Separator for electrochemical device with improved compression resistance, electrochemical device including the same, and method for manufacturing the same

Abstract

The present invention relates to a separator for an electrochemical device, an electrochemical device including the same, and a method for manufacturing the same. The separator for an electrochemical device according to the present invention includes a polymer substrate having small and uniform pores, and includes a water-based organic / inorganic composite porous coating layer and an adhesive coating layer, and has an effect of improving compression resistance.

Description

[Technical Field]

[0001] The present invention claims the benefit of the filing date of Patent Application No. 10-2022-0082782 filed with the Korean Intellectual Property Office on July 5, 2022, and the benefit of the filing date of Patent Application No. 10-2023-0086258 filed with the Korean Intellectual Property Office on July 4, 2023, all of the contents of which are incorporated herein.

[0002] The present invention relates to a separator for an electrochemical device such as a secondary battery, an electrochemical device including the separator, and a method for manufacturing the same. [Background technology]

[0003] Secondary batteries are basically composed of a positive electrode, a negative electrode, a separator, and an electrolyte solution. They are capable of reversibly converting chemical energy and electrical energy, allowing them to be charged and discharged. Lithium-ion secondary batteries are a typical example. Lithium-ion secondary batteries are high-energy-density energy storage devices and are widely used in small electronic devices such as mobile phones and laptops. In recent years, in response to environmental issues, high oil prices, and the need for energy efficiency and storage, their application in hybrid electric vehicles (HEVs), plug-in electric vehicles (Plug-in EVs), electric bicycles (e-bikes), and energy storage systems (ESSs) has rapidly expanded.

[0004] Ensuring the safety of lithium secondary batteries is an important issue to be resolved during their manufacture and use. In particular, separators commonly used in lithium secondary batteries exhibit extreme thermal shrinkage under high temperatures due to their material properties and manufacturing process characteristics, which can lead to safety issues such as internal short circuits. Recently, to ensure the safety of lithium secondary batteries, organic / inorganic composite porous separators have been proposed, in which a porous coating layer is formed by coating a porous polymer substrate with a mixture of inorganic particles and a binder. However, when an electrode and a separator are stacked to form an electrode assembly, there is a high risk of the electrode and the separator separating from each other due to insufficient interlayer adhesion. In this case, inorganic particles detached from the porous coating layer during the separation process may act as local defects within the lithium secondary battery device.

[0005] To address these issues, an adhesive layer containing an adhesive binder resin has been considered for providing adhesive strength to the porous coating layer. However, when both an organic / inorganic composite porous coating layer and an adhesive layer are disposed on the surface of a porous polymer substrate, the binder resin may flow into the pores of the porous polymer substrate, resulting in reduced resistance. Furthermore, during the lamination process with the electrodes during the manufacture of an electrode assembly, the organic / inorganic porous coating layer may excessively press the polymer substrate or tear the polymer substrate, resulting in damage. Therefore, there is a growing demand for the development of a new separator that has excellent adhesion to electrodes and durability. Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a separator for an electrochemical device having improved compression resistance. Another object of the present invention is to provide an electrochemical device including the separator. Another object of the present invention is to provide a method for manufacturing the separator. It will be readily apparent that other objects and advantages of the present invention can be achieved by the means or methods recited in the claims and combinations thereof. [Means for solving the problem]

[0007] A first aspect of the present invention relates to a separator for an electrochemical device, the separator comprising: a porous polymer substrate; a porous organic / inorganic composite porous coating layer disposed on at least one surface of the polymer substrate; and an adhesive coating layer disposed on one surface of the organic / inorganic porous coating layer, the opposite surface of the polymer substrate; wherein the polymer substrate is a polymer membrane having an average pore size of 40 nm or less, and the pore distribution is such that the full width at half maximum (FWHM) of a Gaussian distribution measured through a pore size distribution is 8.0 nm or less; the organic / inorganic composite porous coating layer comprises a particulate binder resin and inorganic particles; the particulate binder resin comprises an acrylic binder resin and a PVdF binder resin; and the adhesive coating layer comprises a PVdF binder resin.

[0008] In a second aspect of the present invention, in the first aspect, the polymer-based material has an air permeability of 100 sec / 100 cc or less and a resistance of 0.6 ohms or less.

[0009] In a third aspect of the present invention, in the first or second aspect, the separator has an air permeability of 100 sec / 100 cc or less and a resistance of 0.6 ohms or less.

[0010] A fourth aspect of the present invention is any one of the first to third aspects, wherein the polymer-based material has a porosity of 20 vol % to 50 vol %.

[0011] A fifth aspect of the present invention is any one of the first to fourth aspects, wherein the organic / inorganic composite porous coating layer contains the inorganic particles and the binder resin in a weight ratio of 75:25 to 90:10.

[0012] A sixth aspect of the present invention is any one of the first to fifth aspects, wherein the organic / inorganic composite porous coating layer is 100 wt% or more of a mixture of the inorganic particles and the binder resin.

[0013] A seventh aspect of the present invention is any one of the first to sixth aspects, wherein in the organic / inorganic composite porous coating layer, the PVdF-based binder resin and the acrylic-based binder resin are contained in a weight ratio of 30:70 to 5:95.

[0014] An eighth aspect of the present invention is any one of the first to seventh aspects, wherein the adhesive coating layer contains 90% by weight or more of the PVdF-based binder resin relative to 100% by weight of the entire adhesive coating layer.

[0015] In a ninth aspect of the present invention, in the eighth aspect, the PVdF-based binder resin of the adhesive coating layer has a weight average molecular weight of 600,000 or less.

[0016] A tenth aspect of the present invention is any one of the first to ninth aspects, wherein the PVdF-based binder resin of each of the organic / inorganic composite porous coating layer and the adhesive coating layer contains, as polymerization units, a copolymer of vinylidene fluoride and a monomer copolymerizable with vinylidene fluoride, and the copolymer contains 70 wt % or more of vinylidene fluoride.

[0017] An eleventh aspect of the present invention is the tenth aspect, wherein the PVdF binder resin has a degree of substitution with the monomer of 1 wt % to 40 wt %.

[0018] In a twelfth aspect of the present invention, in any one of the first to eleventh aspects, the particulate binder resin is maintained in particulate form within the separation membrane.

[0019] A thirteenth aspect of the present invention is any one of the first to twelfth aspects, wherein the thickness of the adhesive coating layer is 8% to 30% of the thickness of the organic / inorganic composite porous coating layer (100%).

[0020] A fourteenth aspect of the present invention relates to a method for producing the separation membrane according to any one of the first to thirteenth aspects, the method comprising:

[0021] (S10) preparing a porous polymer substrate; (S20) forming an organic / inorganic composite porous coating layer on a surface of the polymer substrate; and (S30) forming an adhesive coating layer on a surface of the organic / inorganic composite porous coating layer opposite to the surface on which the polymer substrate is disposed,

[0022] The step (S20) is carried out by dispersing inorganic particles and a particulate binder resin in an aqueous solvent as a dispersion medium to prepare a slurry for forming an organic / inorganic composite porous coating layer, applying the slurry to the surface of the polymer substrate, and drying the slurry.

[0023] The step (S30) is carried out by dispersing a particulate binder resin in an aqueous solvent as a dispersion medium to prepare a composition for forming an adhesive coating layer, applying the composition to the surface of the organic / inorganic composite porous coating layer, and drying the composition. [Effects of the Invention]

[0024] The separator for an electrochemical device according to the present invention includes a polymer substrate having small and uniform pores, and is provided with a water-based organic / inorganic composite porous coating layer and an adhesive coating layer, thereby improving compression resistance.

[0025] The separator may be damaged during the lamination process, which bonds the electrode and separator by applying heat and pressure, and during charge / discharge cycles inside the battery. In particular, where the thickness of the substrate is significantly reduced locally, insulation breakdown can occur, resulting in a short circuit. This can cause the pores formed by the separator to deform, altering the path and speed of lithium ion transport, affecting the battery's lifespan and rate-limiting characteristics. Furthermore, if the separator is deformed, causing overvoltage, the possibility of lithium plating (Li-plating), in which the negative electrode potential rapidly drops to 0 V, increases. Therefore, the use of a separator with improved compression resistance can withstand applied pressure and prevent separator deformation. In particular, when pressure is applied to the separator of the present invention, the coating layer structure acts as a buffer, reducing the pressure on the porous substrate and preventing separator deformation.

[0026] The drawings attached to this specification illustrate preferred embodiments of the present invention and serve to facilitate a better understanding of the technical concept of the present invention together with the contents of the invention described above, and therefore the present invention should not be interpreted as being limited to only the matters shown in such drawings. Meanwhile, the shape, size, scale, or ratio of elements in the drawings described in this specification may be exaggerated to emphasize a clearer description. [Brief explanation of the drawings]

[0027] [Figure 1] 1(a) is a schematic diagram showing the cross-sectional structure of a separation membrane according to one embodiment of the present invention, and FIG. 1(b) is a schematic diagram showing Example 1. FIG. [Figure 2] 1 is a schematic diagram illustrating the cross-sectional structure of the separation membrane of Comparative Example 1. [Figure 3] 1 is a schematic diagram illustrating the cross-sectional structure of the separation membrane of Comparative Example 2. [Figure 4] 1 is a schematic diagram illustrating the cross-sectional structure of the separation membrane of Comparative Example 3. [Figure 5] 1 is a schematic diagram illustrating the cross-sectional structure of the separation membrane of Comparative Example 4. [Figure 6] This relates to the full width at half maximum (FWHM) of the PSD (pore size distribution) distribution, and the full width at half maximum can be expressed as the difference between two points X2 and X1 on the x-axis that correspond to 1 / 2 (1 / 2T) of the mode (T) on the y-axis. [Figure 7] The air permeability curves for the dry and wet samples are shown. DETAILED DESCRIPTION OF THE INVENTION

[0028] The present invention will now be described in detail. Prior to that, the terms and words used in the specification and claims should not be construed as being limited to their ordinary or dictionary meanings, but should be construed as meanings and concepts consistent with the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of terms to best describe his or her invention. Therefore, it should be understood that the embodiments described in this specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention and do not represent the entire technical idea of ​​the present invention, and that various equivalents and modifications may be available at the time of filing this application.

[0029] Throughout this specification, when a part is said to "comprise" certain elements, this means that it can further include other elements, rather than excluding other elements, unless specifically stated to the contrary.

[0030] Furthermore, the terms "about," "substantially," and the like used throughout the specification of this application are used to mean a numerical value or a value close to that value when the manufacturing and material tolerances inherent in the stated meaning are given, and are used to prevent unscrupulous infringers from unfairly taking advantage of the disclosure in which exact or absolute numerical values ​​are mentioned to aid in the understanding of this application.

[0031] Throughout this specification, the phrase "A and / or B" means "A or B, or both."

[0032] Certain terminology used in the following detailed description of the invention is for convenience only and is not limiting. The words "right," "left," "top," and "bottom" designate directions in the drawings to which reference is made. The words "inwardly" and "outwardly" designate directions toward or away from the geometric center of the designated device, system, and components thereof, respectively. "Front," "rear," "upper," "lower," and related words and phrases designate locations and orientations in the drawings to which reference is made and are not intended to be limiting. Such terms include the above-listed words, derivatives thereof, and words of similar import.

[0033] The present invention relates to a separator for an electrochemical device. In the present invention, the electrochemical device is a device that converts chemical energy into electrical energy through an electrochemical reaction and is a concept that includes primary batteries and secondary batteries. The secondary batteries are capable of being charged and discharged and include lithium ion batteries, nickel-cadmium batteries, nickel-metal hydride batteries, etc.

[0034] 1.Separation membrane In the present invention, a separator refers to a material that electrically insulates a cathode and an anode to prevent a short circuit between them, while providing a path for the movement of metal ions, such as lithium ions, between the anode and the cathode. FIG. 1(a) is a schematic cross-sectional view of a separator 10 according to one embodiment of the present invention. The separator 10 according to the present invention includes a porous polymer substrate 11 having a plurality of pores and an organic / inorganic composite porous coating layer 12 disposed on at least one surface of the polymer substrate. The separator also includes an adhesive coating layer 13 formed on the outermost surface of the separator. In a preferred embodiment, the separator includes a polymer substrate, an organic / inorganic composite porous coating layer formed on one surface of the polymer substrate, and an adhesive coating layer formed on the organic / inorganic composite porous coating layer, which is disposed on one side of the organic / inorganic composite porous coating layer opposite the polymer substrate. The organic / inorganic composite porous coating layer and the adhesive coating layer may be formed on one or both surfaces of the polymer substrate. Hereinafter, the separation membrane of the present invention will be described in detail for each component.

[0035] 1) Porous polymer substrate The polymer substrate is a porous polymer membrane with a plurality of pores formed therein, which functions as an ion-conducting barrier that allows ions to pass through while blocking electrical contact between the anode and cathode. The pores include open pores that are interconnected, allowing gas or liquid to pass from one side of the substrate to the other.

[0036] In one embodiment of the present invention, the polymer substrate includes a polymer material, and the polymer material may include a thermoplastic resin to impart a shutdown function to the separator. The shutdown function refers to a function in which, when the battery temperature rises, the polymer material contained in the substrate dissolves and closes the pores of the polymer substrate, thereby blocking ion movement and preventing thermal runaway of the battery. In one embodiment of the present invention, the thermoplastic resin may include a polyolefin-based resin having a melting temperature (melting point) of less than 200°C. Examples of the polyolefin-based resin include polyethylene, polypropylene, polybutene, and polypentene, and may include one or a mixture of two or more of these. As a specific example, the polyolefin-based resin may include two or more selected from polyethylene, polypropylene, and polypentene. As another example, the polyolefin-based resin may be polyethylene and / or polypropylene.

[0037] In one embodiment of the present invention, the weight average molecular weight (Mw) of the polyolefin resin may be 300,000 to 1,500,000. When the molecular weight is within this range, the polymer substrate has excellent mechanical properties and good film formability. When the molecular weight (Mw) is too high, film formation becomes difficult.

[0038] Meanwhile, in the present invention, the weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC, PL GPC220, Agilent Technologies), and the measurement conditions can be set as follows.

[0039] Column: PL Olexis (Polymer Laboratories) -Solvent: TCB (Trichlorobenzene) -Flow rate: 1.0ml / min -Sample concentration: 1.0mg / ml -Injection volume: 200μl -Column temperature: 160℃ -Detector: Agilent High Temperature RI detector -Standard: Polystyrene (corrected by a cubic function)

[0040] The method for measuring the weight average molecular weight can be applied to the measurement of the weight average molecular weight of the polyolefin resin as well as to the polymer materials mentioned in the specification of the present application.

[0041] In addition to the polyolefin resin, the resin may include one or more selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyamide, polycarbonate, polyimide, polyether ether ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, and polyethylene naphthalene.

[0042] In one embodiment of the present invention, the porous polymer substrate may comprise one or more nonwoven fabric sheets or one or more polymer films. Alternatively, the porous polymer substrate may comprise one or more nonwoven fabrics and one or more polymer films. In one embodiment of the present invention, the polymer substrate may be a single layer. Alternatively, the porous substrate may have a laminated structure in which two or more layers of nonwoven fabrics and / or films are laminated. The polymer film may refer to a film formed into a sheet by melting / extrusion of a polymer resin.

[0043] In the present invention, the polymer substrate preferably has a thickness of 7 μm to 15 μm. If the thickness exceeds this range and is too thick, the lithium ion (Li-ion) conduction path becomes longer, causing an increase in resistance and possibly deteriorating battery performance. On the other hand, if the thickness is too thin, the conductive barrier function may be impaired, increasing the incidence of short circuits.

[0044] Meanwhile, in one embodiment of the present invention, the thickness of the polymer substrate or the like can be measured using a contact-type thickness gauge, such as Mitutoyo's VL-50S-B.

[0045] Meanwhile, in one embodiment of the present invention, the average diameter of the pores of the polymer-based material may be 40 nm or less, and preferably, for example, 30 nm or less. If the pore size is excessively large exceeding this range, when pressure is applied during the manufacturing process of the battery, such as the lamination process, deformation before and after compression may be significant, which is undesirable.

[0046] The average pore diameter can be calculated using image processing software (e.g., SigmaScan Pro 5.0) on a scanning electron microscopy (SEM) image. Alternatively, a capillary flow porometer can be used to obtain the permeability curves of a half-dried sample and a wet sample, and the intersection of these two curves can be determined as the average pore diameter.

[0047] Meanwhile, in one embodiment of the present invention, the polymer-based material may have an air permeability of 100 sec / 100 cc or less, for example, 60 to 85 sec / 100 cc. If the air permeability is too low, i.e., below this range, the separator substrate has poor mechanical properties. On the other hand, if the air permeability is too high, the path of lithium ions (Li-ions) may become long, which may shorten the battery life.

[0048] In the present invention, the permeability time refers to the time it takes for 100 ml of air to pass through a sample, such as a polymer substrate or a separation membrane, of 1 square inch under a certain air pressure, and may be expressed in units of seconds / 100 cc. It may also be used interchangeably with the permeation time, and is usually expressed as a Gurley value. In one embodiment of the present invention, the permeability may be measured according to the standard in the art. For example, the permeability may be measured using a known Gurley Densometer in accordance with ASTM D726-58 or ASTM D726-94, for example, using air at a pressure of 0.304 kPa or 1.215 kN / m. 2 of water pressure in one square inch (or 6.54 cm 2 In another embodiment, the air permeability can be expressed in seconds as the time it takes for 100 ml of air to pass through a 1 inch square sample at room temperature under a constant pressure of 4.8 inches H2O according to the Gurley measurement method of the Japanese Industrial Standard (JIS-P8117). In one embodiment of the present invention, the air permeability can be measured, for example, using an EG01-55-1MR instrument manufactured by Asahi Seiko Co., Ltd. in accordance with the standard.

[0049] In addition, in the present invention, the polymer-based material has a full width at half maximum (FWHM) of 8.0 nm or less in the pore diameter distribution according to a normal distribution (Gaussian distribution) measured through the pore size distribution. The full width at half maximum may be defined as the difference in size between two points on the x-axis that are half the maximum value on the y-axis (the most frequent value among pore sizes) in a normal distribution of pore size distributions that classify pores formed inside a polymer-based material according to size. In the distribution, the x-axis represents the pore size (diameter), and the y-axis represents the frequency of the number of pores corresponding to the pore size on the x-axis (e.g., the number of pores or the percentage of the number of pores). In the present invention, the x-axis may be expressed in nm or μm. FIG. 6 shows the full width at half maximum (FWHM) of a pore size distribution (PSD), which can be expressed as the difference between two points X2 and X1 on the x-axis that correspond to 1 / 2 (1 / 2T) of the mode (T) on the y-axis. Referring to FIG. 6, the full width at half maximum (FWHM) can be expressed as the difference between two points X2 and X1 on the x-axis that correspond to 1 / 2 (1 / 2T) of the mode (T) on the y-axis. The difference can be expressed as an absolute value. Meanwhile, the normal distribution can be symmetrical, asymmetrical, or any distribution other than normal, based on the maximum value.

[0050] Meanwhile, in one embodiment of the present invention, the half-width can be determined from the distribution of the remaining pores excluding the pore with the largest diameter. Meanwhile, in the present invention, the shape of the pores can be circular, elliptical, or amorphous, and the cross section can be a closed curve. The pore diameter means the longest distance between any two points on the closed curve. When the above range is satisfied, the polymer substrate has small pore sizes and high pore size uniformity. A polymer substrate with these characteristics can exhibit high dimensional stability and a high breakdown voltage.

[0051] In one embodiment of the present invention, the polymer substrate may have a resistance of 0.6 ohms or less. Excessively high resistance is undesirable because it may deteriorate the battery's life characteristics during repeated charge and discharge. As described herein, the polymer substrate of the present invention has small pore sizes and a low porosity, but as described above, the half-width is uniformly distributed at 8.0 nm or less, allowing the resistance to be maintained at a low level.

[0052] Meanwhile, in one embodiment of the present invention, the porosity of the polymer substrate may be 20 vol% to 50 vol%. If the porosity is too low, by-products may be generated due to the degradation of lithium ions (Li-ions) during charge / discharge and may accumulate in the pores, shortening the battery life. On the other hand, if the porosity is too high, the mechanical properties of the separator may be reduced, making it difficult to ensure uniform mechanical properties across the entire surface of the separator.

[0053] The term "porosity" refers to the ratio of the volume occupied by pores to the total volume, and is expressed in vol%. It can be used interchangeably with terms such as porosity and porosity. In the present invention, the porosity can be measured by any method known in the art, including the Brunauer-Emmett-Teller (BET) method using nitrogen gas, water intrusion porosimetry, capillary flow porosimetry, or mercury porosimetry. Alternatively, in one embodiment of the present invention, the true density of the porous substrate can be calculated from the density (apparent density) of the obtained porous substrate, the composition ratio of the materials contained in the porous substrate, and the density of each component. The porosity of the porous substrate can then be calculated from the difference between the apparent density and the true density (net density). For example, the porosity can be calculated using the following Equation 1:

[0054] [Formula 1] Porosity (vol%) = {1 - (apparent density / true density)} x 100

[0055] On the other hand, in the above formula, the apparent density can be calculated from the following [Formula 2].

[0056] [Formula 2] Apparent density (g / cm 3 ) = {Weight of porous substrate [g] / (Thickness of porous substrate [cm] × Area of ​​porous substrate [cm 2 ])}

[0057] In one embodiment of the present invention, the porous substrate can be manufactured by a method for manufacturing a polymer film, preferably a wet manufacturing method, which includes the steps of (S1) preparing a mixture, (S2) extruding the mixture and forming an extruded sheet, (S3) stretching the extruded sheet, (S4) removing the pore-forming agent, and (S5) heat-setting the extruded sheet.

[0058] In step (S1), an appropriate type of polymer resin is selected depending on the final physical properties of the separator, and the selected polymer resin is mixed with a pore-forming agent. The polymer resin may be a polyolefin-based polymer resin. Examples of the polyolefin-based polymer resin include polyethylene (e.g., high-density polyethylene, linear low-density polyethylene, low-density polyethylene, or ultra-high-molecular-weight polyethylene), polypropylene, polybutylene, polypentene, and the like, or a combination of two or more of these.

[0059] The pore-forming agent is a substance dispersed in a polymer and causes heterogeneity in the substrate produced through extrusion, drawing, etc., and is subsequently removed from the substrate. Therefore, the portions of the substrate where the pore-forming agent was located remain in the form of pores in the substrate. The pore-forming agent is preferably a substance that is liquid during the extrusion process, but a substance that maintains a solid state can also be used. The pore-forming agent can be an aliphatic hydrocarbon solvent such as liquid paraffin, paraffin oil, mineral oil, or paraffin wax; a vegetable oil such as soybean oil, sunflower oil, rapeseed oil, palm oil, palm oil, coconut oil, corn oil, grapeseed oil, or cottonseed oil; or a plasticizer such as dialkyl phthalate. In particular, the plasticizer may be di-2-ethylhexyl phthalate (DOP), di-butyl phthalate (DBP), di-isononyl phthalate (DINP), di-isodecyl phthalate (DIDP), butyl benzyl phthalate (BBP), etc. Among these, liquid paraffin (LP, also referred to as "liquid paraffin") is particularly preferred.

[0060] Furthermore, the content of the pore-forming agent used in the preparation of the separator can be appropriately adjusted to achieve the desired level of porosity. To improve air permeability, a high content of the pore-forming agent is preferable, but excessive content can adversely affect the strength of the final substrate. Therefore, the content of the pore-forming agent may be 1 wt% to 80 wt% based on 100 wt% of the total weight of the polymer resin and pore-forming agent. If necessary, the content may be adjusted to 70 wt% or less, 60 wt% or less, or 50 wt% or less, or 1 wt% or more, 20 wt% or more, or 40 wt% or more. Meanwhile, in a specific embodiment of the present invention, to achieve an appropriate porosity in the porous substrate, for example, to achieve a porosity of about 45% or less, the pore-forming agent may be included in a range of 1 wt% to 60 wt% based on the total weight of the polymer resin and pore-forming agent.

[0061] Next, the mixture prepared in the above step is extruded through an extruder to obtain an extruded sheet. The extruder is not particularly limited and may be an extruder commonly used in the art, such as an extruder equipped with a T-die or a tubular die. The extrusion process can be carried out at a standard extrusion temperature, preferably at a temperature 10°C to 100°C higher than the melting point of the polymer resin used. Extrusion temperatures that exceed this range are undesirable because they can cause thermal degradation of the polymer resin, making film formation difficult and degrading the physical properties of the resulting substrate. An extruded sheet can be obtained through this extrusion process.

[0062] The extruded sheet is then subjected to a stretching process. This stretching process is carried out using a stretching machine commonly used in the art. The stretching machine may be, but is not limited to, a sequential biaxial stretching machine. Stretching the extruded sheet in this manner can increase the mechanical strength of the porous substrate. The stretching process is carried out in the machine direction (MD) and / or the transverse direction (TD). Stretching in all or one of these directions increases the tensile strength in the corresponding stretching direction. If necessary, the separator membrane of the present invention may be stretched in the machine direction (MD) and / or the transverse direction (TD) independently (e.g., uniaxial stretching), simultaneously, or sequentially (e.g., biaxial stretching) during the stretching process. Meanwhile, in one embodiment of the present invention, the temperature of the membrane during the stretching process may be controlled to 100°C to 130°C, preferably 110°C to 125°C. For example, the temperature of the membrane during the stretching can be controlled within a range of 115° C. to 121° C. When the stretching step is carried out within the above temperature range, a uniform membrane with small pores can be obtained.

[0063] Next, the pore-former is removed from the extruded sheet. The pore-former is removed by extraction using a solvent and drying. This removal process results in the formation of pores in the spaces previously occupied by the pore-former. Any solvent capable of extracting the pore-former can be used to extract the pore-former, but preferred solvents include methyl ethyl ketone, methylene chloride, and hexane, which have high extraction efficiency and fast drying times. Preferably, the solvent is methylene chloride, e.g., methylene dichloride (MC). The extraction method can be any common solvent extraction method, such as immersion, solvent spray, or ultrasonic, either individually or in combination. After the extraction of the pore-forming agent, the substrate is heat-set, resulting in a separator membrane with the desired physical properties, porosity, and air permeability. The heat-set step can be performed using a heating device, such as an oven, capable of applying the appropriate temperature required for heat-set. In particular, the previously dried membrane undergoes heat-set to reduce the shrinkage rate of the final membrane by removing residual stress. Heat-set involves fixing the membrane and applying heat to forcibly hold the membrane, which tends to shrink, to remove residual stress. While a higher heat-set temperature is advantageous for reducing shrinkage, if the heat-set temperature is too high, the membrane may partially melt, causing the formed pores to close and reducing permeability. The preferred heat-set temperature is selected within a temperature range in which approximately 10 wt% to 30 wt% of the crystalline portion of the membrane melts. If the heat setting temperature is selected to be lower than the temperature at which about 10 wt% of the crystalline portion of the film melts, the reorientation of the polyethylene molecules in the film is insufficient, and the film is not effective in removing residual stress. If the heat setting temperature is selected to be higher than the temperature at which about 30 wt% of the crystalline portion of the film melts, the pores will be blocked due to partial melting, resulting in reduced permeability.

[0064] 2) Organic / inorganic composite porous coating layer In the present invention, the separator includes an organic / inorganic composite porous coating layer formed on at least one surface of a polymer substrate. The organic / inorganic composite porous coating layer contains a binder resin and inorganic particles, and has a structure in which a number of micropores are formed therein and these micropores are connected to each other, making it a porous layer that allows gas or liquid to pass from one side to the other.

[0065] In a specific embodiment of the present invention, the organic / inorganic composite porous coating layer includes inorganic particles and a binder resin and is formed on the surface of a polymer substrate. The organic / inorganic composite porous coating layer may be formed using an aqueous method in which an aqueous slurry obtained by dispersing a water-dispersible binder resin in an aqueous solvent such as water is applied and dried. As a result, the binder resin is introduced into the organic / inorganic composite porous coating layer in the form of particles having a predetermined diameter. That is, the organic / inorganic composite porous coating layer may exhibit a mixed phase of inorganic particles and particulate organic binder resin. As the binder resin is introduced into the organic / inorganic composite porous coating layer in the form of particles, the organic / inorganic composite porous coating layer is sufficiently porous, resulting in excellent ion permeability and preventing the binder resin from entering the polymer substrate, thereby preventing a decrease in the breathability and resistance properties of the polymer substrate.

[0066] The organic / inorganic composite porous coating layer includes a binder resin and inorganic particles. The inorganic particles and the binder resin may be contained in a weight ratio of 75:25 to 90:10, and the "mixture of inorganic particles and binder resin" may account for 99 wt% or more of the entire organic / inorganic composite porous coating layer.

[0067] In one embodiment of the present invention, the organic / inorganic composite porous coating layer may have an average pore size of 10 nm to 900 nm, preferably 20 nm to 100 nm. The porosity of the organic / inorganic composite porous coating layer is preferably 50% to 85%. A porosity of 85% or less ensures mechanical properties that allow the coating layer to maintain its shape during the pressing process for bonding to the electrode, and is suitable for ensuring adhesive strength because the surface opening ratio is not too high. Furthermore, a porosity of 50% or more is higher than the porosity of most polymer substrates, which is advantageous from the perspective of ion permeability.

[0068] In one embodiment of the present invention, the thickness of the organic / inorganic composite porous coating layer on one side of the polymer substrate may be 0.1 μm to 10 μm, for example, 0.5 μm to 6 μm, or 1 μm to 5 μm. Within the above numerical range, a thickness of 1 μm or more is preferable from the viewpoint of increasing the adhesive strength and strength with the electrode. On the other hand, a thickness of 10 μm or less is advantageous from the viewpoint of the cycle characteristics and resistance characteristics of the battery.

[0069] a. Inorganic particles In a specific embodiment of the present invention, the inorganic particles are not particularly limited as long as they are electrochemically stable within the range of the battery operating voltage. That is, the inorganic particles that can be used in the present invention are those that are electrochemically stable within the operating voltage range of the applied electrochemical device (for example, Li / Li + There are no particular limitations on the dielectric constant as long as oxidation and / or reduction reactions do not occur at a potential of 0 to 5 V relative to the reference potential. In particular, when inorganic particles with a high dielectric constant are used as the inorganic particles, they can contribute to an increase in the degree of dissociation of the electrolyte salt, for example, lithium salt, in the liquid electrolyte, thereby improving the ionic conductivity of the electrolyte solution.

[0070] For the reasons mentioned above, it is preferable that the inorganic particles include inorganic particles with a high dielectric constant, having a dielectric constant of 5 or more, preferably 10 or more. Non-limiting examples of inorganic particles with a dielectric constant of 5 or more include BaTiO3, Pb(Zr,Ti)O3 (PZT), b 1-x La x Zr 1-y Ti y O3(PLZT, 0 <x<1、0<y<1)、Pb(Mg 1 / 3 Nb 2 / 3 )O3-PbTiO3 (PMN-PT), hafnia (HfO2), SrTiO3, SnO2, CeO2, MgO, Mg(OH)2, NiO, CaO, ZnO, ZrO2, SiO2, Y2O3, Al2O3, AlOOH, Al(OH)3, SiC and TiO2, or mixtures thereof.

[0071] In addition, as the inorganic particles, inorganic particles having lithium ion transfer ability, that is, inorganic particles that contain lithium element but have a function of moving lithium ions without storing lithium can be used. Non-limiting examples of inorganic particles having lithium ion transfer ability include lithium phosphate (Li3PO4), lithium titanium phosphate (Li x Ti y (PO4)3, 0 < x < 2, 0 < y < 3), lithium aluminum titanium phosphate (Li x Al y Ti z (PO4)3, 0 < x < 2, 0 < y < 1, 0 < z < 3), (LiAlTiP) x O y -based glass such as 14Li2O - 9Al2O3 - 38TiO2 - 39P2O5 (0 < x < 4, 0 < y < 13), lithium lanthanum titanate (Li x La y TiO3, 0 < x < 2, 0 < y < 3), Li 3.25 Ge 0.25 P 0.75 S4 and other lithium germanium thiophosphate (Li x Ge y P z S w , 0 < x < 4, 0 < y < 1, 0 < z < 1, 0 < w < 5), lithium nitride such as Li3N (Li x N y , 0 < x < 4, 0 < y < 2), SiS2 - based glass such as Li3PO4 - Li2S - SiS2 (Li x Si y S z , 0 < x < 3, 0 < y < 2, 0 < z < 4), P2S5 - based glass such as LiI - Li2S - P2S5 (Li x P y S z , 0 < x < 3, 0 < y < 3, 0 < z < 7), or mixtures thereof, etc.

[0072] In addition, the average particle size (D 50Although there are no particular limitations on the thickness of the coating layer, it is preferably in the range of 0.1 μm to 2.5 μm to ensure the formation of a coating layer with a uniform thickness and an appropriate porosity. If it is less than 0.1 μm, dispersibility may decrease due to a high specific surface area, and if it exceeds 2.5 μm, the thickness of the coating layer may increase.

[0073] b. Binder resin In the present invention, the organic / inorganic composite porous coating layer includes a binder resin, and the binder resin may include 90 wt% or more of a particulate binder resin relative to 100 wt% of the binder resin. The particulate binder resin has adhesive properties and accumulates the binder resin and inorganic particles in a layer structure on the surface of the polymer substrate by adhesion between particles or between the binder particles and inorganic particles. In addition, the particulate binder resin may include a water-dispersible binder resin that disperses but does not dissolve in water or aqueous solvents containing water.

[0074] The particulate binder resin is a material that can change to a gel or liquid state when heat and / or pressure is applied and can return to a solid state after the heat and pressure are removed, while being electrochemically stable. In a specific embodiment of the present invention, the particulate binder resin may have a glass transition temperature (Tg) in the range of about -100°C to about 50°C and a melting temperature (Tm) in the range of about 50°C to about 150°C. When the Tg of the particulate binder resin falls within this range, it is advantageous for achieving a predetermined adhesive strength. However, when the Tg exceeds this range, especially at room temperature or higher, ionic conductivity may decrease. In one embodiment of the present invention, the Tg can be measured by thermogravimetric analysis using a TA instrument.

[0075] According to a specific embodiment of the present invention, the particulate binder resin includes a polyvinylidene fluoride-based polymer (PVdF-based polymer) (first binder polymer) and a (meth)acrylic polymer (second binder polymer). The first binder polymer (PVdF-based) and the second binder polymer (acrylic-based) may be included in a weight ratio of 40:60 to 5:95. For example, the first binder polymer (PVdF-based) and the second binder polymer (acrylic-based) may be included in a weight ratio of 30:70 to 5:95. If the content of the first binder polymer is excessively high, although the adhesive strength may be improved, excessive adhesion may occur during the lamination process, resulting in an excessive increase in the resistance of the separator. On the other hand, if the content of the first binder polymer is below the above range, it may be difficult to achieve a desired level of adhesive strength.

[0076] In this specification, the PVdF-based polymer may include a homopolymer resin of vinylidene fluoride monomer; a copolymer (PVdF-based copolymer) containing vinylidene fluoride and another monomer (comonomer) copolymerizable with vinylidene fluoride; or both. According to a specific embodiment of the present invention, the particulate polymer may include a copolymer resin in consideration of the adhesive strength of the electrode adhesive layer. The PVdF copolymer may also be a copolymer in which vinylidene fluoride and a comonomer are copolymerized in a ratio of 60:40 to 96:4 based on parts by weight. For example, within the above range, the vinylidene fluoride and the comonomer may be copolymerized in a ratio of 80:20 to 96:4 or 90:10 to 97:3 based on parts by weight. That is, in the present invention, the degree of substitution by the comonomer of the PVdF copolymer may be appropriately adjusted within a range of 1 wt% to 40 wt%. In one embodiment of the present invention, the degree of substitution may be in the range of 1 wt% to 10 wt%.

[0077] In the present invention, the degree of substitution of the comonomer can be measured based on the integral value of the characteristic peak of the monomer confirmed in the 1H NMR (Nuclear Magnetic Resonance) spectrum. For substitution degree analysis, see Journal of Materials Chemistry, 2012, 22, 341, or AMT-3412-0k. The NMR spectrum can be confirmed using a suitable device such as a Bruker Avance III HD 700 MHz NMR or a Varian 500 MHz NMR.

[0078] The comonomer may be a fluorinated monomer or a chlorine-based monomer, preferably a fluorinated monomer. Non-limiting examples of the fluorinated monomer include one or more selected from the group consisting of vinyl fluoride, trifluoroethylene (VF3), chlorofluoroethylene (CTFE), 1,2-difluoroethylene, tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro(alkyl vinyl) ethers such as perfluoro(methyl vinyl) ether (PMVE), perfluoro(ethyl vinyl) ether (PEVE), and perfluoro(propyl vinyl) ether (PPVE), perfluoro(1,3-dioxole), and perfluoro(2,2-dimethyl-1,3-dioxole) (PDD). According to a specific embodiment of the present invention, the comonomer includes hexafluoropropylene.

[0079] In the present invention, the weight average molecular weight (Mw) of the PVdF polymer in the particulate binder resin is not particularly limited, but is preferably 10,000 to 500,000, and more preferably 50,000 to 500,000.

[0080] According to a specific embodiment of the present invention, the particulate binder resin may contain a (meth)acrylic polymer. According to a specific embodiment of the present invention, the (meth)acrylic polymer contains a (meth)acrylic acid ester as a monomer, and non-limiting examples thereof include (meth)acrylic polymers containing butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, n-oxyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, and tetradecyl (meth)acrylate as monomers. The (meth)acrylic polymer may be contained in an amount of 30% by weight or less relative to 100% by weight of the particulate binder resin.

[0081] Meanwhile, in one specific embodiment of the present invention, the particle size of the particulate binder resin may be 100 nm to 1 μm, 100 nm to 500 nm, 200 nm to 500 nm, 200 nm to 350 nm, or 200 nm to 300 nm.

[0082] In the present invention, the method for producing the particulate binder resin is not particularly limited, and a method for producing a typical particulate polymer, such as a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method, can be applied. Among these, the emulsion polymerization method and the suspension polymerization method are preferred because they can be polymerized in water and can be used as a slurry for forming an organic / inorganic composite porous coating layer.

[0083] c. Other additives In a specific embodiment of the present invention, the organic / inorganic composite porous coating layer may further contain additives as needed. Examples of such additives include thickeners. By including a dispersant or a thickener in the organic / inorganic composite porous coating layer, the coating properties of the slurry described below and the charge / discharge characteristics of the resulting electrochemical device can be further improved.

[0084] Examples of the thickener include cellulose compounds such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose; ammonium salts or alkali metal salts of the cellulose compounds; polycarboxylic acids such as poly(meth)acrylic acid and modified poly(meth)acrylic acid; alkali metal salts of the polycarboxylic acids; polyvinyl alcohol (co)polymers such as polyvinyl alcohol, modified polyvinyl alcohol, and ethylene-vinyl alcohol copolymers; and water-soluble polymers such as saponified copolymers of unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid, and fumaric acid with vinyl esters. Among these, particularly preferred thickeners include alkali metal salts of carboxymethyl cellulose and alkali metal salts of poly(meth)acrylic acid.

[0085] In one embodiment of the present invention, when the organic / inorganic composite porous coating layer contains a thickener, the usage ratio of the thickener is preferably 5 wt% or less, and more preferably 0.1 mass% to 3 mass%, relative to 100 wt% of the entire organic / inorganic composite porous coating layer.

[0086] Examples of the dispersing agent include acrylic copolymers, cyanoethyl polyvinyl alcohol, baicalin, luteolin, taxifolin, myricetin, quercetin, rutin, catechin, epigallocatechin gallate, butein, piceatannol, phenolic compounds including tannic acid, pyrogallol, amylose, amylopectin, xanthan gum, fatty acid compounds, and polymer compounds of two or more of these.

[0087] In one embodiment of the present invention, when the organic / inorganic composite porous coating layer contains a dispersant, the usage ratio of the dispersant is preferably 5 wt% or less, more preferably 0.1 mass% to 3 mass%, relative to 100 wt% of the entire organic / inorganic composite porous coating layer.

[0088] d. Manufacturing method of organic / inorganic composite porous coating layer In the present invention, the organic / inorganic composite porous coating layer is formed by dispersing inorganic particles and a particulate binder resin in an appropriate aqueous solvent as a dispersion medium to prepare a slurry for forming the organic / inorganic composite porous coating layer, and then coating the slurry on the surface of the polymer substrate and drying it.

[0089] The slurry may be prepared by mixing inorganic particles and a particulate binder resin with an aqueous solvent, or may be a polymer emulsion obtained by suspension polymerization, liquid phase polymerization, emulsion polymerization, etc. The aqueous solvent is preferably an aqueous medium containing water. The use of an aqueous medium in the slurry reduces adverse effects on the environment, improves stability for handling workers, and enables the formation of a thin organic / inorganic composite porous coating layer.

[0090] Meanwhile, in one embodiment of the present invention, the solid content of the slurry may be adjusted to 30 wt% or less. If the solid content of the slurry exceeds 30 wt%, the viscosity of the slurry becomes too high, making it difficult to control the thickness when coating the slurry. On the other hand, if the solid content of the slurry is too low, uncoated areas may occur, and the surface of the polymer substrate may be exposed without being covered with the slurry, which may cause a short circuit.

[0091] The method for applying the slurry may be a doctor blade coating method, a bar coating method, a dip coating method, a reverse roll coating method, a direct roll coating method, a gravure coating method, an extrusion coating method, a brush coating method, or the like, and from the viewpoint of being able to control the thickness uniformly, a bar coating method, a doctor blade coating method, a gravure coating method, or the like is preferred.

[0092] The method for drying the slurry is not particularly limited, but examples thereof include drying with warm air, hot air, low humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams.

[0093] In the present invention, the organic / inorganic composite porous coating layer has a structure in which polymer particles are dispersed between the separator and the electrode, and therefore does not interfere with ion conduction between the electrode and the separator, resulting in a low resistance increase rate and excellent life characteristics.

[0094] 3) Adhesive coating layer The adhesive coating layer is formed on the surface of the organic / inorganic composite porous coating layer opposite the surface on which the polymer substrate is disposed, and includes a polyvinylidene fluoride (PVdF) binder resin. The adhesive coating layer preferably contains 90 wt% or more of the PVdF binder resin relative to 100 wt% of the total adhesive coating layer. For example, the adhesive coating layer may contain 90 wt% or more, 95 wt% or more, or 99 wt% or more of the PVdF binder resin relative to 100 wt% of the total adhesive coating layer. Alternatively, the entire amount of the binder resin may be a PVdF binder resin.

[0095] In the present invention, the binder resin may contain 90 wt% or more of particulate binder resin relative to 100 wt% of the binder resin. The particulate binder resin has adhesive properties, and the binder resin accumulates in a layer structure on the surface of the organic / inorganic composite porous coating layer through adhesion between particles. That is, in the present invention, the adhesive coating layer contains a particulate PVdF-based binder resin. For example, the binder resin in the adhesive coating layer may include a particulate PVdF-based binder resin.

[0096] In one embodiment of the present invention, the PVdF-based binder resin of the adhesive coating layer preferably has a weight-average molecular weight of 600,000 or less, 400,000 or less, or 300,000 or less. A weight-average molecular weight of 600,000 or less is advantageous for improving flexibility and adhesive strength. However, if the weight-average molecular weight is less than 50,000, the PVdF-based binder resin may dissolve in the electrolyte solution, increasing the viscosity of the electrolyte and thereby reducing ionic conductivity. Therefore, a PVdF-based binder resin with a weight-average molecular weight of 50,000 or more may be used. The weight-average molecular weight of the PVdF-based binder resin can be determined by gel permeation chromatography (GPC). Such PVdF-based binder resins with relatively low molecular weights can be obtained preferably by emulsion polymerization or suspension polymerization, and more preferably by suspension polymerization.

[0097] In the present invention, the PVdF-based binder resin may include a homopolymer of vinylidene fluoride (i.e., polyvinylidene fluoride), a copolymer of vinylidene fluoride and another copolymerizable monomer, or a mixture thereof. Examples of the monomer copolymerizable with vinylidene fluoride include one or more selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, trifluoroethylene, chlorofluoroethylene, 1,2-difluoroethylene, perfluoro(methyl vinyl) ether, perfluoro(ethyl vinyl) ether, perfluoro(propyl vinyl) ether, perfluoro(1,3-dioxole), perfluoro(2,2-dimethyl-1,3-dioxole), trichloroethylene, and vinyl fluoride. In one embodiment of the present invention, the PVdF-based binder resin has a melting temperature (Tm) of 150°C or lower, preferably 140°C or lower, from the viewpoint of adhesive strength during thermal adhesion. For this purpose, the binder resin includes a copolymer of vinylidene fluoride and a monomer copolymerizable with vinylidene fluoride as polymerization units, and the copolymer may contain 70 wt% or more of vinylidene fluoride. Also, the copolymer may have a substitution degree with the other copolymerizable monomers such as those described above of 10 wt% to 40 wt%, for example, 1 wt% to 10 wt%.

[0098] Meanwhile, in one embodiment of the present invention, the adhesive coating layer may be formed to a thickness of 8% to 30% of the thickness of the organic / inorganic composite porous coating layer (first coating layer).

[0099] The adhesive coating layer can be formed by, for example, the following method, but is not particularly limited thereto.

[0100] In the present invention, the adhesive coating layer is formed by dispersing a particulate binder resin in an appropriate aqueous solvent as a dispersion medium to prepare a composition for forming the adhesive coating layer, applying the composition to the surface of the organic / inorganic composite porous coating layer, and drying the composition. The composition may be prepared by mixing a particulate binder resin with an aqueous solvent, or may be a polymer emulsion obtained by suspension polymerization, liquid phase polymerization, emulsion polymerization, etc. The aqueous solvent is preferably an aqueous medium containing water. The use of an aqueous medium for the slurry reduces adverse effects on the environment, improves stability for handling workers, and enables the formation of a thin adhesive coating layer.

[0101] The composition can be applied by a method such as bar coating, doctor blade coating, dip coating, reverse roll coating, direct roll coating, gravure coating, extrusion coating, or brush coating. From the viewpoint of being able to control the thickness uniformly, the bar coating, doctor blade coating, and gravure coating are preferred.

[0102] The method for drying the composition is not particularly limited, and examples thereof include drying with warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams.

[0103] In the present invention, the adhesive coating layer has a structure in which polymer particles are dispersed between the separator and the electrode, and therefore does not interfere with ion conduction between the electrode and the separator, resulting in a low resistance increase rate and excellent life characteristics.

[0104] Meanwhile, the separator according to the present invention having the above-described structural characteristics may have a resistance of 0.6 ohms or less. It may also have an air permeability of 100 sec / 100 cc or less. Excessively high separator resistance and / or air permeability is undesirable because it may deteriorate the battery's life characteristics during repeated charge / discharge cycles. Since the separator according to the present invention has the composite coating layer and adhesive coating layer prepared using an aqueous method, even when the composite coating layer and adhesive coating layer are disposed on the surface of the polymer substrate, the separator may maintain a resistance of 0.6 ohms or less and, simultaneously or independently, a low air permeability of 100 sec / 100 cc or less.

[0105] In the present invention, the resistance is a value measured when the separator is immersed in an electrolyte solution. In one embodiment of the present invention, the resistance may be a value measured by an AC method (frequency 10,000 to 100,000 Hz) at 25°C after immersing the polymer substrate in the electrolyte solution. The electrolyte solution may be a solvent obtained by mixing ethylene carbonate and ethyl methyl carbonate in a volume ratio of 3:7, further containing vinylene carbonate at a ratio of 2 wt% based on the total solvent, and containing LiPF6 at a concentration of 1M.

[0106] 2. An electrode assembly including the separator Meanwhile, the present invention provides a secondary battery including the separator, which includes an anode, a cathode, and a separator interposed between the anode and the cathode, and the separator is a low-resistance separator having the above-mentioned characteristics.

[0107] In the present invention, the positive electrode comprises a positive electrode current collector and a positive electrode active material layer on at least one surface of the current collector, the positive electrode active material layer including a positive electrode active material, a conductive material, and a binder resin. The positive electrode active material can be a layered compound such as lithium manganese composite oxide (LiMn2O4, LiMnO2, etc.), lithium cobalt oxide (LiCoO2), or lithium nickel oxide (LiNiO2), or a compound substituted with one or more transition metals; 1+x Mn 2-x O4 (where x is 0 to 0.33), lithium manganese oxides such as LiMnO3, LiMn2O3, and LiMnO2; lithium copper oxide (Li2CuO2); vanadium oxides such as LiV3O8, LiFe3O4, V2O5, and Cu2V2O7; and the chemical formula LiNi 1-x M x Ni-site type lithium nickel oxide represented by the chemical formula LiMnO2 (where M=Co, Mn, Al, Cu, Fe, Mg, B, or Ga, and x is 0.01 to 0.3). 2-x M xA lithium manganese composite oxide represented by O2 (where M is Co, Ni, Fe, Cr, Zn or Ta, and x is 0.01 to 0.1) or Li2Mn3MO8 (where M is Fe, Co, Ni, Cu or Zn); LiMn2O4 in which part of Li in the chemical formula is substituted with an alkaline earth metal ion; a disulfide compound; It can contain one or a mixture of two or more of Fe2(MoO4)3.

[0108] In the present invention, the negative electrode includes a negative electrode current collector and a negative electrode active material layer containing a negative electrode active material, a conductive material, and a binder resin on at least one surface of the current collector. As the negative electrode active material, the negative electrode includes carbon such as lithium metal oxide, graphitized carbon, and graphite-based carbon; Li x Fe2O3(0≦x≦1), Li x WO2(0≦x≦1), 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), etc. metal composite oxides; lithium metal; lithium alloy; silicon-based alloy; tin-based alloy; metal oxides such as SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4, and Bi2O5; conductive polymers such as polyacetylene; Li-Co-Ni-based materials; It can contain one or a mixture of two or more selected from titanium oxides.

[0109] In one specific embodiment of the present invention, the conductive material may be, for example, any one selected from the group consisting of graphite, carbon black, carbon or metal fiber, metal powder, conductive whisker, conductive metal oxide, activated carbon, and polyphenylene derivatives, or a mixture of two or more conductive materials thereof. More specifically, the conductive material may be any one selected from the group consisting of natural graphite, artificial graphite, Super-P, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, Denka black, aluminum powder, nickel powder, zinc oxide, potassium titanate, and titanium oxide, or a mixture of two or more conductive materials thereof.

[0110] The current collector is not particularly limited as long as it has high conductivity without inducing chemical changes in the battery. For example, stainless steel, copper, aluminum, nickel, titanium, baked carbon, or aluminum or stainless steel whose surface has been treated with carbon, nickel, titanium, silver, or the like can be used.

[0111] The binder resin may be a polymer commonly used in electrodes in the art. Non-limiting examples of such binder resins include polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polymethylmethacrylate, polyethylhexyl acrylate, polybutylacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate, ethylene-vinyl acetate copolymer, polyethylene oxide, polyarylate, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate. Examples of suitable cellulose acetate copolymers include, but are not limited to, cyanoethyl acetate propionate, cyanoethyl pullulan, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, cyanoethyl sucrose, pullulan, and carboxyl methyl cellulose.

[0112] The electrode assembly prepared as described above can be placed in a suitable case and an electrolyte injected to manufacture a battery.

[0113] In the present invention, the electrolyte is A+ B - A salt having the structure: + Li + , Na + , K. + or a combination thereof, - is PF6 - , BF4 - , Cl - , Br - , I - , ClO4 - , AsF6 - , CH3CO2 - , CF3SO3 - , N(CF3SO2)2 - , C(CF2SO2)3 - or a salt containing an anion such as, or a combination thereof, dissolved or dissociated in an organic solvent such as, but not limited to, 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), ethyl methyl carbonate (EMC), gamma butyrolactone (g-butyrolactone), or a mixture thereof.

[0114] The present invention also provides a battery module including a battery having the electrode assembly as a unit cell, a battery pack including the battery module, and a device including the battery pack as a power source. Specific examples of the device include, but are not limited to, power tools powered by a battery-powered motor, electric vehicles including electric vehicles (EVs), hybrid electric vehicles (HEVs), and plug-in hybrid electric vehicles (PHEVs), electric two-wheeled vehicles including electric bicycles (E-bikes) and electric scooters, electric golf carts, and power storage systems.

[0115] The present invention will be described in detail below with reference to examples. However, the examples of the present invention can be modified in various different forms, and the scope of the present invention should not be construed as being limited to the examples detailed below. The examples of the present invention are provided to more completely explain the present invention to those skilled in the art.

[0116] [Example] In Examples 1 and 2, a polymer substrate made of polypropylene material having the thickness and porosity shown in Table 1 below was prepared.

[0117] [Table 1]

[0118] Example 1 PVdF-HFP (Arkema, particle size 0.2 μm, HFP substitution degree approximately 5 wt%) was added and dispersed in an acrylic water-dispersed emulsion (Toyo Ink, CSB130, solid content 40%, particle size 177 nm). The acrylic and PVdF were mixed at a weight ratio of 80:10. Next, Al2O3 (Nippon Light Metal Co., Ltd., LS235, particle size 510 nm) was added and dispersed. Carboxymethyl cellulose (Delchem, SG-L02) was added and dispersed as a thickener to prepare a slurry for forming an organic / inorganic composite porous coating layer. The solid content of the slurry was 30 wt%, and the weight ratio of the binder resin (acrylic binder particles and PVdF particles) to the inorganic particles was 15:85. The slurry was mixed for 2 hours using a basket milling device, and then coated onto one side of a polymer substrate using a doctor blade and dried to form an organic / inorganic composite porous coating layer.

[0119] PVdF-HFP (Arkema, particle size 0.2 μm, HFP substitution degree approximately 5 wt%) was dispersed in deionized water to prepare a composition for forming an adhesive coating layer. The solid content of the composition was 20 wt%. The composition was applied to one side of the organic / inorganic composite porous coating layer using a doctor blade and dried to form an adhesive coating layer.

[0120] In the separator obtained in Example 1, the total thickness (one side) of the organic / inorganic composite porous coating layer and the adhesive coating layer was 4.1 μm, and the thickness ratio of the organic / inorganic composite porous coating layer to the adhesive coating layer was about 7:1. Figure 1(b) is a schematic diagram of Example 1.

[0121] Example 2 A separator was prepared in the same manner as in Example 1, except that the total thickness (one side) of the organic / inorganic composite porous coating layer and the adhesive coating layer was 4.2 μm. In the separator of Example 2, the thickness ratio of the organic / inorganic composite porous coating layer to the adhesive coating layer was about 7:1.

[0122] [Comparative Example] Comparative Example 1 A polymer substrate made of polypropylene material having the thickness and porosity shown in Table 2 below was prepared.

[0123] [Table 2]

[0124] PVdF-HFP (Arkema, particle size 0.2 μm, HFP substitution degree approximately 5 wt%) was added and dispersed in an acrylic water-dispersed emulsion (Toyo Ink, CSB130, solid content 40%, particle size 177 nm). The acrylic and PVdF were mixed at a weight ratio of 80:20. Next, Al2O3 (Nippon Light Metal Co., Ltd., LS235, particle size 510 nm) was added and dispersed. Carboxymethylcellulose (Delchem, SG-L02) was added and dispersed as a thickener to prepare a slurry for forming an organic / inorganic composite porous coating layer. The solid content of the slurry was 30 wt%, and the weight ratio of the binder resin (acrylic binder particles and PVdF particles) to the inorganic particles was 15:85. The slurry was mixed for 2 hours using a basket milling machine. The slurry was applied to one side of a polymer substrate using a doctor blade and dried to form an organic / inorganic composite porous coating layer. In the separation membrane obtained in Comparative Example 1, the thickness (one side) of the organic / inorganic composite porous coating layer was 4.1 μm. Figure 2 shows a schematic diagram of the cross-sectional structure of the separation membrane of Comparative Example 1.

[0125] Comparative Example 2 A polypropylene polymer substrate with the thickness and porosity shown in Table 2 was prepared. PVdF-HFP (Arkema, particle size 0.2 μm, HFP substitution degree approximately 5 wt%) was added and dispersed in an acrylic water-dispersed emulsion (Toyo Ink, CSB130, solid content 40%, particle size 177 nm). The acrylic and PVdF were mixed at a weight ratio of 80:10. Next, Al2O3 (Nippon Light Metal Co., Ltd., LS235, particle size 510 nm) was added and dispersed. Carboxymethyl cellulose (Delchem, SG-L02) was added and dispersed as a thickener to prepare a slurry for forming an organic / inorganic composite porous coating layer. The solid content of the slurry was 30 wt%, and the weight ratio of the binder resin (acrylic binder particles and PVdF particles) to the inorganic particles was 15:85. The slurry was mixed for 2 hours using a basket milling machine, and then coated onto one side of a polymer substrate using a doctor blade and dried to form an organic / inorganic composite porous coating layer.

[0126] PVdF-HFP (Arkema, particle size 0.2 μm, HFP substitution degree approximately 5 wt%) was dispersed in deionized water to prepare a composition for forming an adhesive coating layer. The solid content of the composition was 20 wt%. The composition was applied to one side of the organic / inorganic composite porous coating layer using a doctor blade and dried to form an adhesive coating layer.

[0127] In the separation membrane obtained in Comparative Example 2, the total thickness of the organic / inorganic composite porous coating layer and the adhesive coating layer was 4.2 μm. The thickness ratio of the organic / inorganic composite porous coating layer to the adhesive coating layer was approximately 7:1. Figure 3 shows a schematic diagram of the cross-sectional structure of the separation membrane of Comparative Example 2.

[0128] Comparative Example 3 A polymer substrate made of polypropylene having the thickness and porosity shown in Table 2 above was prepared.

[0129] PVdF-HFP (Arkema, particle size 0.2 μm, HFP substitution degree approximately 5 wt%) was added and dispersed in an acrylic water-dispersed emulsion (Toyo Ink, CSB130, solid content 40%, particle size 177 nm). The acrylic and PVdF were mixed at a weight ratio of 80:20. Next, Al2O3 (Nippon Light Metal Co., Ltd., LS235, particle size 510 nm) was added and dispersed. Carboxymethylcellulose (Delchem, SG-L02) was added and dispersed as a thickener to prepare a slurry for forming an organic / inorganic composite porous coating layer. The solid content of the slurry was 30 wt%, and the weight ratio of the binder resin (acrylic binder particles and PVdF particles) to the inorganic particles was 15:85. The slurry was mixed for 2 hours using a basket milling machine. The slurry was applied to one side of a polymer substrate using a doctor blade and dried to form an organic / inorganic composite porous coating layer. In the separation membrane obtained in Comparative Example 3, the thickness (one side) of the organic / inorganic composite porous coating layer was 4.1 μm. Figure 4 shows a schematic diagram of the cross-sectional structure of the separation membrane of Comparative Example 3.

[0130] Comparative Example 4 PVdF-HFP (Arkema, particle size 0.2 μm, HFP substitution degree approximately 5 wt%) was dissolved in acetone as a binder resin, and then Al2O3 (Nippon Light Metal Co., Ltd., LS235, particle size 510 nm) was added and dispersed. Carboxymethyl cellulose (Delchem, SG-L02) was added and dispersed as a thickener to prepare a slurry for forming an organic / inorganic composite porous coating layer. The solid content of the slurry was 30 wt%, and the binder resin to inorganic particle ratio was 15:85 by weight. The slurry was mixed for 2 hours using a basket milling device. The slurry was applied to one side of a polymer substrate using a doctor blade and dried to form an organic / inorganic composite porous coating layer.

[0131] PVdF-HFP (Arkema, particle size 0.2 μm, HFP substitution degree approximately 5 wt%) was dispersed in deionized water to prepare a composition for forming an adhesive coating layer. The solid content of the composition was 20 wt%. The composition was applied to one side of the organic / inorganic composite porous coating layer using a doctor blade and dried to form an adhesive coating layer.

[0132] In the separation membrane obtained in Comparative Example 4, the total thickness (one side) of the organic / inorganic composite porous coating layer and the adhesive coating layer was 4.1 μm, and the thickness ratio of the organic / inorganic composite porous coating layer to the adhesive coating layer was about 7:1. Figure 5 shows a schematic diagram of the cross-sectional structure of the separation membrane of Comparative Example 4.

[0133] [Physical property measurements] The thickness, air permeability, and resistance (ER) of the separation membranes obtained in each example and comparative example were measured before and after compression. Furthermore, a pressure of 5.2 MPa was applied to the separation membranes of each example and comparative example at 70°C for 10 seconds, and then the physical properties were measured. Table 3 shows the physical properties of the separation membrane before compression, and Table 4 shows the physical properties of the separation membrane after compression. The separation membranes were immersed in acetone and sonicated for 15 minutes to remove the coating layers and extract the porous substrate.

[0134] (1) Thickness measurement The thickness of the polymer substrate and the separation membrane was measured using a contact type thickness measuring instrument (Mitutoyo, VL50S-B).

[0135] (2) Air permeability measurement The time required for 100 ml of air to pass through the separation membrane was measured using an Oken type air permeability measuring device (Asahi Seiko).

[0136] (3) ER (resistance measurement) An electrolyte solution was prepared by mixing ethylene carbonate and ethyl methyl carbonate in a ratio of 3:7, adding vinylene carbonate at 2 wt % relative to the solvent, and adding LiPF6 to a concentration of 1 M. The separators of each example and comparative example were immersed in the electrolyte solution, and measurements were performed at 25°C using an AC method (frequency 10,000 to 100,000 Hz).

[0137] (4) Pore size distribution A sample measuring 5 cm in the TD direction and 5 cm in the MD direction was obtained from the center of the width of the polymer substrate for each example and comparative example. A drying curve was obtained for each sample using a Perm-Porometer (CFP-1500A) manufactured by Porous Materials Inc. (PMI). A wet curve was also obtained after filling the porous substrate with Galwick solution. The measurement pressure ranged from 0 to 3500 MPa. The pore distribution and half-width of the polymer substrate were calculated from the results. The bubble point in the obtained curve represents the maximum pore diameter, and the intersection of the wet and dry sample curves represents the minimum pore diameter. Figure 7 shows the permeability curves for the dry and wet samples. Referring to Figure 7, the intersection of the half-dry sample permeability curve and the wet sample curve, which corresponds to half the value of the dry sample permeability curve, represents the average pore diameter.

[0138] [Table 3]

[0139] [Table 4]

[0140] [Table 5]

[0141] As can be seen from Table 5, the thickness reduction rate of the polymer substrate in the separators of the Examples was lower than that of the Comparative Examples. The thickness reduction rate of the porous coating layer was in a similar range between the Examples and Comparative Examples. Meanwhile, the air permeability of the separator before and after compression showed a difference of approximately 200 sec / 100 cc in the Comparative Example, but only increased by approximately 50 sec / 100 cc in the Examples, demonstrating excellent compression resistance. This change was also confirmed to affect the resistance of the separator; the resistance of the separator increased by more than 0.3 ohms in the Comparative Example, but only by 0.2 ohms in the Examples. Meanwhile, the change in the porosity of the polymer substrate was confirmed to increase by less than 4 vol% in the Examples, but by more than 10 vol% in the Comparative Example. As confirmed above, the separators of the present invention were confirmed to have improved compression resistance. [Explanation of symbols]

[0142] 10: Separation membrane 11: Polymer base material 12: Organic / inorganic composite porous coating layer 13: Adhesive coating layer

Claims

1. a porous polymer substrate; a porous organic / inorganic composite coating layer disposed on at least one surface of the polymer substrate; an adhesive coating layer disposed on one side of the organic / inorganic composite porous coating layer, the adhesive coating layer being the opposite side to the polymer substrate; the polymer substrate is a polymer membrane having an average pore size of 40 nm or less, and the pore distribution has a full width at half maximum (FWHM) value of a Gaussian distribution measured through a pore size distribution of 8.0 nm or less; the organic / inorganic composite porous coating layer includes a particulate binder resin and inorganic particles, and the particulate binder resin includes an acrylic binder resin and a PVdF binder resin; The separator for an electrochemical device, wherein the adhesive coating layer contains a PVdF-based binder resin.

2. 2. The separator for an electrochemical device according to claim 1, wherein the polymer substrate has an air permeability of 100 sec / 100 cc or less and a resistance of 0.6 ohm or less.

3. 2. The separator for an electrochemical device according to claim 1, wherein the separator has an air permeability of 100 sec / 100 cc or less and a resistance of 0.6 ohm or less.

4. 2. The separator for an electrochemical device according to claim 1, wherein the polymer substrate has a porosity of 20 vol % to 50 vol %.

5. 2. The separator for an electrochemical device according to claim 1, wherein the organic / inorganic composite porous coating layer contains the inorganic particles and the particulate binder resin in a weight ratio of 75:25 to 90:

10.

6. 2. The separator for an electrochemical device according to claim 1, wherein the organic / inorganic composite porous coating layer has a mixture of the inorganic particles and the particulate binder resin in an amount of 99 wt % or more relative to 100 wt % of the entire layer.

7. 2. The separator for an electrochemical device according to claim 1, wherein the organic / inorganic composite porous coating layer contains the PVdF-based binder resin and the acrylic-based binder resin in a weight ratio of 30:70 to 5:

95.

8. 2. The separator for an electrochemical device according to claim 1, wherein the adhesive coating layer contains the PVdF-based binder resin in an amount of 90% by weight or more relative to 100% by weight of the entire adhesive coating layer.

9. The separator for an electrochemical device according to claim 8 , wherein the PVdF-based binder resin of the adhesive coating layer has a weight average molecular weight of 600,000 or less.

10. 2. The separator for an electrochemical device according to claim 1, wherein the PVdF-based binder resin of each of the organic / inorganic composite porous coating layer and the adhesive coating layer contains, as polymerization units, a copolymer of vinylidene fluoride and a monomer copolymerizable with vinylidene fluoride, and the copolymer contains 70 wt % or more of vinylidene fluoride.

11. 11. The separator for an electrochemical element according to claim 10, wherein the PVdF-based binder resin has a substitution degree with the monomer of 1 wt % to 10 wt %.

12. 2. The separator for an electrochemical device according to claim 1, wherein the particulate binder resin is maintained in particulate form within the separator.

13. 2. The separator for an electrochemical device according to claim 1, wherein the adhesive coating layer has a thickness of 8% to 30% of the thickness of the organic / inorganic composite porous coating layer (100%).

14. An electrochemical device comprising: a negative electrode; a positive electrode; and the separator according to claim 1 interposed between the negative electrode and the positive electrode.

15. A method for producing the separation membrane according to any one of claims 1 to 13, (S10) preparing a porous polymer substrate; (S20) forming an organic / inorganic composite porous coating layer on the surface of the polymer substrate; (S30) forming an adhesive coating layer on the surface of the organic / inorganic composite porous coating layer opposite to the surface on which the polymer substrate is disposed; The step (S20) is performed by dispersing inorganic particles and a particulate binder resin in an aqueous solvent as a dispersion medium to prepare a slurry for forming an organic / inorganic composite porous coating layer, applying the slurry to the surface of the polymer substrate, and drying the slurry. The step (S30) is performed by dispersing a particulate binder resin in an aqueous solvent as a dispersion medium to prepare a composition for forming an adhesive coating layer, applying the composition to the surface of the organic / inorganic composite porous coating layer, and drying the composition.

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