KR101773364B1 - A separator and an electrochemical battery comprising the separator - Google Patents

Abstract

The present invention relates to a separator comprising a porous substrate and a porous adhesive layer formed on one or both surfaces of the porous substrate, wherein the porous adhesive layer comprises a repeating unit derived from an alkyl (meth) acrylate monomer and a repeating unit derived from a monomer having a heterocyclic group And a polyvinylidene fluoride-based polymer, and an electrochemical cell including the separator.

Description

TECHNICAL FIELD [0001] The present invention relates to a separator and an electrochemical cell including the separator.

The present invention relates to a separation membrane excellent in adhesion to a substrate or an electrode, and an electrochemical cell including the separation membrane.

[0002] Portable electronic devices such as video cameras, mobile phones, and portable computers are generally made lighter and more sophisticated, and thus much research has been conducted on electrochemical cells used as driving power sources. Such electrochemical cells include, for example, nickel-cadmium batteries, nickel-hydrogen batteries, nickel-zinc batteries, lithium secondary batteries and the like. Of these, lithium secondary batteries are used in many fields because of their small size and large size, high operating voltage, and high energy density per unit weight.

A separator for an electrochemical cell means an interlayer capable of charging and discharging the battery by keeping the ion conductivity constant while isolating the positive electrode and the negative electrode from each other in the battery.

Due to the increase of the area and / or the weight of the separator due to the enlargement of the separator in the environment in the electrochemical cell or the use of the exterior material having a weak shape preservation such as a pouch type, the separation membrane wound between the electrode and the electrode may be detached, The adhesive force of the adhesive layer tends to be weakened and an increase in the adhesion between the separator film and the electrode and between the separator film substrate and the separator film adhesive layer is required.

In this connection, it has been known to form an organic / inorganic mixed coating layer on one side or both sides of a base film of a separator (Korean Patent Registration No. 10-0775310) in order to improve the adhesion between the separator and the electrode, By including the inorganic particles, the adhesive force between the separation membrane coating material and the separation membrane substrate is weakened, and the coated materials are easily peeled off from the substrate.

Therefore, it has an adhesive force applicable to a secondary battery using an external material such as a large-sized electrochemical cell or a pouch-type external appearance material, And to develop an electrochemical cell using the separator.

Korean Registered Patent No. 10-0775310 (published on November 11, 2007)

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Disclosed is a separator having an excellent ion conductivity and an excellent adhesion to a substrate, a positive electrode or a negative electrode while maintaining an adhesive force even after charge / discharge in an electrochemical cell including an electrolyte, And an electrochemical cell using the same.

According to an embodiment of the present invention, there is provided a separation membrane including a porous substrate and a porous adhesive layer formed on one or both sides of the porous substrate, wherein the porous adhesive layer comprises a repeating unit derived from an alkyl (meth) acrylate monomer and a heterocyclic group An acrylic copolymer containing a monomer-derived repeating unit, and a polyvinylidene fluoride-based polymer.

According to another embodiment of the present invention, there is provided an acrylic copolymer comprising a repeating unit derived from an alkyl (meth) acrylate monomer and a repeating unit derived from a monomer having a heterocyclic group, wherein the separator of the cathode active material Of a transfer ratio of 15% or more is provided.

[Formula 1]

Transfer rate (%) = (A ₁ / A ₀ ) X 100

In Equation (1)

A ₀ is the total area of the anode, A ₁ is an electrode assembly in which an anode, a separator, and a cathode are sequentially stacked, and this is formed at a temperature of 20 ° C to 110 ° C for 1 second to 5 seconds at 1 kgf / cm ² to 30 the primary compression with a force of kgf / cm ^2, and an electrolyte solution is injected to the electrode assembly is squeezed and 60 ℃ to 110 ℃, 30 seconds to 180 seconds, 1 kgf / cm ² To 30 kgf / cm < ² >, followed by charging, discharging, and charging in that order, the area of the cathode active material transferred to the separator.

According to another embodiment of the present invention, there is provided an electrochemical cell, particularly a lithium secondary battery, including the separation membrane according to the above embodiment.

The separator according to an embodiment of the present invention is excellent in adhesion to a porous substrate or a negative electrode and a positive electrode, thereby preventing deterioration of the performance of the battery due to a decrease in adhesion. In addition, the electrolytic solution impregnation rate of the separator is improved, and the electrolytic solution is retained in the porous adhesive layer to have a high electrolyte ion conduction ability, thereby improving the cell performance. Also, as the battery is repeatedly charged and discharged, the adherence to the anode or the cathode is maintained even in the environment where the expansion and contraction of the battery are repeated, thereby minimizing changes in the battery shape and securing a short ion transfer distance to improve the output efficiency And an electrochemical cell using the separator.

1 is an exploded perspective view of an electrochemical cell according to one embodiment.

Hereinafter, the present invention will be described in more detail. Those skilled in the art will appreciate that those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

According to an embodiment of the present invention, there is provided a separation membrane comprising a porous substrate and a porous adhesive layer formed on one or both surfaces of the porous substrate, wherein the porous adhesive layer is a separator comprising an alkyl (meth) acrylate monomer-derived repeating unit and a heterocyclic group An acrylic copolymer containing a monomer-derived repeating unit, and a polyvinylidene fluoride-based polymer.

The porous substrate may have a plurality of pores and may be a porous substrate that can be used in an electrochemical device. Porous substrates include but are not limited to polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyester, polyacetal, polyamide, polyimide, polycarbonate, polyetheretherketone, polyaryletherketone, polyetherimide , A polyimide imide, a polybenzimidazole, a polyether sulfone, a polyphenylene oxide, a cyclic olefin copolymer, a polyphenylene sulfide, and a polyethylene naphthalene, or a mixture of two or more thereof Lt; / RTI > In one example, the porous substrate may be a polyolefin-based substrate, and the polyolefin-based substrate is excellent in shut down function, thereby contributing to safety improvement of the cell. The polyolefin-based substrate may be selected from the group consisting of, for example, a polyethylene single film, a polypropylene single film, a polyethylene / polypropylene double film, a polypropylene / polyethylene / polypropylene triple film and a polyethylene / polypropylene / polyethylene triple film. In another example, the polyolefin-based resin may include, in addition to the olefin resin, a non-olefin resin or a copolymer of an olefin and a non-olefin monomer. The thickness of the porous substrate may be from 1 탆 to 40 탆, specifically from 5 탆 to 20 탆, more specifically from 5 탆 to 16 탆. When a base film within the above-mentioned thickness range is used, it is possible to produce a separator having an appropriate thickness which is thick enough to prevent a short circuit between the positive and negative electrodes of the battery, but not thick enough to increase the internal resistance of the battery. The air permeability of the porous substrate may be 250 sec / 100cc or less, specifically 200 sec / 100cc or less, more specifically 150 sec / 100cc, and the porosity may be 30% to 80%, for example, 40% to 60% .

The porous adhesive layer may include an acrylic copolymer including a repeating unit derived from an alkyl (meth) acrylate monomer and a repeating unit derived from a monomer having a heterocyclic group. Examples of the alkyl (meth) acrylate monomers include n-butyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (Meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, isooctyl (meth) acrylate, octyl (Meth) acrylate, lauryl (meth) acrylate, methyl (meth) acrylate, isobonyl (meth) acrylate and cyclohexyl But is not limited thereto. Specifically, straight or branched alkyl (meth) acrylates having 1 to 5 carbon atoms or alkyl (meth) acrylates having 1 to 4 straight or branched carbon atoms can be used.

Examples of the monomer having a heterocyclic group include acryloylmorpholine, vinylcaprolactam, tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, or 2,5-di And the like, but is not limited thereto.

The separator includes an acrylic copolymer including the repeating unit derived from the alkyl (meth) acrylate monomer and the repeating unit derived from a monomer having a heterocyclic group in the porous adhesive layer, so that the substrate adhesion, the electrode adhesion, the electrolyte impregnation, or the swelling Can be improved. In particular, the swelling property means the degree to which the binder absorbs and swells the electrolyte. Although not wishing to be bound by any particular theory, it is believed that the heteroatom of the heterocyclic group has high electronegativity and therefore affinity to lithium ions in the electrolytic solution improves the electrolyte-impregnating property or swelling property of the porous adhesive layer. When the electrolyte impregnating property or the swelling property is increased, the electrolyte can be retained in the porous adhesive layer, and the electrolyte may have a high electrolyte ion conduction capability, thereby improving battery performance. Therefore, the separation membrane disclosed herein can improve the electrolyte ion conduction ability due to the high electrolyte impregnation property of the porous adhesive layer.

The acrylic copolymer may be prepared by polymerizing an alkyl (meth) acrylate monomer and a monomer having a heterocyclic group. The polymerization method is not particularly limited and a method known to those skilled in the art can be used. For example, the monomer may be introduced into the reactor at an appropriate weight ratio, and then a solvent such as acetone or deionized water may be added. A peroxide initiator such as ammonium persulfate or benzoyl peroxide or an azo compound such as azobisisobutyl nitrile while maintaining the temperature at 45 ° C to 80 ° C and heating at 50 ° C to 100 ° C for 1 hour to 30 Lt; / RTI > In this case, the monomer having an alkyl (meth) acrylate monomer and a heterocyclic group is polymerized in a weight ratio of 9: 1 to 4: 6, specifically 8: 2 to 4: 6, more specifically 7: 3 to 5: . The weight ratio in the above range may be advantageous in terms of electrolyte impregnability, adhesion to electrodes and porous substrate.

The acrylic copolymer which can be used in one embodiment of the present invention is at least one selected from the group consisting of butyl (meth) acrylate, propyl (meth) acrylate, ethyl (meth) acrylate and methyl (meth) A monomer having at least one heterocyclic group selected from the group consisting of alkyl (meth) acrylates, tetrahydrofurfuryl (meth) acrylate, and caprolactone modified tetrahydrofurfuryl (meth) acrylate . In the acrylic copolymer, the weight ratio of butyl (meth) acrylate, methyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate is 2.5 to 8.5: 0.5 to 1.5: 1 to 6, , 2.5 to 7.5: 0.5 to 1.5: 2 to 6, more specifically 3.5 to 6.5: 0.5 to 1.5: 3 to 5. In another example, the acrylic copolymer may be prepared by polymerizing butyl methacrylate, methyl methacrylate, butyl acrylate, and tetrahydrofurfuryl (meth) acrylate, and the polymerization weight ratio is 3.5 to 6: 1: 1 to 2: 1 to 5: 1.5: 0.5 to 2.5: 0.5 to 6, specifically, 4: 1: 1 to 2:

The glass transition temperature of the acrylic copolymer may be in the range of 0 ° C to 50 ° C, specifically 0 ° C to 40 ° C, more specifically 0 ° C to 15 ° C, for example, 10 ° C to 20 ° C. Within the above range, the binder can form good adhesion with the electrode of the separator or with the porous substrate, and the shape stability can be ensured. The weight average molecular weight (Mw) of the acrylic copolymer may be 100,000 to 1,000,000. Specifically, it may be 500,000 to 1,000,000. The use of a binder having a molecular weight in the above range can enhance the adhesion between the porous adhesive layer and the porous substrate to improve the morphological stability of the separator. Also, it is possible to produce a separator having a sufficiently improved impregnation property of an electrolytic solution, and it is advantageous to produce a cell in which an electric output is efficiently generated.

The polyvinylidene fluoride-based polymer may be a homopolymer of polyvinylidene fluoride (PVdF), a polyvinylidene fluoride-based copolymer, or a mixture thereof. The term " polyvinylidene fluoride homopolymer " means a polymer containing only VDF-derived repeating units as repeating units, and the polyvinylidene fluoride-based copolymer includes at least two repeating units other than VDF- Means a polymer comprising at least two repeating units. The polyvinylidene fluoride-based copolymer may be a copolymer of PVdF and one or more other monomers such as HFP (hexafluoropropylene) and TFE (trichlorethylene). Specifically, it is a copolymer of PVdF and HFP, wherein HFP can be up to 10 mol%, for example, up to 5 mol%, of the copolymer. The weight average molecular weight of the polyvinylidene fluoride-based polymer may range from 500,000 to 1,700,000. The polyvinylidene fluoride-based polymer may have a weight average molecular weight of 1,000,000 or more. Use of a PVdF binder within the molecular weight range enhances the adhesive force between the adhesive layer and the porous substrate, thereby effectively restraining the heat-sensitive porous substrate from being shrunk by heat. Further, the electrolyte impregnability is sufficiently improved, Can be maintained. In the present invention, two kinds of binders different in electrolyte swelling degree are mixed and used to strengthen the adhesive force between the adhesive layer and the porous substrate, thereby effectively suppressing the heat-sensitive contraction of the porous substrate with heat. It is also possible to provide a highly adhesive separation membrane with sufficiently improved electrolyte stability.

The weight ratio of the acrylic copolymer to the PVdF polymer may be 9: 1 to 4: 6. Specifically from 8: 2 to 5: 5, more specifically from 7: 3 to 6: 4. When used within the above range, an electrochemical cell having excellent shape stability can be manufactured while maintaining the adhesive force after the separation membrane is sufficiently charged and discharged. As a result, deterioration in the performance of the produced battery can be prevented, and the battery can have charge / discharge characteristics of high efficiency.

The acrylic copolymer and the PVdF polymer are dissolved or mixed in a solvent to prepare a porous adhesive layer composition solution. The solvent used for preparing the porous adhesive layer composition solution is not particularly limited as long as it is a solvent capable of dissolving the binders. Non-limiting examples of the solvent usable in the present invention include acetone, dimethyl formamide, dimethyl sulfoxide, dimethylacetamide, dimethyl carbonate or N-methylpiperazine. N-methylpyrrolone, cyclohexane, and the like. The content of the solvent based on the weight of the porous adhesive layer composition may be 20 to 99% by weight, specifically 50 to 95% by weight, and more specifically 70 to 95% by weight. When the solvent is contained in the above range, the production of the porous adhesive layer composition is facilitated and the drying process of the adhesive layer can be performed smoothly.

The separation membrane according to another embodiment of the present invention may further include inorganic particles in the porous adhesive layer. The inorganic particles used in the present invention are not particularly limited and inorganic particles commonly used in the art can be used. Non-limiting examples of the inorganic particles usable in the present invention include Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , Ga ₂ O ₃ , TiO _2, and SnO ₂ . These may be used alone or in combination of two or more. As the inorganic particles used in the present invention, for example, Al ₂ O ₃ (alumina) can be used. The size of the inorganic particles used in the present invention is not particularly limited, but may be an average particle diameter of 1 nm to 2,000 nm, for example, 100 nm to 1,000 nm. It is possible to prevent degradation of the dispersibility of the inorganic particles in the porous adhesive layer and the processability of forming the porous adhesive layer and to appropriately control the thickness of the porous adhesive layer, An increase in resistance can be prevented. In addition, the size of the pores generated in the porous adhesive layer is appropriately controlled, thereby reducing the probability of an internal short circuit occurring during charging and discharging of the battery.

In the porous adhesive layer, the inorganic particles may be contained in an amount of 60 to 95% by weight, specifically 75 to 90% by weight, more specifically 80 to 90% by weight, based on the total weight of the porous adhesive layer. When inorganic particles are contained within the above range, the heat radiation characteristics of the inorganic particles can be sufficiently exhibited. Specifically, the weight ratio of the acrylic copolymer and the PVDF polymer in the porous adhesive layer to the weight ratio of the inorganic particles may be in the range of 2: 8 to 1: 9.

The method of forming the porous adhesive layer on the porous substrate is not particularly limited, and a method commonly used in the technical field of the present invention such as a coating method, a lamination method, and a coextrusion method can be used. Non-limiting examples of the coating method include a dip coating method, a die coating method, a roll coating method, and a comma coating method. These may be applied alone or in combination of two or more methods. The porous adhesive layer of the separator of the present invention may be formed by, for example, a dip coating method. The porous adhesive layer may be formed on one side or both sides of the porous substrate, and the thickness thereof may be in the range of 1 μm to 10 μm, specifically 1 μm to 6 μm.

Another embodiment of the present invention includes an acrylic copolymer comprising a repeating unit derived from an alkyl (meth) acrylate monomer and a monomer-derived repeating unit having a heterocyclic group, wherein the copolymer A separation membrane having a transfer ratio of 15% or more is provided.

[Formula 1]

Transfer rate (%) = (A ₁ / A ₀ ) X 100

In the formula 1, A ₀ is the total area of the positive electrode, A ₁ is the positive, from the separator and the cathode is the temperature of forming the electrode assembly, it is sequentially stacked, and this 20 ℃ to 110 ℃, 1 second to 5 seconds, 1 kgf / cm ² To 30 primary compression with a force of kgf / cm ^2, and the injection of an electrolyte solution in the electrode assembly, and crimp 60 ℃ to 110 ℃, 30 seconds to 180 seconds, 1 kgf / cm ² To 30 kgf / cm < ² >, followed by charging, discharging, and charging in that order, the area of the cathode active material transferred to the separator.

The method of measuring the area of the cathode active material is not particularly limited as long as the area of the active material can be measured. For example, the separator is photographed with a known image photographing machine (e.g., lumenera high resolution camera) Easy Measure converter 1.0.0.4) can be used to measure the transferred area of the cathode active material.

Examples of conditions of the charging, discharging and charging are shown in Table 1 below.

Char / Room / Charge (Charge) 4.35V, 0.2C, 50 mA cut-off 5 hrs (Room) 0.2C, 3V cut-off 5 hrs (Charge) 0.5C, 4V cut-off 2 hrs

The transfer rate of the cathode active material to the separator after charge / discharge may be 15% or more, for example, 15% to 30%. The high transfer rate of the cathode active material is related to the shape stability and adhesion of the battery after charge and discharge.

As the acrylic copolymer, the same acrylic copolymer as described in the above-mentioned embodiments can be used.

In the above embodiment, the separation membrane may further include a polyvinylidene fluoride-based polymer and / or an inorganic particle in addition to the acrylic copolymer. The polyvinylidene fluoride-based polymer and the inorganic particles may be the same as those described in the above-mentioned embodiment.

According to another embodiment of the present invention, there is provided a separation membrane including a porous substrate and a porous adhesive layer formed on one or both sides of the porous substrate, wherein the porous adhesive layer comprises a repeating unit derived from an alkyl (meth) acrylate monomer and a heterocyclic group And a transfer ratio of the positive electrode active material to the separator after charge and discharge of the formula 1 is 15% or more. The adhesion of the porous adhesive layer to the porous substrate may be, for example, 820 mN / 25 mm to 1300 mN / 25 mm, or 840 mN / 25 mm to 1200 mN / 25 mm, and the adhesion may be measured by a known method. For example, it can be measured by the following method: It is tested in accordance with Clause 8 of Korean Industrial Standard KS-A-01107 (Test Method for Adhesive Tape and Adhesive Sheet). The separator film was used as a test piece having a width of 25 mm and a length of 250 mm, and a tape (nitto 31B) was attached to each side of the separating film to complete the evaluation test piece, and the test piece was reciprocated once at a speed of 300 mm / And the specimen is squeezed. After a lapse of 30 minutes from the pressing, one side of the specimen was turned 180 ° to remove about 25 mm. The tape 31B attached to one side of the separator and separator was fixed to the upper clip of the tensile strength device, The tape 31B was fixed to the lower clip and pulled at a pulling rate of 60 mm / min to measure the pressure when the porous adhesive layer was peeled from the porous substrate. The tensile strength tester uses, for example, Instron Series IX / s Automated materials Tester-3343.

The anode adhesive strength of the separator is in the range of 200 mN / 25 mm to 500 mN / 25 mm, and the anode adhesive strength of the separator may be 130 mN / 25 mm to 300 mN / 25 mm. The positive electrode or negative electrode adhesion force means an adhesion force between the separator and the anode or the cathode. The anodic or cathodic adhesive strength can be measured by a known method, and in one example, it can be measured by the following method, but it is not limited thereto. The test shall be carried out in accordance with Clause 8 of Korean Industrial Standard KS-A-01107 (Test Method for Adhesive Tape and Adhesive Sheet). The separator film is used as a test piece with a width of 25 mm and a length of 250 mm, and a tape (nitto 31B) is attached to one surface of the separator to complete the test piece. On the other side of the separator, a positive electrode film (LCO (LiCoO 2) as a positive electrode active material was coated on an aluminum foil having a thickness of 14 μm on both sides with a total thickness of 94 μm and dried and rolled to obtain a positive electrode having a total thickness of 108 μm) or a negative electrode film Natural graphite and artificial graphite (1: 1) were coated on a copper foil having a thickness of 8 占 퐉 with a total thickness of 120 占 퐉, and dried and rolled) using a compression roller having a weight of 2 kg. Min, and then squeezed. After a lapse of 30 minutes from the pressing, one side of the test piece was turned 180 ° to peel off about 25 mm, and a tape 31B attached to one side of the separating film and the separating film was attached to the upper clip of the tensile strength device, The film is fixed to the lower clip and pulled at a pulling rate of 60 mm / min to measure the pressure when the anode or cathode film is peeled off from the separator. The tensile strength tester uses, for example, Instron Series IX / s Automated materials Tester-3343.

The anode adhesive force may be more specifically 300 mN / 25 mm to 400 mN / 25 mm, for example, 310 mN / 25 mm to 380 mN / 25 mm. The negative electrode adhesive force may be more specifically from 140 mN / 25 mm to 280 mN / 25 mm, for example, from 160 mN / 25 mm to 270 mN / 25 mm. Within the above range, the separator and the anode or the cathode can be sufficiently bonded.

In the separator according to this embodiment, the acrylic copolymer may be an acrylic copolymer as described herein, and the porous adhesive layer may be formed from the porous adhesive layer composition described herein. The separation membrane according to the embodiment may have an air permeability of 400 sec / 100cc or less, specifically 300 sec / 100cc or less, more specifically 250 sec / 100cc. In addition, the separation membrane thickness may be from 5 탆 to 45 탆, specifically from 6 탆 to 22 탆, more specifically from 6 탆 to 16 탆.

According to an embodiment of the present invention, cathode; A separator disclosed herein between the anode and the cathode; And an electrolyte.

The type of the electrochemical cell is not particularly limited and may be a battery of a kind known in the technical field of the present invention.

The electrochemical cell of the present invention may specifically be a lithium secondary battery such as a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.

The method for producing the electrochemical cell of the present invention is not particularly limited and a method commonly used in the technical field of the present invention can be used.

A method of manufacturing the electrochemical cell is as follows: A separator comprising the porous adhesive layer of the present invention is placed between the positive electrode and the negative electrode of the battery, and then the battery is manufactured in such a manner that the electrolyte is filled in the separator. can do.

1 is an exploded perspective view of an electrochemical cell according to one embodiment. The electrochemical cell according to one embodiment is a secondary battery, and the present invention is not limited thereto, but may be applied to various types of batteries such as a pouch type battery, a lithium polymer battery, and a cylindrical battery.

Referring to FIG. 1, a secondary battery 100 according to an embodiment includes an electrode assembly 40 wound around a separator 30 between an anode 10 and a cathode 20, And a case 50 in which the case 50 is embedded. The anode 10, the cathode 20 and the separator 30 are impregnated with an electrolyte (not shown).

The separation membrane 30 is as described above.

The anode 10 may include a cathode current collector and a cathode active material layer formed on the cathode current collector. The cathode active material layer may include a cathode active material, a binder, and optionally a conductive material.

The cathode current collector may be aluminum (Al), nickel (Ni) or the like, but is not limited thereto.

As the cathode active material, a compound capable of reversible intercalation and deintercalation of lithium may be used. Concretely, at least one of cobalt, manganese, nickel, aluminum, iron or a composite oxide or composite phosphorus of a metal and lithium in combination thereof may be used. More specifically, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium iron phosphate or a combination thereof may be used.

The binder not only adheres the positive electrode active materials to each other well but also adheres the positive electrode active material to the positive electrode current collector. Specific examples thereof include polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, diacetylcellulose, polyvinyl chloride , Carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide containing polymer, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, Acrylated styrene-butadiene rubber, epoxy resin, nylon, and the like. These may be used alone or in combination of two or more.

The conductive material imparts conductivity to the electrode. Examples of the conductive material include, but are not limited to, natural graphite, artificial graphite, carbon black, carbon fiber, metal powder, and metal fiber. These may be used alone or in combination of two or more. The metal powder and the metal fiber may be made of metals such as copper, nickel, aluminum, and silver.

The cathode 20 may include a negative electrode collector and a negative electrode active material layer formed on the negative collector.

The negative electrode current collector may be copper (Cu), gold (Au), nickel (Ni), copper alloy, or the like, but is not limited thereto.

The negative electrode active material layer may include a negative electrode active material, a binder, and optionally a conductive material.

Examples of the negative electrode active material include a material capable of reversibly intercalating and deintercalating lithium ions, a lithium metal, an alloy of lithium metal, a material capable of doping and dedoping lithium, a transition metal oxide, Can be used.

Examples of the material capable of reversibly intercalating and deintercalating lithium ions include carbonaceous materials, and examples thereof include crystalline carbon, amorphous carbon, and combinations thereof. Examples of the crystalline carbon include amorphous, plate-like, flake, spherical or fibrous natural graphite or artificial graphite. Examples of the amorphous carbon include soft carbon or hard carbon, mesophase pitch carbide, fired coke, and the like. As the lithium metal alloy, a lithium-metal alloy may be selected from the group consisting of lithium, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, An alloy of a selected metal may be used. As the material capable of doping and dedoping lithium, Si, SiO _x (0 <x <2), Si-C composite, Si-Y alloy, Sn, SnO ₂ , Sn-C composite, Sn- And at least one of them may be mixed with SiO ₂ . The element Y may be at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Tl, Ge, P, As, Se, Te, Po, and combinations thereof. Examples of the transition metal oxide include vanadium oxide, lithium vanadium oxide, and the like.

The kinds of the binder and the conductive material used for the cathode are the same as those used for the anode and the conductive material.

The positive electrode and the negative electrode may be prepared by mixing each active material and a binder with a conductive material in a solvent to prepare each active material composition and applying the active material composition to each current collector. The solvent may be N-methyl pyrrolidone or the like, but is not limited thereto. The method of manufacturing the electrode is well known in the art, and therefore, a detailed description thereof will be omitted herein.

The electrolytic solution includes an organic solvent and a lithium salt.

The organic solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can move. Specific examples thereof may be selected from a carbonate-based solvent, an ester-based solvent, an ether-based solvent, a ketone-based solvent, an alcohol-based solvent and an aprotic solvent.

Examples of the carbonate solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), ethyl methyl carbonate Carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC). Specifically, when a mixture of a chain carbonate compound and a cyclic carbonate compound is used, it can be prepared from a solvent having a high viscosity and a high dielectric constant. Here, the cyclic carbonate compound and the chain carbonate compound may be mixed in a volume ratio of 1: 1 to 1: 9.

Examples of the ester solvent include methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate,? -Butyrolactone, decanolide, valerolactone, Mevalonolactone, caprolactone, and the like. Examples of the ether solvent include dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran and the like. Examples of the ketone-based solvent include cyclohexanone, and examples of the alcohol-based solvent include ethyl alcohol, isopropyl alcohol, and the like.

The organic solvents may be used alone or in combination of two or more. When two or more of them are used in combination, the mixing ratio may be appropriately adjusted according to the performance of the desired cell.

The lithium salt is dissolved in an organic solvent to act as a source of lithium ions in the cell to enable operation of a basic secondary cell and accelerate the movement of lithium ions between the positive electrode and the negative electrode.

For example the lithium salt _{is, LiPF 6, LiBF 4, LiSbF} 6, LiAsF 6, LiN (SO 3 C 2 F 5) 2, LiN (CF 3 SO 2) 2, LiC 4 F 9 SO 3, LiClO 4, LiAlO 2 , LiAlCl ₄ , LiN (C _x F _{2x + 1} SO ₂ ) (C _y F _{2y + 1} SO ₂ ) where x and y are natural numbers, LiCl, LiI, LiB (C ₂ O ₄ ) _2, .

The concentration of the lithium salt can be used within the range of 0.1M to 2.0M. When the concentration of the lithium salt is within the above range, the electrolytic solution has an appropriate conductivity and viscosity, and thus can exhibit excellent electrolytic solution performance, and lithium ions can effectively move.

Hereinafter, the present invention will be described in more detail by describing Examples, Comparative Examples and Experimental Examples. However, the following examples, comparative examples and experimental examples are merely examples of the present invention and should not be construed as limiting the scope of the present invention.

Example

Manufacturing example  1: Production of first binder

1: 5) of butyl methacrylate (BMA), methyl methacrylate (MMA), and tetrahydrofurfuryl acrylate (THF-A) in deionized water (DIW) (SDS, 85.0%) was used as an emulsifier and ammonium persulfate (APS, 98.0%) was used as a polymerization initiator. The amounts of the dodecyl sulfate and sodium dodecyl sulfate were 0.8 wt% And 0.3% by weight, were prepared. Then, the mixed solution was put into a thermostatic chamber, stirred, heated to 75 캜 and reacted for 3 hours to synthesize an acrylic copolymer. The resulting emulsion was cooled to room temperature, and then added with stirring into an aqueous 2 wt% ammonium sulfate solution to obtain a precipitated polymer resin. The obtained polymer was separated from the solvent, washed with distilled water several times and dried to prepare a first binder having a weight average molecular weight of 640,000 ± 50,000.

Manufacturing example  2: Preparation of second binder

A second binder was prepared in the same manner as in Preparation Example 1, except that BMA, MMA and THF-A were added at a ratio of 5: 1: 4.

Manufacturing example  3: Preparation of the third binder

A third binder was prepared in the same manner as in Preparation Example 1, except that BMA, MMA and THF-A were added in the ratio of 6: 1: 3.

Manufacturing example  4: Manufacture of the fourth binder

MMA, BA and THF-A in a ratio of 4: 1: 2: 3 in addition to BMA, MMA, and THF-A in Production Example 1 and further polymerizing the monomer using butyl acrylate (BA) The procedure of Preparation Example 1 was repeated to prepare a fourth binder.

Example  1: Preparation of membrane

The first binder prepared in Preparation Example 1 was dissolved in acetone to prepare a first binder solution having a solid content of 10% by weight. The first binder solution and the PVdF binder solution were mixed so that the weight ratio of the first binder to the PVdF binder (KF9300, Kureha, Mw: 1,200,000) was 7: 3. Acetone was added so that the total solid content was 15 wt% To prepare a porous adhesive layer composition. On both sides of a polyethylene fabric (SK) having a thickness of 7 占 퐉, To prepare a separation membrane having a total thickness of about 9 mu m.

Example  2: Preparation of membrane

In Example 1, the separation membrane of Example 2 was fabricated in the same manner as in Example 1, except that a second binder was used instead of the first binder.

Example  3: Preparation of membrane

In Example 1, the separation membrane of Example 3 was fabricated in the same manner as in Example 1, except that a third binder was used instead of the first binder.

Example  4: Preparation of membrane

In Example 1, the separation membrane of Example 4 was fabricated in the same manner as in Example 1, except that a fourth binder was used instead of the first binder.

Example  5: Preparation of membrane

In Example 1, the separation membrane of Example 5 was fabricated in the same manner as in Example 1, except that the weight ratio of the first binder to the PVdF binder was 9: 1.

Example  6: Preparation of membrane

In Example 1, the separation membrane of Example 6 was fabricated in the same manner as in Example 1, except that the weight ratio of the first binder to the PVdF binder was 8: 2.

Example  7: Preparation of membrane

In Example 1, the separation membrane of Example 7 was fabricated in the same manner as in Example 1, except that the weight ratio of the first binder to the PVdF binder was 6: 4.

Example  8: Preparation of membrane

In Example 1, 25 wt% of alumina (LS235, Japan light metal) was added to acetone in an amount of 25 wt%, and the mixture was subjected to a bead mill dispersion at 25 DEG C for 2 hours to prepare an alumina dispersion. The binder solid content and alumina solid content were 1/5 The separation membrane of Example 8 was prepared in the same manner as in Example 1 except that the binder solution and the alumina dispersion were mixed so that acetone was added so that the total solid content was 15% by weight.

Comparative Example  1: Preparation of membrane

In Example 1, a PVDF binder was dissolved in a mixed solvent of acetone and DMAc without a first binder to prepare a binder solution having a solid content of 7 wt%, and in the same manner as in Example 1 except that the binder solution was used To prepare a separator of Comparative Example 1. The compositions of the separators according to Examples 1 to 8 and Comparative Example 1 are shown in Table 2 below.

Substrate / Thickness (탆) Binder composition Acrylic polymerization weight ratio Example 1 PE / 7 Acrylic / PVdF system, 7/3 BMA + MMA + THF-A 4: 1: 5 Example 2 PE / 7 Acrylic / PVdF system, 7/3 BMA + MMA + THF-A 5: 1: 4 Example 3 PE / 7 Acrylic / PVdF system, 7/3 BMA + MMA + THF-A 6: 1: 3 Example 4 PE / 7 Acrylic / PVdF system, 7/3 BMA + MMA + BA + THF-A 4: 1: 2: 3 Example 5 PE / 7 Acrylic / PVdF system, 9/1 BMA + MMA + THF-A 4: 1: 5 Example 6 PE / 7 Acrylic / PVdF system, 8/2 BMA + MMA + THF-A 4: 1: 5 Example 7 PE / 7 Acrylic / PVdF system, 6/4 BMA + MMA + THF-A 4: 1: 5 Example 8 PE / 7 Acrylic / PVdF system, 7/3 BMA + MMA + THF-A 4: 1: 5 Comparative Example 1 PE / 7 PVdF system, 100% - -

Experimental Example

The separator films prepared in Examples 1 to 8 and Comparative Example 1 were measured for substrate adhesion, anode adhesive force and anode adhesive force, transfer rate of the cathode active material after charge and discharge, and 100 cycle charge / discharge retention ratio by the measurement method described below, The results are shown in Table 3.

Substrate adhesion

The test was carried out in accordance with Clause 8 of Korean Industrial Standard KS-A-01107 (Test Method for Adhesive Tape and Adhesive Sheet). The separator film prepared in the above examples and comparative examples was used as a test piece having a width of 25 mm and a length of 250 mm, and a tape (nitto 31B) was attached to each side of the separation film to complete an evaluation test piece. And the test piece was pressed by using a pressing roller having a load of 2 kg once and reciprocating at a speed of 300 mm / min. After a lapse of 30 minutes from the pressing, one side of the specimen was turned 180 ° to remove about 25 mm. The tape 31B attached to one side of the separator and separator was fixed to the upper clip of the tensile strength device, The tape 31B was fixed to the lower clip and pulled at a pulling rate of 60 mm / min to measure the pressure when the porous adhesive layer was peeled from the porous substrate. The tensile strength machine used was Instron Series IX / s Automated materials Tester-3343.

Anode adhesive force

The test was carried out in accordance with Clause 8 of Korean Industrial Standard KS-A-01107 (Test Method for Adhesive Tape and Adhesive Sheet). The separator film prepared in the above Examples and Comparative Examples was used as a test piece having a width of 25 mm and a length of 250 mm and a tape (nitto 31B) was attached to one surface of the separator to complete the test piece. On the other side of the separator, a positive electrode film (LCO (LiCoO2) as a positive electrode active material was coated on an aluminum foil having a thickness of 14 占 퐉 on both sides with a total thickness of 94 占 퐉, dried and rolled, using an anode having a total thickness of 108 占 퐉) And was reciprocated once at a speed of 300 mm / min. After a lapse of 30 minutes from the pressing, one side of the test piece was turned 180 ° to peel off about 25 mm. The tape 31B attached to one side of the separating film and the separating film was attached to the upper clip of the tensile strength device, And then pulled at a pulling rate of 60 mm / min to measure the pressure when the anode film was peeled off from the separator. The tensile strength machine used was Instron Series IX / s Automated materials Tester-3343.

Cathode adhesion

The test was carried out in accordance with Clause 8 of Korean Industrial Standard KS-A-01107 (Test Method for Adhesive Tape and Adhesive Sheet). The separator film prepared in the above Examples and Comparative Examples was used as a test piece having a width of 25 mm and a length of 250 mm and a tape (nitto 31B) was attached to one surface of the separator to complete the test piece. On the other side of the separator, a negative electrode film (anode active material, natural graphite and artificial graphite (1: 1) was coated on a copper foil having a thickness of 8 탆 with a total thickness of 120 탆 and dried and rolled, using a negative electrode having a total thickness of 128 탆) Was reciprocated once at a speed of 300 mm / min using a pressing roller having a load of 2 kg, and then pressed. After a lapse of 30 minutes after the pressing, one side of the test piece was turned 180 ° to peel off about 25 mm. The tape 31B attached to one side of the separating film and the separating film was attached to the upper clip of the tensile strength device, And then pulled at a pulling rate of 60 mm / min to measure the pressure when the negative electrode film was peeled off from the separator. The tensile strength machine used was Instron Series IX / s Automated materials Tester-3343.

Charging and discharging  The transfer ratio of the cathode active material

LCO (LiCoO2) was coated on aluminum foil with a thickness of 94 ㎛ as a cathode active material and dried and rolled to make a total thickness of 108 ㎛. Natural graphite and artificial graphite (1: 1) were coated on both sides of copper foil with thickness of 8μm as anode active material and dried and rolled to prepare a negative electrode having a total thickness of 128 ㎛. The electrolyte solution was 1.5M LiPF6 (PANAX ETEC CO., LTD.) Mixed in an organic solvent of EC / EMC / DEC + 0.2% LiBF4 + 5.0% FEC + 1.0% VC + 3.00% SN + 1.0% PS + 1.0% Were used.

The separator prepared in the above Examples and Comparative Examples was interposed between the positive and negative electrodes and wound into an electrode assembly of 7 cm x 6.5 cm. The electrode assembly was first pressed at 100 ° C. for 3 seconds under a pressure of 5 kgf / cm ² and placed in an aluminum coated pouch (8 cm × 12 cm). The two adjacent corners were sealed at a temperature of 143 ° C., And the battery was sealed using a degassing machine for 3 minutes or more so that no air remained in the battery. 120 seconds at 110 ℃ after aging (aging) of the manufactured battery at 12 hours 25 ℃, were secondary compression under a pressure of 20kgf / cm ^2. After aging and secondary pressing, the electrode assembly was aged for 12 hours at 25 DEG C for 2 hours, pre-charged at 4.35 V, 0.2C for 1 hour, After charging and discharging under the conditions of discharging and charging, the battery was disassembled, and the area of the anode active material transferred to the separator was photographed (lumenera high resolution camera). Using the image analyzer (Easy Measure converter 1.0.0.4) And the charge / discharge ratio was determined.

100 cycles Charging and discharging  Retention rate (%)

The lithium secondary battery was assembled by using the separation membrane obtained in the examples and the comparative example and charged with a constant current until the voltage reached 4.2 V by a constant current constant voltage charging method at 60 캜 and 1 C and then charged at a constant voltage Followed by discharging to 3.0 V with a constant current of 1C. The charge-discharge cycle test was performed up to 100 cycles. The ratio of the discharge capacity at the 100th cycle to the initial discharge capacity was defined as the capacity retention rate. The higher the retention rate value, the smaller the capacity decrease during charging and discharging. Which means that the deterioration is large.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Base Adhesion (mN / 25mm) 1086 1180 1077 1098 1132 1098 979 901 600 Anodic bonding force (mN / 25 mm) 322 330 340 348 321 352 300 272 210 Cathode Adhesion (mN / 25mm) 200 212 220 233 194 210 185 180 110 Transfer rate of cathode active material after charge / discharge (%) 23 23 23 24 25 24 22 18 30 100 cycle charge / discharge retention (%) 95 95 96 96 97 96 94 95 98

With reference to Table 3, it was confirmed that the separator of Examples 1 to 8 having the porous adhesive layer using the acrylic copolymer and the PVdF polymer containing the repeating unit derived from the alkyl (meth) acrylate monomer and the monomer-derived repeating unit having the heterocyclic group The swelling degree, the swelling degree, the positive electrode adhering force and the negative electrode adhering force as well as the high rate of transfer of the positive electrode active material after charging and discharging, and maintaining the adhesive force even in the electrolytic solution state.

Claims (19)

1. A separation membrane comprising a porous substrate and a porous adhesive layer formed on one or both sides of the porous substrate,
Wherein the porous adhesive layer comprises an acrylic copolymer comprising a repeating unit derived from an alkyl (meth) acrylate monomer and a repeating unit derived from a monomer having a heterocyclic group, and a polyvinylidene fluoride polymer,
Wherein the monomer having a heterocyclic group is at least one selected from the group consisting of tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, and 2,5-dihydrofuran, . The composition of claim 1, wherein the alkyl (meth) acrylate monomer is selected from the group consisting of n-butyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (Meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, hexyl (meth) acrylate, heptyl (Meth) acrylate, isobornyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, methyl (meth) acrylate, isobonyl At least one separator. delete The separation membrane according to claim 1, wherein the acrylic copolymer is produced by polymerizing the alkyl (meth) acrylate monomer and the monomer having the heterocyclic group at a weight ratio of 9: 1 to 4: 6. The method according to claim 1, wherein the polyvinylidene fluoride-based polymer is selected from the group consisting of polyvinylidene fluoride (PVdF) homopolymer and polyvinylidene fluoride-based copolymer, or a mixture thereof, Membrane. The separation membrane according to claim 5, wherein the polyvinylidene fluoride-based copolymer is a polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP) copolymer. The separation membrane according to claim 5 or 6, wherein the polyvinylidene fluoride-based polymer has a weight average molecular weight ranging from 500,000 to 1,700,000. The separation membrane according to claim 1, wherein the weight ratio of the acrylic copolymer to the polyvinylidene fluoride-based polymer is from 9: 1 to 4: 6. The separation membrane according to any one of claims 1, 2, and 4 to 6, wherein the porous adhesive layer further comprises inorganic particles. The separation membrane according to claim 9, wherein the inorganic particles are selected from the group consisting of Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , Ga ₂ O ₃ , TiO _2, and SnO ₂ . The separation membrane according to claim 9, wherein a weight ratio of the acrylic copolymer to the PVDF polymer in the porous adhesive layer and a weight ratio of the inorganic particles is in the range of 2: 8 to 1: 9. The separation membrane according to any one of claims 1, 2, and 4 to 6, wherein the separation membrane has an air permeability of 400 sec / 100 cc 占 퐉 or less. An acrylic copolymer comprising a repeating unit derived from an alkyl (meth) acrylate monomer and a repeating unit derived from a monomer having a heterocyclic group,
Wherein the monomer having a heterocyclic group is at least one selected from the group consisting of tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, and 2,5-dihydrofuran,
Wherein the cathode active material has a transfer ratio of 15% or more to the separator after the charge and discharge of formula (1).
[Formula 1]
Transfer rate (%) = (A ₁ / A ₀ ) X 100
In Equation (1)
A ₀ is the total area of the anode,
A ₁ is an electrode assembly in which an anode, a separator, and a cathode are sequentially laminated, and is formed at a temperature of 20 ° C to 110 ° C for 1 second to 5 seconds at a primary force of 1 kgf / cm ² to 30 kgf / cm ² The electrolyte solution is injected into the squeezed electrode assembly, and is secondarily squeezed at a pressure of 1 kgf / cm ² to 30 kgf / cm ^{2 at} a temperature of 60 ° C to 110 ° C for 30 seconds to 180 seconds, Is the area of the cathode active material transferred to the separator. The separator according to claim 13, wherein the separator has an anode adhesive strength in the range of 200 mN / 25 mm to 500 mN / 25 mm and a cathode adhesive strength in the range of 130 mN / 25 mm to 300 mN / 25 mm. 14. The separation membrane according to claim 13, wherein the separation membrane further comprises a polyvinylidene fluoride-based polymer. The separation membrane according to claim 15, wherein the weight ratio of the acrylic copolymer to the polyvinylidene fluoride polymer is 9: 1 to 4: 6. 14. The separation membrane according to claim 13, wherein the separation membrane further comprises inorganic particles. anode; A separation membrane according to any one of claims 1, 2, 4 to 6, and 13 to 17; cathode; And an electrolytic solution. The electrochemical cell according to claim 18, wherein the electrochemical cell is a lithium secondary battery.

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