Electrode assemblies and lithium secondary batteries

Abstract

The electrode assembly according to the present invention includes a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and a coating layer formed on one surface of the separator, and the 90° peel strength between the separator and the coating layer measured at 60° C. is 30 gf / 25 mm to 140 gf / 25 mm.

Description

[Technical Field]

[0001] [Cross-reference of related applications] This application claims priority rights based on Korean Patent Application No. 10-2022-0113106 dated September 6, 2022, and Korean Patent Application No. 10-2023-0117680 dated September 5, 2023, and all content disclosed in the documents of said Korean Patent Applications is incorporated herein by reference.

[0002] This invention relates to an electrode assembly and a lithium secondary battery. [Background technology]

[0003] With the increasing technological development and demand for electric vehicles and energy storage systems (ESS), the demand for batteries as an energy source is surging, leading to research into batteries that can meet a variety of requirements. In particular, there is active research on lithium-ion batteries, which have high energy density while possessing excellent lifespan and cycle characteristics, for use as power sources in such devices.

[0004] Generally, lithium secondary batteries include a positive electrode, a negative electrode, a separator membrane interposed between the positive and negative electrodes, and an electrolyte. The positive electrode has an unstable structure when charged, which can generate oxygen. When oxygen is generated, there is a high risk of ignition, so research and development efforts are being made to improve the safety of lithium secondary batteries.

[0005] Separation membranes are used to ensure electrical insulation between the positive and negative electrodes, and thin membranes made of polyolefin are commonly used. However, polyolefin-based separation membranes tend to shrink in high-temperature environments, which can prevent them from insulating the positive and negative electrodes. If electrical insulation between the positive and negative electrodes becomes impossible, a short circuit can occur, which can react with oxygen generated by the unstable positive electrode and cause a fire. In other words, if a short circuit occurs in a charged lithium secondary battery in a high-temperature environment, there is a possibility that the lithium secondary battery will catch fire.

[0006] Therefore, there is a need for technological development to improve the high-temperature safety of lithium-ion batteries. [Overview of the project] [Problems that the invention aims to solve]

[0007] Therefore, the present invention provides an electrode assembly that improves the high-temperature stability of a lithium secondary battery while maintaining excellent electrochemical properties, and a lithium secondary battery containing the same. [Means for solving the problem]

[0008] According to one embodiment of the invention, an electrode assembly is provided which includes a positive electrode, a negative electrode, a separation membrane disposed between the positive electrode and the negative electrode, and a coating layer formed on one surface of the separation membrane, the coating layer containing polymer particles or ceramic particles having an absolute value of 25 mV or more zeta potential, wherein the 90° peel strength between the separation membrane and the coating layer, measured at 60°C, is 30 gf / 25 mm to 140 gf / 25 mm.

[0009] In the electrode assembly, the coating layer can be in direct contact with the positive electrode.

[0010] In the electrode assembly, the ratio D1 / D2 of the thickness of the coating layer (D1) to the thickness of the separation film (D2) may be 0.1 to 4.

[0011] In the electrode assembly, the thickness (D1) of the coating layer may be 30 μm or less.

[0012] In the electrode assembly, the thickness (D2) of the separation membrane may be 5 μm to 20 μm.

[0013] In the electrode assembly, polymer particles having an absolute value of zeta potential of 25 mV or more may include one or more selected from the group consisting of polyethylene oxide (PEO), polyphenylene sulfide (PPS), polymethyl (meth)acrylate, polystyrene, polyvinyl chloride, polycarbonate, polysulfone, polyethersulfone, polyetherimide, polyphenylsulfone, polyamideimide, polyimide, polybenzimidazole, polyetherketone, polyphthalamide, polybutylene terephthalate, and polyethylene terephthalate.

[0014] Furthermore, the ceramic particles may include one or more selected from the group consisting of boehmite (γ-AlO(OH)), Al2O3, TiO2, Fe2O3, SiO2, ZrO2, Co3O4, SnO2, NiO, ZnO, V2O5, and MnO. In other examples, the ceramic particles may be lithium-containing and ionically conductive ceramic particles, such as lithium-containing oxides or lithium-containing phosphorus oxide particles. Specific examples of such particles may include one or more selected from the group consisting of LAGP (lithium aluminum germanium phosphate) compounds, LLZO (lithium lanthanum zirconium oxide) compounds, LATP (lithium aluminum titanium phosphate) compounds, LLZTO (lithium lanthanum zirconium tantalum oxide) compounds, LLTO (lithium lanthanum titanium oxide) compounds, LSTP (lithium silicon titanium phosphate) compounds, LGPO (lithium germanium phosphate) compounds, and lithium oxides (e.g., Li2O).

[0015] Furthermore, the polymer particles or ceramic particles have an average particle size (D) of 300 nm to 3 μm. 50 The coating layer may have a polymer binder and polymer particles or ceramic particles dispersed on the polymer binder, in which case the polymer binder and polymer particles or ceramic particles may be present in a weight ratio of 1:9 to 5:5.

[0016] According to another embodiment of the invention, a lithium secondary battery is provided comprising the aforementioned electrode assembly and a flame-retardant electrolyte comprising a flame-retardant solvent having a flash point of 100°C or higher or having no flash point, and a lithium salt.

[0017] In this case, the flame-retardant solvent may include one or more organic solvents having functional groups selected from the group consisting of sulfone functional groups, fluorine-containing functional groups, phosphorus-containing functional groups, and nitrile functional groups. More specifically, it may include one or more organic solvents selected from sulfone compounds, nitrile compounds, phosphoric acid compounds, and fluorine-substituted carbonate compounds. [Effects of the Invention]

[0018] In the electrode assembly according to the present invention, the 90° peel strength between the separation membrane and the coating layer, measured at 60°C, is 30 to 140 gf / 25 mm. When the adhesive strength between the separation membrane and the coating layer satisfies the above range, the separation membrane bonded to the coating layer does not easily shrink even in high-temperature environments, thus preventing short circuits between the positive and negative electrodes and improving the high-temperature safety of the lithium secondary battery. Furthermore, when the adhesive strength between the separation membrane and the coating layer satisfies the above range, the problem of increased cell resistance due to decreased lithium ion conductivity at the interface between the separation membrane and the coating layer caused by excessive clogging of pores in the separation membrane by particles contained in the coating layer can be minimized.

[0019] Furthermore, since the polymer particles and / or ceramic particles contained in the coating layer have relatively higher melting points than polyolefin polymers, the coating layer containing these particles does not easily shrink at high temperatures. Therefore, by suppressing the thermal shrinkage of the separation membrane, the coating layer prevents short circuits between the positive and negative electrodes at high temperatures, thereby improving the high-temperature safety of the lithium secondary battery.

[0020] On the other hand, when using a flame-retardant electrolyte to ensure high-temperature safety of lithium secondary batteries, the flame-retardant electrolyte has poor wetting properties for polyolefin-based separation membranes, which leads to a problem of reduced lithium ion mobility in the separation membrane. However, when the coating layer formed on the separation membrane of the present invention contains polymer particles and / or ceramic particles with an absolute value of 25 mV or more for the zeta potential, the flame-retardant electrolyte can be easily impregnated into the coating layer, thereby ensuring lithium ion mobility. [Brief explanation of the drawing]

[0021] [Figure 1] This is a rough sketch showing the voltage-temperature change over time for the lithium secondary battery manufactured in Example 1. [Figure 2] This graph shows the voltage-temperature change over time for the lithium secondary battery manufactured in Example 2. [Figure 3] This graph shows the voltage-temperature change over time for the lithium secondary battery manufactured in Example 3. [Figure 4] This graph shows the voltage-temperature change over time for the lithium secondary battery manufactured in Example 4. [Figure 5] This graph shows the voltage-temperature change over time for the lithium secondary battery manufactured in Comparative Example 1. [Figure 6] This graph shows the voltage-temperature change over time for the lithium secondary battery manufactured in Comparative Example 2. [Figure 7] This graph shows the voltage-temperature change over time for the lithium secondary battery manufactured in Comparative Example 3. [Figure 8] This graph shows the voltage-temperature change over time for the lithium secondary battery manufactured in Comparative Example 4. [Figure 9] This graph shows the voltage-temperature change over time for the lithium secondary battery manufactured in Comparative Example 5. [Modes for carrying out the invention]

[0022] The advantages and features of the present invention, and the methods for achieving them, will become clearer by referring in detail to the embodiments described below, along with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below and can be realized in a variety of different forms, and these embodiments are provided to complete the disclosure of the present invention and to fully inform a person ordinary skill in the art to which the invention pertains of the invention of the scope of the invention, and the present invention is defined only by the scope of the claims. Throughout the specification, the same reference numerals refer to the same components.

[0023] Unless otherwise defined, all terms used herein (including technical and scientific terms) will be used in a sense that can be commonly understood by a person of ordinary skill in the art to which this invention pertains. Furthermore, terms defined in commonly used dictionaries will not be interpreted ideally or excessively unless explicitly defined otherwise.

[0024] The terms used herein are for illustrative purposes only and are not intended to limit the invention. In this specification, the singular form includes the plural form unless otherwise specified. The terms “comprises” and / or “comprising” as used in this specification do not preclude the presence or addition of one or more other components beyond those mentioned.

[0025] In this specification, when a part includes a component, this means that it may include other components, rather than excluding them, unless otherwise stated.

[0026] In this specification, "A and / or B" means A, or B, or A and B.

[0027] In this specification, "%" means weight percent unless otherwise specified.

[0028] In this specification, D 50This refers to the particle size corresponding to 50% of the cumulative volume in the particle size distribution curve. 50 This can be measured, for example, using the laser diffraction method. The laser diffraction method can generally measure particle sizes from the submicron region to several millimeters in size, and can obtain highly reproducible and high-resolution results.

[0029] In this specification, the 90° peel strength between the separation membrane and the coating layer was measured by first manufacturing a separation membrane with a coating layer formed on one surface to a width of 25 mm, attaching it to a glass slide with double-sided tape, rolling it twice with a 2 kg roller, and then peeling the coating layer from the separation membrane at a distance of 90 mm from the separation membrane at a speed of 300 mm / min under a temperature condition of 60°C, and measuring the average value of the 90° peel strength.

[0030] In this specification, "zeta potential" is an indicator of the degree of surface charge of a particle. In the present invention, the zeta potential of a particle can be measured by electrophoretic light scattering using a dynamic light scattering apparatus. Specifically, polymer particles or ceramic particles can be dispersed in water or an alcohol-based solvent without a dispersant, and then the zeta potential of the particles can be measured by electrophoretic light scattering.

[0031] The present invention will be described in more detail below.

[0032] <Electrode Assembly> An electrode assembly according to one embodiment of the invention includes a positive electrode, a negative electrode, a separation membrane disposed between the positive electrode and the negative electrode, and a coating layer formed on one surface of the separation membrane, which contains polymer particles or ceramic particles having an absolute value of zeta potential of 25 mV or more. The 90° peel strength between the separation membrane and the coating layer, measured at 60°C, is 30 gf / 25 mm to 140 gf / 25 mm.

[0033] The coating layer can be formed on one surface of the separation membrane. In this case, the 90° peel strength between the separation membrane and the coating layer, measured at 60°C, may be 30gf / 25mm to 140gf / 25mm, specifically 35gf / 25mm to 135gf / 25mm, or more specifically 35gf / 25mm to 100gf / 25mm. If the 90° peel strength between the separation membrane and the coating layer, measured at 60°C, is too low, the adhesion between the separation membrane and the coating layer is weak, and the separation membrane shrinks due to heat at high temperatures, which can cause a short circuit between the positive and negative electrodes and lead to the battery igniting. If the 90° peel strength between the separation membrane and the coating layer, measured at 60°C, is too high, the pores in the separation membrane become excessively clogged by particles contained in the coating layer, resulting in a decrease in lithium ion conductivity at the interface between the separation membrane and the coating layer, and an increase in cell resistance.

[0034] In the electrode assembly of the above embodiment, the coating layer can be in direct contact with the positive electrode. In this case, a separation film is placed between the coating layer and the negative electrode, preventing the coating layer from being in direct contact with the negative electrode. Therefore, an irreversible reaction in which the polymer in the coating layer is reduced and decomposed when the battery is operated due to direct contact between the coating layer and the negative electrode is prevented, and as a result, the problem of reduced battery cycle life characteristics can be prevented.

[0035] The ratio of the thickness of the coating layer (D1) to the thickness of the separation membrane (D2), D1 / D2, may be 0.1 to 4, specifically 0.2 to 3, or more specifically 0.3 to 2. If D1 / D2 is less than 0.1, the coating layer is excessively thin compared to the separation membrane, and sufficient adhesion between the separation membrane and the coating layer is not ensured, which may cause the separation membrane to shrink at high temperatures. If D1 / D2 is greater than 4, the coating layer is excessively thick compared to the separation membrane, which may reduce the conductivity of lithium ions in the coating layer, and thus increase the cell resistance.

[0036] On the other hand, in an electrode assembly, if only a coating layer is placed between the positive and negative electrodes without a separator membrane, the thickness of the coating layer must be made thick to prevent short circuits between the positive and negative electrodes. However, when both a coating layer and a separator membrane are used in the electrode assembly, as in the embodiment described above, the thickness of the coating layer can be made thin on the separator membrane.

[0037] Specifically, the thickness (D1) of the coating layer may be 30 μm or less, preferably 1 μm to 20 μm, and more preferably 3 μm to 15 μm. When the thickness of the coating layer satisfies the above range, sufficient adhesion between the separation membrane and the coating layer can be ensured, preventing short circuits between the positive and negative electrodes while also preventing shrinkage of the separation membrane at high temperatures.

[0038] In the electrode assembly of the above embodiment, the coating layer on the separation film may include at least one polymer particle or ceramic particle with an absolute value of 25 mV or more for its zeta potential.

[0039] In this case, the zeta potential of the polymer particles or ceramic particles is an indicator of the degree of surface charge of these particles and can define the electrostatic repulsion or dispersibility of these particles. Polymer particles or ceramic particles with a large absolute value of the zeta potential can be uniformly dispersed on the separation membrane and exhibit good and uniform coating properties, and can define a large number of fine and uniform pores that allow lithium ions to pass between these particles. Furthermore, with particles that satisfy such a zeta potential, the coating layer can exhibit excellent impregnation properties with flame-retardant electrolytes containing flame-retardant solvents. With such a combination of coating layer and flame-retardant electrolyte, a lithium secondary battery including the electrode assembly of one embodiment can exhibit excellent electrochemical properties.

[0040] The zeta potential of the polymer particles or ceramic particles can be measured, for example, by electrophoretic light scattering using a dynamic light scattering apparatus. In this case, the zeta potential of the polymer particles or ceramic particles can be measured while they are dispersed in water or an alcohol-based solvent without the use of a separate dispersant. In a specific example, the zeta potential can be measured when the polymer particles or ceramic particles are dispersed in an aqueous solvent at a concentration of 0.1% by weight or less.

[0041] The absolute value of the zeta potential of the polymer particles or ceramic particles may be 25mV or higher, 35mV or higher, or 45mV or higher, and may be 100mV or lower, 90mV or lower, or 80mV or lower. Within this range, good coating properties and porosity of the coating layer are achieved, high impregnation of the flame-retardant electrolyte is ensured, and a uniform reaction occurs throughout the electrode, thereby improving various performance characteristics such as capacity, output, and lifespan of the lithium secondary battery.

[0042] Specific examples of the polymer particles include one or more selected from the group consisting of polyethylene oxide (PEO), polymethyl (meth)acrylate, polystyrene, polyvinyl chloride, polycarbonate, polysulfone, polyethersulfone, polyetherimide, polyphenylsulfone, polyamideimide, polyimide, polybenzimidazole, polyetherketone, polyphthalamide, polybutylene terephthalate and polyethylene terephthalate, and polyphenylene sulfide.

[0043] Furthermore, specific examples of the ceramic particles include one or more selected from the group consisting of boehmite (γ-AlO(OH)), Al2O3, TiO2, Fe2O3, SiO2, ZrO2, Co3O4, SnO2, NiO, ZnO, V2O5, and MnO.

[0044] In other examples, the ceramic particles may be lithium-containing, ionically conductive ceramic particles, such as lithium-containing oxides or lithium-containing phosphorus oxide particles. Specific examples include one or more selected from the group consisting of LAGP (lithium aluminum germanium phosphate) compounds, LLZO (lithium lanthanum zirconium oxide) compounds, LATP (lithium aluminum titanium phosphate) compounds, LLZTO (lithium lanthanum zirconium tantalum oxide) compounds, LLTO (lithium lanthanum titanium oxide) compounds, LSTP (lithium silicon titanium phosphate) compounds, LGPO (lithium germanium phosphate) compounds, and lithium oxides (e.g., Li2O).

[0045] The zeta potential of the polymer particles or ceramic particles can be adjusted not only by the type of particle but also by the particle size or surface properties of these particles. Therefore, in order to achieve the zeta potential, dispersibility, or appropriate porosity of the coating layer of the polymer particles or ceramic particles, the polymer particles or ceramic particles have an average particle size (D) of 300 nm to 3 μm, 500 nm to 2.5 μm, or 700 nm to 2 μm. 50 ) can have.

[0046] Furthermore, in order to control the surface properties of the polymer particles or ceramic particles and thereby adjust the zeta potential, the polymer particles or ceramic particles are included in the coating layer in a state in which they have been surface-treated with plasma or an ion beam.

[0047] On the other hand, the coating layer may have a form that includes a polymer binder and polymer particles or ceramic particles dispersed on such polymer binder. In this case, the polymer binder may be the same type of polymer as the binder contained in the electrode active material layer. Specific examples include polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene (PE), polypropylene, ethylene-propylene-diene monomer, sulfonated ethylene-propylene-diene monomer, nitrile rubber such as hydrogenated nitrile rubber, styrene-butadiene rubber, or fluororubber. A mixture or copolymer of two or more selected from these may also be used. However, the specific composition of the polymer binder can be determined as obvious to a person skilled in the art, taking into account the type and properties of the polymer particles or ceramic particles, and the method of forming the porous coating layer.

[0048] Furthermore, taking into consideration the good coating properties and porosity of the porous coating layer described above, as well as the good dispersibility of the particles, the coating layer may contain the polymer binder and the polymer particles or ceramic particles in a weight ratio of 1:9 to 5:5, or 2:8 to 4:6.

[0049] The aforementioned coating layer may have electrical insulating properties. Furthermore, the coating layer may be a porous insulating layer.

[0050] Furthermore, the coating layer has the property of not easily shrinking even at high temperatures. Therefore, when the separation film on which the coating layer is formed is applied to an electrode assembly, short circuits between the positive and negative electrodes are prevented even in high-temperature environments, thereby improving the high-temperature safety of the battery.

[0051] On the other hand, the coating layer can be formed by coating a coating layer-forming composition containing polymer particles or ceramic particles and a polymer binder onto a separation film, drying it, and rolling it.

[0052] In this case, the solid content of the coating layer-forming composition may be 19% to 25% by weight, more specifically 19% to 23% by weight, or more specifically 19% to 21% by weight. When the solid content of the coating layer-forming composition satisfies the above numerical range, the coating layer-forming composition can have a viscosity at a level that allows it to be coated onto the separation film.

[0053] The viscosity of the coating layer-forming composition at 25°C may be, for example, 1000 cP to 10000 cP at room temperature, specifically 2000 cP to 7000 cP, and more specifically 3000 cP to 5000 cP. When the viscosity of the coating layer-forming composition satisfies the above numerical range, the coating layer-forming composition is coated onto the separation film with a uniform thickness.

[0054] On the one hand, in order for the coating layer to exhibit the above-described peel strength range with respect to the separation membrane, such a coating layer can be formed by coating the coating composition for forming the coating layer on the separation membrane and then drying and rolling. At this time, the drying can be performed, for example, at a temperature of 60°C to 150°C for 0.5 hours to 12 hours. Further, after such drying, the rolling can be performed, for example, under a pressure application of 85 kg / cm 2 ~160 kg / cm 2 or 90 kg / cm 2 ~150 kg / cm 2 for 2 to 4 times or 2 to 3 times. When the pressure during the rolling is more than 100 kg / cm 2 and less than 160 kg / cm 2 , it is preferable to perform the rolling 2 or 3 times. By the progress of such drying and rolling steps, the coating layer is formed on the separation membrane with a predetermined peel strength, and a lithium secondary battery including the electrode assembly of one embodiment can exhibit improved high-temperature stability and excellent electrochemical characteristics.

[0055] On the other hand, the separation membrane can be used without particular limitation as long as it is usually used as a separation membrane in a lithium secondary battery. In particular, those having low resistance to ion movement of the electrolyte and excellent electrolyte moisture retention ability are preferable.

[0056] For example, as the separation membrane, a porous polymer film containing a polyolefin-based polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer, and an ethylene / methacrylate copolymer, or a laminate structure of two or more layers thereof can be used. Also, a normal porous non-woven fabric, for example, a non-woven fabric made of high-melting-point glass fibers, polyethylene terephthalate fibers, etc. can be used as the separation membrane.

[0057] The thickness of the separation membrane (D2) may be 5 μm to 20 μm, preferably 5 μm to 15 μm, and more preferably 6 μm to 13 μm. When the thickness of the separation membrane satisfies the above range, it is possible to prevent short circuits between the positive and negative electrodes while minimizing the cell resistance. As a result, it is possible to prevent a decrease in the energy density of the lithium secondary battery and improve its lifespan characteristics.

[0058] On the other hand, the positive electrode may include a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector.

[0059] The positive electrode current collector is not particularly limited as long as it does not induce a chemical change in the battery and is conductive. For example, the current collector can be made of stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel with a surface treatment of carbon, nickel, titanium, silver, etc.

[0060] The positive electrode current collector can have a thickness of 3 μm to 500 μm, and fine irregularities can be formed on the surface of the positive electrode current collector to enhance adhesion to the positive electrode active material layer. For example, it can be used in various forms such as film, sheet, foil, net, porous material, foam, and nonwoven fabric.

[0061] The positive electrode active material layer may contain a positive electrode active material and may further contain conductive materials, binders, etc., as needed.

[0062] The positive electrode active material is a compound capable of reversible intercalation and deintercalation of lithium, and specifically, it can include compounds such as lithium metal oxides or lithium metal phosphates containing one or more metals such as iron, cobalt, manganese, nickel or aluminum and lithium. More specifically, such compounds include lithium-manganese-based oxides (e.g., LiMnO2, LiMn2O4, etc.), lithium-cobalt-based oxides (e.g., LiCoO2, etc.), lithium-nickel-based oxides (e.g., LiNiO2, etc.), lithium-nickel-manganese-based oxides (e.g., LiNi 1-Y Mn Y O2 (where 0 < Y < 1), LiMn 2-Z Ni Z O4 (where 0 < Z < 2), etc.), lithium-nickel-cobalt-based oxides (e.g., LiNi 1-Y1 Co Y1 O2 (where 0 < Y1 < 1), etc.), lithium-manganese-cobalt-based oxides (e.g., LiCo 1-Y2 Mn Y2 O2 (where 0 < Y2 < 1), LiMn 2-Z1 Co Z1 O4 (where 0 < Z1 < 2), etc.), lithium-nickel-manganese-cobalt-based oxides (e.g., Li(Ni p Co q Mn r )O2 (where 0 < p < 1, 0 < q < 1, 0 < r < 1, p + q + r = 1) or Li(Ni p1 Co q1 Mn r1 O4 (where 0 < p1 < 2, 0 < q1 < 2, 0 < r1 < 2, p1 + q1 + r1 = 2), etc.), or lithium-nickel-cobalt-transition metal (M) oxides (e.g., Li(Ni p2 Co q2 Mn r2 M<000003> s2O2 (where M is selected from the group consisting of Al, Fe, V, Cr, Ti, Ta, Mg, and Mo, and p2, q2, r2, and s2 are atomic fractions of independent elements, 0 < p2 < 1, 0 < q2 < 1, 0 < r2 < 1, 0 < s2 < 1, and p2 + q2 + r2 + s2 = 1), etc.), lithium iron phosphate (e.g., Li 1+a Fe 1-x M x (PO 4-b )X b (where M is one or more selected from Al, Mg, and Ti, X is one or more selected from F, S, and N, -0.5 ≦ a ≦ 0.5, 0 ≦ x ≦ 0.5, 0 ≦ b ≦ 0.1), etc., and any one or two or more of these compounds can be included.

[0063] Among them, in terms of being able to enhance the capacity characteristics and safety of the battery, the lithium metal oxide is LiCoO2, LiMnO2, LiNiO2, lithium nickel manganese cobalt oxide (e.g., Li(Ni 1 / 3 Mn 1 / 3 Co 1 / 3 )O2, Li(Ni 0.6 Mn 0.2 Co 0.2 )O2, Li(Ni 0.5 Mn 0.3 Co 0.2 )O2, Li(Ni 0.7 Mn 0.15 Co 0.15 )O2, and Li(Ni 0.8 Mn 0.1 Co 0.1 )O2, etc.), lithium nickel cobalt aluminum oxide (e.g., Li(Ni 0.8 Co 0.15 Al 0.05 )O2, etc.), or lithium nickel manganese cobalt aluminum oxide (e.g., Li(Ni 0.86 Co 0.05 Mn 0.07 Al 0.02 )O2), lithium iron phosphate (e.g., LiFePO4), etc., and any one or two or more of these mixtures can be used.

[0064] The positive electrode active material is present in an amount of 60% to 99% by weight, preferably 70% to 99% by weight, and more preferably 80% to 98% by weight, based on the total weight of the positive electrode active material layer.

[0065] The positive electrode conductive material is a component for further improving the conductivity of the positive electrode active material. Such a conductive material is not particularly limited as long as it is conductive without inducing a chemical change in the battery, but examples of such materials that can be used include carbon powder such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, or thermal black; graphite powder such as natural graphite, artificial graphite, or graphite with a highly developed crystalline structure; conductive fibers such as carbon fibers or metal fibers; fluorinated carbon powder; conductive powders such as aluminum powder and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as polyphenylene derivatives.

[0066] Typically, the positive electrode conductive material is included in an amount of 1% to 20% by weight, preferably 1% to 15% by weight, and more preferably 1% to 10% by weight, based on the total weight of the positive electrode active material layer.

[0067] The positive electrode binder is a component that helps to bond the active material to the conductive material and to the current collector.

[0068] Examples of such binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, polyethylene (PE), polypropylene, ethylene-propylene-diene monomer, sulfonated ethylene-propylene-diene monomer, styrene-butadiene rubber, fluororubber, and various copolymers.

[0069] Typically, the positive electrode binder is included in an amount of 1% to 20% by weight, preferably 1% to 15% by weight, and more preferably 1% to 10% by weight, based on the total weight of the positive electrode active material layer.

[0070] On the other hand, the negative electrode may include a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector. Alternatively, the negative electrode may be a graphite electrode made of carbon (C). Alternatively, the negative electrode may contain lithium metal or be the metal current collector itself.

[0071] The negative electrode current collector is not particularly limited as long as it does not induce chemical changes in the battery and has high conductivity. For example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel surface treatments with carbon, nickel, titanium, silver, etc., and aluminum-cadmium alloys can be used.

[0072] The negative electrode current collector can typically have a thickness of 3 μm to 500 μm, and, similar to the positive electrode current collector, fine irregularities can be formed on the surface of the negative electrode current collector to strengthen the bonding force of the negative electrode active material. For example, it can be used in various forms such as films, sheets, foils, nets, porous materials, foams, and nonwoven fabrics.

[0073] The negative electrode active material layer may contain a negative electrode active material and may further contain conductive materials, binders, etc., as needed.

[0074] The negative electrode active material may include at least one selected from the group consisting of lithium metal, carbon materials capable of reversibly intercalating / deintercalating lithium ions, metals or alloys of these metals with lithium, metal composite oxides, materials capable of doping and dedoping lithium, and transition metal oxides.

[0075] As the carbon material capable of reversibly intercalating / deintercalating the lithium ions, any carbonaceous negative electrode active material generally used in lithium ion secondary batteries can be used without particular limitation, and typical examples thereof include crystalline carbon, amorphous carbon, or a combination thereof. Examples of the crystalline carbon include graphite such as amorphous, plate-like, flaky, spherical, or fibrous natural graphite or artificial graphite, and examples of the amorphous carbon include soft carbon (low-temperature calcined carbon) or hard carbon, mesophase pitch carbide, calcined coke, and the like.

[0076] As the metal or an alloy of these metals and lithium, a metal selected from the group consisting of Cu, Ni, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn, or an alloy of these metals and lithium is used.

[0077] Examples of the metal composite oxide include PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4, Bi2O5, Li x Fe2O3 (0 ≦ x ≦ 1), Li x WO2 (0 ≦ x ≦ 1) and Sn x Me 1-x Me’ y O z (Me: Mn, Fe, Pb, Ge; Me’: Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen; 0 < x ≦ 1; 1 ≦ y ≦ 3; 1 ≦ z ≦ 8) can be selected and used from the group consisting thereof.

[0078] As the substance capable of doping and undoping lithium, Si, SiO x(0 < x ≤ 2), Si-Y alloy (where Y is an element selected from the group consisting of alkali metals, alkaline earth metals, Group 13 elements, Group 14 elements, transition metals, rare earth elements, and combinations thereof, and is not Si), Sn, SnO2, Sn-Y (where Y is an element selected from the group consisting of alkali metals, alkaline earth metals, Group 13 elements, Group 14 elements, transition metals, rare earth elements, and combinations thereof, and is not Sn), etc. may be mentioned, and it is also possible to mix and use at least one of these with SiO2. As the element Y, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ge, P, As, Sb, Bi, S, Se, Te, Po, and combinations thereof can be selected.

[0079] Examples of the transition metal oxide include lithium-containing titanium composite oxide (LTO), vanadium oxide, lithium vanadium oxide, etc.

[0080] The negative electrode active material is contained at 60% to 99% by weight, preferably 70% to 99% by weight, more preferably 80% to 98% by weight based on the total weight of the negative electrode active material layer.

[0081] The negative electrode conductive material is a component that further improves the conductivity of the negative electrode active material. Such a conductive material is not particularly limited as long as it is conductive without inducing a chemical change in the battery, and can be, for example, carbon powder such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, or thermal black; graphite powder such as natural graphite, artificial graphite, or graphite with a highly developed crystalline structure; conductive fibers such as carbon fibers or metal fibers; fluorinated carbon powder; conductive powders such as aluminum powder and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as polyphenylene derivatives.

[0082] The negative electrode conductive material is included in an amount of 1% to 20% by weight, preferably 1% to 15% by weight, and more preferably 1% to 10% by weight, based on the total weight of the negative electrode active material layer.

[0083] The negative electrode binder is a component that helps to bond the negative electrode conductive material, negative electrode active material, and negative electrode current collector. Examples of such binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, polyethylene, polypropylene, ethylene-propylene-diene monomer, sulfonated ethylene-propylene-diene monomer, styrene-butadiene rubber, fluororubber, and various copolymers thereof.

[0084] Typically, the negative electrode binder is included in an amount of 1% to 20% by weight, preferably 1% to 15% by weight, and more preferably 1% to 10% by weight, based on the total weight of the negative electrode active material layer.

[0085] When using the metal itself without forming a negative electrode active material layer on the negative electrode, it can be manufactured by physically bonding, rolling, or vapor-depositing the metal onto the metal thin film itself or onto the negative electrode current collector. The vapor deposition method can be either electro-deposition or chemical vapor deposition.

[0086] For example, the metal bonded / rolled / deposited onto the metal thin film itself or the negative electrode current collector may include one metal selected from the group consisting of lithium (Li), nickel (Ni), tin (Sn), copper (Cu), and indium (In), or an alloy of two such metals.

[0087] <Lithium-ion secondary battery> Next, a lithium secondary battery according to another embodiment of the invention will be described.

[0088] Such a lithium secondary battery may include the electrode assembly and flame-retardant electrolyte described above. In this case, the electrode assembly is as previously described.

[0089] The flame-retardant electrolyte may be an electrolyte that does not volatilize well and does not ignite. Specifically, the flame-retardant electrolyte can be defined as an electrolyte containing a flame-retardant solvent and a lithium salt that have a flash point of 100°C or higher, or no flash point at all. In this case, the flame-retardant solvent can include substantially insoluble organic solvents with no flash point and organic solvents with a high flash point of 100°C or higher, or 100°C to 250°C, or 110°C to 200°C and low volatility. By including such a flame-retardant electrolyte containing a flame-retardant solvent and a lithium salt, lithium secondary batteries of other embodiments can exhibit excellent high-temperature safety. The flash point defining the flame-retardant solvent can be measured by a closed or open method according to the standard method of ASTM D3278.

[0090] On the other hand, the flame-retardant electrolyte has poor wetting properties for separation membranes used in lithium secondary batteries (e.g., polyolefin-based separation membranes), which reduces lithium ion mobility in the separation membrane. However, if the coating layer formed on the separation membrane contains polymer particles and / or ceramic particles with an absolute zeta potential of 25 mV or higher, the flame-retardant electrolyte is easily impregnated into the coating layer, thereby ensuring lithium ion mobility. Consequently, the electrochemical properties of the lithium secondary battery can be improved.

[0091] The flame-retardant electrolyte may contain a flame-retardant solvent and a lithium salt. In this case, the flame-retardant solvent can act as a medium through which ions involved in the electrochemical reactions of the battery can move.

[0092] In specific examples, the flame-retardant solvent may be an organic solvent having low volatility and a functional group that can contribute to flame retardancy or non-flammability, such as a sulfone functional group, a fluorine-containing functional group such as a fluorine-substituted hydrocarbon group, a phosphorus-containing functional group such as a phosphate group or a phosphonate group, and a nitrile functional group, and one or more such organic solvents may be used in mixture. More specifically, the flame-retardant solvent may contain one or more organic solvents selected from the group consisting of sulfone compounds, nitrile compounds, phosphoric acid compounds, and fluorine-substituted carbonate compounds.

[0093] Of these, the sulfone compound may be a cyclic sulfone compound or a linear sulfone compound, and specifically may contain one or more selected from the group consisting of sulfolane, tetramethylene sulfone, dibutyl sulfone, ethyl vinyl sulfone, methyl propyl sulfone, ethyl-i-propyl sulfone, ethyl-i-butyl sulfone, i-propyl-i-butyl sulfone, i-propyl-s-butyl sulfone, and butyl-i-butyl sulfone.

[0094] Furthermore, the nitrile compound may include one or more selected from the group consisting of acetonitrile, succinotril, adiponitrile, malonitrile, glutalonitrile, suberonitrile, and sebaconitrile.

[0095] Furthermore, the phosphate compound may include one or more selected from the group consisting of dimethylmethyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, diethylethyl phosphate, dimethyl(2-methoxyethoxy)methyl phosphonate, diethyl(2-methoxyethoxy)methyl phosphonate, and triphenyl phosphate.

[0096] Furthermore, the fluorine-substituted carbonate compounds include bis(2,2,3,3-tetrafluoropropyl) carbonate, methyl-2,2,2-trifluoroethyl carbonate, ethyl-2,2,2-trifluoroethyl carbonate, propyl-2,2,2-trifluoroethyl carbonate, methyl-2,2,2,2',2',2'-hexafluoro-i-propyl carbonate, and ethyl-2,2,2,2',2',2'-hexafluoro-i It may contain one or more substances selected from the group consisting of -propyl carbonate, di-2,2,2-trifluoroethyl carbonate, 2,2,2-trifluoroethyl-N,N-dimethyl carbonate, hexafluoro-i-propyl-N,N-dimethyl carbonate, 4-(2,2,3,3-tetrafluoropropoxymethyl)-[1,3]-dioxolan-2-one, and bis(2,2,3,3-pentafluoropropyl) carbonate.

[0097] On the other hand, the lithium salt is used as a medium for transferring ions within a lithium secondary battery. The lithium salt is, for example, Li as a cation. + It includes, and as an anion, F - Cl - , Br - , I - NO3 - , N(CN)2 - BF4 -, ClO4 - , B 10 Cl 10 - , AlCl4 - , AlO2 - , PF6 - , CF3SO3 - , CH3CO2 - , CF3CO2 - , AsF6 - , SbF6 - , CH3SO3 - , (CF3CF2SO2)2N - , (CF3SO2)2N - , (FSO2)2N - , BF2C2O4 - , BC4O8 - , PF4C2O4 - , PF2C4O8 - , (CF3)2PF4 - , (CF3)3PF3 - , (CF3)4PF2 - , (CF3)5PF - , (CF3)6P - , C4F9SO3 - , CF3CF2SO3 - , CF3CF2(CF3)2CO - , (CF3SO2)2CH - , CF3(CF2)7SO3 - and SCN - can include at least any one selected from the group consisting of.

[0098] Specifically, the lithium salt is LiCl, LiBr, LiI, LiBF4, LiClO4, LiB 10 Cl 10The electrolytes may include a single substance or a mixture of two or more substances selected from the group consisting of LiAlCl4, LiAlO2, LiPF6, LiCF3SO3, LiCH3CO2, LiCF3CO2, LiAsF6, LiSbF6, LiCH3SO3, LiFSI (Lithium bis(fluorosulfonyl)imide, LiN(SO2F)2), LiBETI (lithium bis(perfluoroethanesulfonyl)imide, LiN(SO2CF2CF3)2), and LiTFSI (lithium bis(trifluoromethanesulfonyl)imide, LiN(SO2CF3)2), but it is preferable to include LiN(SO2CF3)2 due to its superior stability. In addition to these, lithium salts commonly used as electrolytes in lithium secondary batteries can be used without limitation.

[0099] The concentration of the lithium salt can be appropriately changed within a range that is normally usable, but in order to obtain the optimal effect of forming a protective film to prevent corrosion on the electrode surface, it is included in the electrolyte at a concentration of 1M to 3M, preferably 1M to 2.5M, and more preferably 1M to 2M. When the concentration of the lithium salt satisfies the above range, the effect of improving the cycle characteristics of the lithium secondary battery during high-temperature storage is sufficient, the viscosity of the flame-retardant electrolyte is appropriate, and the impregnation of the flame-retardant electrolyte is improved.

[0100] The lithium secondary battery described above can be manufactured by placing the aforementioned electrode assembly into a cylindrical or rectangular battery case and then injecting a flame-retardant electrolyte. Alternatively, it can be manufactured by impregnating the aforementioned electrode assembly with a flame-retardant electrolyte, then placing the resulting product into a battery case and sealing it.

[0101] The aforementioned battery case may be one of those commonly used in this field, and there are no restrictions on its external shape depending on the battery's application. For example, it may be cylindrical, rectangular, pouch-type, or coin-type, but is not limited to these.

[0102] Lithium secondary batteries according to other embodiments of the invention can be used not only as battery cells used as power sources for small devices, but also preferably as unit batteries in medium- and large-sized battery modules containing a large number of battery cells. Preferred examples of such medium- and large-sized devices include electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, and energy storage systems (ESS).

[0103] The present invention will be described in more detail below through specific examples. However, the following examples are illustrative to aid in understanding the present invention and do not limit its scope. It will be apparent to those skilled in the art that various changes and modifications are possible within the scope and technical concept described herein, and such variations and modifications will naturally fall within the scope of the appended claims.

[0104] Examples and Comparative Examples First, in the following examples, the zeta potential of polymer particles or ceramic particles was measured using electrophoretic light scattering with a dynamic light scattering apparatus (product name: ELS-Z) while the polymer particles or ceramic particles were dispersed in a water solvent at a temperature of 25°C at a concentration of 0.1% by weight or less.

[0105] Furthermore, the flash point of the (flame-retardant) organic solvent contained in the (flame-retardant) electrolyte was measured using a closed-enclosure method according to the ASTM D93 standard method. Specifically, the organic solvent sample was filled into a sample container, the lid of the container was covered and sealed, and then the sample container was heated at a constant rate according to the standard method. During heating, the sample container was opened periodically to check for flame generation, and the temperature at the time of flame generation was measured as the flash point.

[0106] Example 1 Manufacturing of separation membrane-coating layer composites A separation membrane made of polyolefin material (thickness: 10 μm) was prepared.

[0107] It has a zeta potential of -50mV and an average particle size D 50 A composition for forming a coating layer (solids content: 21% by weight, viscosity: 4000 cP) was prepared by dispersing 1 μm polymethyl methacrylate (PMMA) polymer particles, hydrogenated nitrile rubber (H-NBR), and polyvinylidene fluoride (PVDF) in an N-methyl-2-pyrrolidone (NMP) solvent in a weight ratio of 7:1:2.

[0108] The aforementioned coating layer-forming composition was coated onto a polyolefin separation membrane (thickness: 10 μm), then dried at 80°C for 1 hour, and weighed 100 kg / cm². 2 A separation membrane-coating layer composite was manufactured by rolling the separation membrane twice under the specified pressure, thereby forming a 10 μm thick coating layer on one surface of the separation membrane.

[0109] (2) Manufacturing of electrode assemblies A 20 μm thick copper (Cu) metal thin film was prepared as the negative electrode current collector, and a negative electrode with a thickness of 75 μm was manufactured by forming a negative electrode active material layer containing artificial graphite as the negative electrode active material on one surface of the copper metal thin film.

[0110] A 15 μm thick aluminum (Al) metal thin film is prepared as the positive electrode current collector, and Li(Ni) is used as the positive electrode active material on one surface of the aluminum metal thin film. 0.8 Mn 0.1 Co 0.1 A positive electrode with a thickness of 60 μm was manufactured by forming a positive electrode active material layer containing O2.

[0111] An electrode assembly was manufactured by bringing the coating layer formed on one side of the separation membrane into contact with the positive electrode, and the other side of the separation membrane into contact with the negative electrode.

[0112] (3) Manufacturing of lithium secondary batteries A flame-retardant electrolyte was prepared by dissolving LiN(SO2CF3)2(LiFSI) in a flame-retardant solvent sulfolane (flash point: approximately 165°C) to a concentration of 1.5 M. After placing the electrode assembly in a battery case, the flame-retardant electrolyte was injected to produce a lithium secondary battery.

[0113] Example 2 After coating the separation film with the aforementioned coating layer-forming composition, it is dried at 80°C for 1 hour, and then weighed 100 kg / cm². 2 A separation membrane-coating layer composite was manufactured in the same manner as in Example 1, except that a coating layer with a thickness of 8 μm was formed on one surface of the separation membrane by rolling it four times at a pressure.

[0114] An electrode assembly and a lithium secondary battery were manufactured in the same manner as in Example 1, except that the separation membrane-coating layer composite manufactured by the method described above was used.

[0115] Example 3 After coating the separation film with the aforementioned coating layer-forming composition, it is dried at 80°C for 1 hour, resulting in a yield of 90 kg / cm². 2 A separation membrane-coating layer composite was manufactured in the same manner as in Example 1, except that a coating layer with a thickness of 11 μm was formed on one surface of the separation membrane by rolling it twice at a pressure.

[0116] An electrode assembly and a lithium secondary battery were manufactured in the same manner as in Example 1, except that the separation membrane-coating layer composite manufactured by the method described above was used.

[0117] Example 4 After coating the separation film with the aforementioned coating layer-forming composition, it is dried at 80°C for 1 hour, resulting in a yield of 150 kg / cm². 2 A separation membrane-coating layer composite was manufactured in the same manner as in Example 1, except that a 7 μm thick coating layer was formed on one surface of the separation membrane by rolling it twice at a pressure.

[0118] An electrode assembly and a lithium secondary battery were manufactured in the same manner as in Example 1, except that the separation membrane-coating layer composite manufactured by the method described above was used.

[0119] Comparative Example 1 A separation membrane made of polyolefin material (thickness: 10 μm) was prepared.

[0120] An electrode assembly and a lithium secondary battery were manufactured in the same manner as in Example 1, except that a separation membrane without a coating layer formed on one surface was placed in contact between the positive and negative electrodes.

[0121] Comparative Example 2 After coating the separation film with the aforementioned coating layer-forming composition, it is dried at 80°C for 1 hour, resulting in a load of 60 kg / cm². 2 A separation membrane-coating layer composite was manufactured in the same manner as in Example 1, except that a 12 μm thick coating layer was formed on one surface of the separation membrane by rolling it twice at a pressure.

[0122] An electrode assembly and a lithium secondary battery were manufactured in the same manner as in Example 1, except that the separation membrane-coating layer composite manufactured by the method described above was used.

[0123] Comparative Example 3 After coating the separation film with the aforementioned coating layer-forming composition, it is dried at 80°C for 1 hour, and weighed 200 kg / cm². 2 A separation membrane-coating layer composite was manufactured in the same manner as in Example 1, except that a 6 μm thick coating layer was formed on one surface of the separation membrane by rolling it twice at a pressure.

[0124] An electrode assembly and a lithium secondary battery were manufactured in the same manner as in Example 1, except that the separation membrane-coating layer composite manufactured by the method described above was used.

[0125] Comparative Example 4 After coating the separation film with the aforementioned coating layer-forming composition, it is dried at 80°C for 1 hour, resulting in a load of 80 kg / cm². 2 A separation membrane-coating layer composite was manufactured in the same manner as in Example 1, except that a coating layer with a thickness of 11.5 μm was formed on one surface of the separation membrane by rolling it twice at a pressure of .

[0126] An electrode assembly and a lithium secondary battery were manufactured in the same manner as in Example 1, except that the separation membrane-coating layer composite manufactured by the method described above was used.

[0127] Comparative Example 5 After coating the separation film with the aforementioned coating layer-forming composition, it is dried at 80°C for 1 hour, resulting in a yield of 150 kg / cm². 2 A separation membrane-coating layer composite was manufactured in the same manner as in Example 1, except that a 6.5 μm thick coating layer was formed on one surface of the separation membrane by rolling it four times at a pressure of .

[0128] An electrode assembly and a lithium secondary battery were manufactured in the same manner as in Example 1, except that the separation membrane-coating layer composite manufactured by the method described above was used.

[0129] Experimental Example 1 - Evaluation of peel strength between separation membrane and coating layer The 90° peel strength between the separation membrane and the coating layer was measured for the separation membrane-coating layer composites produced in Examples 1 to 4 and Comparative Examples 1 to 5.

[0130] Specifically, the separation membrane-coating layer composites produced in Examples 1 to 4 and Comparative Examples 1 to 5 were cut to a width of 25 mm, attached to a glass slide with double-sided tape, and then rolled twice with a 2 kg roller. The average value of the 90° peel strength was measured while peeling the coating layer from the separation membrane at a distance of 90 mm from the separation membrane at a speed of 300 mm / min under a temperature condition of 60°C. The measurement results are shown in Table 1 below.

[0131] [Table 1]

[0132] Experimental Example 2 - High-Temperature Safety Evaluation of Lithium-ion Secondary Batteries Figures 1 to 9 show the results of hot box tests performed on each lithium secondary battery manufactured in Examples 1 to 4 and Comparative Examples 1 to 5. Specifically, the hot box test was performed by raising the temperature from 25°C at a rate of 10°C / min, holding the temperature at 100°C, 120°C, 140°C, 150°C, 160°C, 170°C, and 180°C for 30 minutes each, and then raising the temperature to 200°C at a rate of 2°C / min.

[0133] Figures 1 to 4 are graphs showing the voltage-temperature changes over time for lithium secondary batteries manufactured in Examples 1 to 4, and Figures 5 to 9 are graphs showing the voltage-temperature changes over time for lithium secondary batteries manufactured in Comparative Examples 1 to 5.

[0134] Furthermore, Table 2 below shows the temperatures at which the lithium secondary batteries of Examples 1 to 4 and Comparative Examples 1 to 5 ignited in the hot box test.

[0135] [Table 2]

[0136] As shown in Figures 1 to 9 and Table 2, in Examples 1 to 4, where the 90° peel strength between the separation membrane and the coating layer is 30 gf / 25 mm to 140 gf / 25 mm, the strong adhesive force between the separation membrane and the coating layer prevents thermal shrinkage of the separation membrane even at high temperatures, thus confirming that the battery does not ignite and exhibits excellent high-temperature safety.

[0137] On the other hand, in Comparative Example 1, where no coating layer was formed on the separation membrane, and in Comparative Examples 2 and 4, where the 90° peel strength between the separation membrane and the coating layer was lower than 30 gf / 25 mm, it can be confirmed that the separation membrane shrinks due to heat at high temperatures, causing a short circuit between the positive and negative electrodes, and the battery ignites at temperatures above 170°C.

[0138] Experimental Example 3 - Evaluation of Cell Resistance of Lithium Secondary Battery The cell resistance values ​​were measured for each lithium secondary battery manufactured in Examples 1 to 4 and Comparative Examples 1 to 5, and the results are shown in Table 3 below.

[0139] Specifically, a lithium secondary battery was charged to 50% of its state of charge (SOC) at 25°C with a constant current of 0.1C, then discharged for 10 seconds with a constant current of 1.5C. The resistance at 0.1 seconds and the resistance between 0.1 seconds and 10 seconds were calculated from the voltage drop that occurred during this time.

[0140] [Table 3]

[0141] As shown in Table 3, in Examples 1 to 4, where the 90° peel strength between the separation membrane and the coating layer satisfies 30 gf / 25 mm to 140 gf / 25 mm, the cell resistance value increases compared to Comparative Example 1, where no coating layer was formed on the separation membrane, but it can be confirmed that the difference is not large.

[0142] On the other hand, in Comparative Examples 3 and 5, where the 90° peel strength between the separation membrane and the coating layer is greater than 140 gf / 25 mm, it can be confirmed that the cell resistance is higher compared to Examples 1 to 4 because the lithium ion conductivity at the interface between the separation membrane and the coating layer is lower.

Claims

1. positive electrode; Negative electrode; A separation membrane disposed between the positive electrode and the negative electrode; and A coating layer formed on one surface of the separation membrane, comprising polymer particles or ceramic particles having an absolute value of 25 mV or more for zeta potential; The 90° peel strength between the separation membrane and the coating layer is 30 gf / 25 mm to 140 gf / 25 mm. The aforementioned coating layer does not come into direct contact with the negative electrode in the electrode assembly.

2. The electrode assembly according to claim 1, wherein the coating layer is in direct contact with the positive electrode.

3. Thickness of the separation membrane (D ２ ) The thickness of the coating layer (D １ ) ratio D １ / D ２ The electrode assembly according to claim 1, wherein the value is 0.1 to 4.

4. The thickness of the coating layer (D １ The electrode assembly according to claim 1, wherein the diameter of the electrode is 30 μm or less.

5. The thickness of the separation membrane (D ２ The electrode assembly according to claim 1, wherein the diameter of the electrode is 5 μm to 20 μm.

6. The electrode assembly according to claim 1, wherein the polymer particles include one or more selected from the group consisting of polyethylene oxide (PEO), polyphenylene sulfide (PPS), polymethyl (meth)acrylate, polystyrene, polyvinyl chloride, polycarbonate, polysulfone, polyethersulfone, polyetherimide, polyphenylsulfone, polyamideimide, polyimide, polybenzimidazole, polyetherketone, polyphthalamide, polybutylene terephthalate, and polyethylene terephthalate.

7. The ceramic particles are boehmite (γ-AlO(OH)), Al ２ O ３ TiO ２ Fe ２ O ３ SiO ２ ZrO ２ Co ３ O ４ SnO ２ NiO, ZnO, V ２ O ５ MnO, LAGP (lithium aluminum germanium phosphate) - based compound, LLZO (lithium lanthanum zirconium oxide) - based compound, LATP (lithium aluminum titanium phosphate) - based compound, LLZTO (lithium lanthanum zirconium tantalum oxide) - based compound, LLTO (lithium lanthanum titanium oxide) - based compound, LSTP (lithium silicon titanium phosphate) - based compound, LGPO (lithium germanium phosphate) - based compound, and lithium oxide, and the electrode assembly according to claim 1, comprising at least one selected from the group consisting of.

8. The polymer particles or ceramic particles have an average particle size (D) of 300 nm to 3 μm. ５０ The electrode assembly according to claim 1, having )

9. The electrode assembly according to claim 1, wherein the coating layer comprises a polymer binder and polymer particles or ceramic particles dispersed on the polymer binder.

10. The electrode assembly according to claim 9, wherein the coating layer comprises the polymer binder and the polymer particles or ceramic particles in a weight ratio of 1:9 to 5:

5.

11. The electrode assembly according to any one of claims 1 to 10; and A lithium secondary battery comprising a flame-retardant electrolyte containing a flame-retardant solvent having a flash point of 100°C or higher, or having no flash point, and a lithium salt.

12. The lithium secondary battery according to claim 11, wherein the flame-retardant solvent comprises one or more organic solvents having a functional group selected from the group consisting of sulfone-based functional groups, fluorine-containing functional groups, phosphorus-containing functional groups, and nitrile-based functional groups.

13. The lithium secondary battery according to claim 11, wherein the flame-retardant solvent comprises one or more organic solvents selected from the group consisting of sulfone compounds, nitrile compounds, phosphoric acid compounds, and fluorine-substituted carbonate compounds.

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