of the examples generally exhibit superior capacity and lifespan characteristics compared to the batteries of the comparative examples. In particular, it is confirmed that Examples 1 to 4 exhibit superior battery performance compared to the comparative examples.

Claims

Electrode current collector; An electrolyte layer disposed on one or both sides of the above electrode current collector and comprising a first composition; An electrode active material layer disposed between the electrode current collector and the electrolyte layer; and A support layer disposed between the electrode active material layer and the electrolyte layer, comprising a second composition; Includes, The first composition above comprises a binder, a crosslinking agent, an initiator, and an electrolyte, and The above second composition comprises a first inorganic particle and a second inorganic particle, and An electrode in which the true density of the first inorganic particle is less than or equal to the true density of the second inorganic particle. In Article 1, The green density of the first inorganic particle is greater than the green density of the second inorganic particle, and The electrode in which the content of the first inorganic particles and the second inorganic particles of the second composition is greater than the binder content of the first composition. In Article 1, The active layer comprises a cured product of the first composition, and The above support layer is an electrode comprising a dried product of the second composition. In Article 1, An electrode in which the content of the second inorganic particle of the second composition is 5% by weight or more of the total content of the first inorganic particle and the second inorganic particle of the second composition. In Article 1, The average size of the first inorganic particle is in the range of 100 nm to 500 nm, and The average longitudinal length of the second inorganic particle is in the range of 100 nm to 200 nm, and An electrode in which the average transverse length of the second inorganic particle is within the range of 25 nm to 50 nm. In Article 1, The first inorganic particle and the second inorganic particle are each independently an electrode comprising a lithium-containing metal oxide, a lithium-non-containing metal oxide, or a combination thereof. In Article 1, The above binder comprises a fluorine-based binder, and the fluorine-based binder comprises a first unit derived from vinylidene fluoride and a second unit derived from a fluorine-containing alkyl vinyl compound, and The second unit content of the above fluorine-based binder is in the range of 10 weight% to 50 weight%, and An electrode in which the weight average molecular weight of the above-mentioned fluorine-based binder is within the range of 300,000 g / mol to 1,000,000 g / mol. In Article 1, The above-mentioned crosslinking agent comprises a first polyfunctional crosslinking agent and a second polyfunctional crosslinking agent, and An electrode having more functional groups than the number of functional groups of the first polyfunctional crosslinking agent. In Article 1, The above initiator is an electrode comprising a photopolymerization initiator. In Article 1, The above electrolyte comprises a non-aqueous solvent, a lithium salt, and an electrolyte additive, and The above-mentioned non-aqueous solvent comprises ethylene carbonate and ethyl methyl carbonate, and The above lithium salt includes LiN(CF3SO2)2, and The above electrolyte additive is an electrode containing vinylene carbonate. Electrode current collector; An electrolyte layer disposed on one or both sides of the above electrode current collector; An electrode active material layer disposed between the electrode current collector and the electrolyte layer; and A support layer disposed between the electrode active material layer and the electrolyte layer; Includes, The above electrolyte layer comprises a polymeric cross-linked structure and an electrolyte impregnated in the polymeric cross-linked structure, and The above support layer includes a first inorganic particle and a second inorganic particle, and An electrode in which the true density of the first inorganic particle is less than or equal to the true density of the second inorganic particle. In Article 11, The electrode active material layer and the support layer are electrodes in contact with each other. In Article 11, The first inorganic particle and the second inorganic particle are electrodes comprising boehmite (AlO(OH)). In Article 11, The first inorganic particle mentioned above is a polygonal inorganic particle, and The above second inorganic particle is an electrode that is a plate-shaped inorganic particle or a needle-shaped inorganic particle. In Article 11, The thickness per layer of the above electrolyte layer is greater than the thickness of the above electrode current collector, and The thickness per layer of the above electrolyte layer is greater than the thickness per layer of the above inorganic layer, and The thickness per layer of the above-mentioned inorganic layer is greater than the thickness of the above-mentioned electrode current collector. It includes an anode and a cathode, At least one of the anode and the cathode comprises: an electrode current collector; an electrolyte layer disposed on one or both sides of the electrode current collector; an electrode active material layer disposed between the electrode current collector and the electrolyte layer; and a support layer disposed between the electrode active material layer and the electrolyte layer. The above electrolyte layer comprises a polymeric cross-linked structure and an electrolyte impregnated in the polymeric cross-linked structure, and The above support layer includes a first inorganic particle and a second inorganic particle, and A battery in which the true density of the first inorganic particle is less than or equal to the true density of the second inorganic particle. In Article 16, The above positive electrode includes a positive current collector and a positive active material layer disposed on one or both sides of the positive current collector, and The above cathode comprises: a cathode current collector; a cathode electrolyte layer disposed on one or both sides of the cathode current collector; a cathode active material layer disposed between the cathode current collector and the cathode electrolyte layer; and a cathode support layer disposed between the cathode active material layer and the cathode electrolyte layer. The above cathode electrolyte layer comprises a first polymeric crosslinked structure and a first electrolyte impregnated in the first polymeric crosslinked structure, and The above cathode support layer comprises a first inorganic particle and a second inorganic particle, and A battery in which the true density of the first inorganic particle is less than or equal to the true density of the second inorganic particle. In Article 17, The above anode further includes an anode electrolyte layer, and The above positive active material layer is disposed between the positive current collector and the positive electrolyte layer, and The above positive electrolyte layer comprises a second polymeric crosslinking structure and a second electrolyte impregnated in the second polymeric crosslinking structure. It includes a first electrode and a second electrode, The first electrode comprises a first electrode current collector, a negative electrode electrolyte layer disposed on one side of the first electrode current collector, a positive electrode active material layer disposed on the other side of the first electrode current collector, a negative electrode active material layer disposed between the first electrode current collector and the negative electrode electrolyte layer, and a negative electrode support layer disposed between the negative electrode electrolyte layer and the negative electrode active material layer. The second electrode comprises a second electrode current collector, a negative electrode electrolyte layer disposed on one side of the second electrode current collector, a positive electrode active material layer disposed on the other side of the second electrode current collector, a negative electrode active material layer disposed between the second electrode current collector and the negative electrode electrolyte layer, and a negative electrode support layer disposed between the negative electrode electrolyte layer and the negative electrode active material layer. The above cathode electrolyte layer comprises a first polymeric crosslinked structure and a first electrolyte impregnated in the first polymeric crosslinked structure, and The above cathode support layer comprises a first inorganic particle and a second inorganic particle, and A battery in which the true density of the first inorganic particle is less than or equal to the true density of the second inorganic particle. In Article 19, The first electrode and the second electrode further include an anode electrolyte layer, and The positive active material layer is disposed between the first electrode current collector and the positive electrolyte layer and between the second electrode current collector and the positive electrolyte layer, and The above positive electrolyte layer comprises a second polymeric crosslinking structure and a second electrolyte impregnated in the second polymeric crosslinking structure.

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