Transfer release film and lithium electrodes using same and manufacturing method thereof

Abstract

A transfer release film according to the present invention comprises: a substrate; a release layer formed by applying a release composition including an ion conductive polymer resin and a solvent onto one surface of the substrate; and a lithium deposition layer formed by being deposited on the upper surface of the release layer. In the transfer release film according to the present invention having this configuration, the release layer is detached from the substrate and transferred to an electrode together with the lithium deposition layer, thereby serving as a protective layer of the lithium deposition layer.

Description

Transfer-use release film, lithium electrode using the same, and manufacturing method thereof

[0001] The present invention relates to a transfer release film, and more specifically, to a transfer release film in which a lithium deposition layer is formed on the surface of a release layer so that the release layer and the lithium deposition layer are transferred together, a lithium electrode using the same, and a method for manufacturing the same.

[0002] Recently, with the increasing proliferation of mobile phones, camcorders, laptops, PCs, and even electric vehicles, interest in energy storage technology has been growing. This expansion in application areas has led to increasingly concrete efforts in research and development of electrochemical devices. Electrochemical devices are receiving the most attention in this regard, and among them, the development of rechargeable secondary batteries is receiving particular attention. Recently, active research and development is underway on novel electrode and battery designs to improve the capacity, density, and specific energy of these batteries.

[0003] In relation to research and development of secondary battery electrodes and cells, research is being conducted to improve cycle characteristics and alleviate volume expansion by using semi-metal oxides such as silicon oxide (SiOx). Among these, a silicon (Si) composite, which uses both silicon-based and carbon-based materials, was developed to minimize the volume expansion of the silicon-based material and simultaneously increase high capacity and charge / discharge life. By coating the silicon-based material with carbon, it improves the electrical conductivity between the active material particles and the electrochemical properties for the electrolyte, while reducing the volume expansion of the silicon-based particles, thereby increasing the life of the secondary battery. In addition, in this case, to solve the problem of the formation of an irreversible phase due to the silicon-based material during the initial charge / discharge, the semi-metal oxide and lithium are pre-complexed so that the semi-metal oxide contains lithium, so that the formation of less irreversible phases such as lithium oxide or lithium metal oxide during the initial charge / discharge of the battery can be increased, thereby increasing the initial efficiency of the negative active material.

[0004] However, as described above, secondary batteries using lithium have limitations in the manufacturing process due to the reactivity of lithium metal, and because contact with oxygen and moisture in the air is inevitable during secondary battery assembly, the lifespan and performance of the battery are reduced, and there is also a problem that the charge / discharge efficiency of the lithium electrode is reduced due to the growth of lithium dendrites.

[0005] The present invention has been made to solve the above-described problems, and the problem to be solved by the present invention is to provide a transfer release film for manufacturing a lithium electrode having a structure capable of preventing the growth of lithium dendrites by blocking contact with the atmosphere and lowering the diffusion barrier of lithium metal during the process of forming a lithium electrode of a lithium secondary battery, a lithium electrode using the same, and a method for manufacturing the same.

[0006] In addition, another problem to be solved by the present invention is to provide a transfer release film capable of controlling the transferability of a lithium deposition layer and the reactivity between lithium and a substrate and the reactivity with heat and moisture during the formation of a lithium deposition layer by first depositing the lithium deposition layer on a separate release film rather than directly depositing the lithium deposition layer on a current collector and then transferring the lithium deposition layer together with the release layer to a current collector, and a lithium electrode using the same and a method for manufacturing the same.

[0007] In addition, another problem to be solved by the present invention is to provide a transfer release film capable of minimizing exposure of lithium metal to the atmosphere during the manufacturing process of a lithium electrode, a lithium electrode using the same, and a manufacturing method thereof.

[0008] The above and other objects and advantages of the present invention will become apparent from the following description of preferred embodiments.

[0009] The above object is achieved by a transfer release film comprising a release layer formed by applying a release composition comprising a substrate, an ion conductive polymer resin and a solvent to one surface of a substrate, and a lithium deposition layer formed by depositing on the upper surface of the release layer.

[0010] Preferably, the heterolayer may be detached from the substrate and transferred to the electrode together with the lithium deposition layer.

[0011] Preferably, it may further include a coating layer formed on the other surface of the substrate and including an ion-conductive polymer resin.

[0012] Preferably, the ion conductive polymer resin may be dissolved by an electrolyte provided in the electrode assembly.

[0013] Preferably, the transfer film may have a peeling strength satisfying the following equations 1 and 2.

[0014] (Formula 1)

[0015] 1 < TR < 100

[0016] (Formula 2)

[0017] 1 < FR < 20

[0018] Here, TR is the peeling force when peeling the release layer from the substrate at a speed of 0.3 mpm while holding the Nitto-31B tape in a state where the substrate is fixed after Nitto-31B tape is adhered to the surface of the release layer at room temperature (23°C) before forming a lithium deposition layer on the release layer, and FR is the peeling force when peeling the substrate from the release layer at a speed of 0.3 mpm while holding the Nitto-31B tape in a state where the substrate is fixed after Nitto-31B tape is adhered to the surface of the release layer at room temperature (23°C) before forming a lithium deposition layer on the release layer, and the unit of peeling force is gf / inch.

[0019] Preferably, the transfer release film may have a peeling force that satisfies the following equation 3 when Nitto-31B tape is adhered to the surface of the release layer and then peeled at a speed of 0.3 mpm.

[0020] (Formula 3)

[0021] 1 < TR1 / TR0 < 5

[0022] TR0 is the peel strength of the release layer before heat treatment, TR1 is the peel strength of the release layer after heat treatment at 80℃ for 5 hours, and the unit of peel strength is gf / inch.

[0023] Preferably, the transfer release film may be one in which, when Nitto-31B tape is adhered to the surface of the lithium deposition layer and then peeled at a speed of 0.3 mpm, the peeling force of the release layer peeled together with the lithium deposition layer from the substrate interface satisfies the following equation 4.

[0024] (Formula 4)

[0025] 1 ≤ LR ≤ 200

[0026] The above LR is the peeling force of the release layer that is peeled together with the lithium deposition layer, and the unit of peeling force is gf / inch.

[0027] Preferably, the ion conductive polymer resin may include at least one selected from among cyclic olefin copolymer, polymethylmethacrylate, polyacrylate, polycarbonate, polystyrene, polyurethane, polyimide, and polyethylene naphthalate.

[0028] Preferably, the glass transition temperature (Tg) of the ion conductive polymer resin may be 80 to 150°C.

[0029] Preferably, the heterogeneous composition may contain 3 to 50 parts by weight of the ion conductive polymer resin per 100 parts by weight of the total.

[0030] Preferably, the solvent may be at least one selected from ethyl acetate (EA), methyl acetate (MA), methyl ethyl ketone (MEK), toluene, tetrahydrofolic acid (THF), and cyclohexane.

[0031] Preferably, the water contact angle of the heterogeneous layer surface may be 65 to 90°.

[0032] Preferably, the moisture permeability of the heterogeneous layer may be 200 g / ㎡·day or less.

[0033] Preferably, the ionic conductivity of the heterogeneous layer is 10 -6 10 inland -1 It could be S / cm.

[0034] Preferably, the surface pencil hardness of the heterogeneous layer may be 3H or higher.

[0035] Preferably, the arithmetic mean roughness (Ra) of the substrate may be 10 to 2,000 nm.

[0036] Preferably, the thickness of the heterogeneous layer may be 0.2 to 2 μm.

[0037] Preferably, the thickness of the lithium deposition layer may be 1.5 to 10 μm.

[0038] Preferably, after the lithium deposition layer is cross-cut into 100 pieces and Nitto-31B tape is attached to the surface and removed, the residual lithium deposition layer remaining on the tape may be 10 or less.

[0039] In addition, the above object is achieved by a lithium electrode comprising a current collector, a lithium deposition layer formed on at least one surface of the current collector, and a protective layer formed on the lithium deposition layer, wherein the lithium deposition layer and the protective layer are formed of a lithium deposition layer and a release layer transferred from the above-described transfer release film.

[0040] In addition, the above object is achieved by a method for manufacturing a lithium electrode, which comprises the steps of forming a release layer by coating a release composition including an ion-conductive polymer resin and a solvent on at least one surface of a substrate, depositing lithium metal on the release layer to form a lithium deposition layer, and attaching the surface of the lithium deposition layer to a current collector and then transferring the release layer and the lithium deposition layer to the current collector.

[0041] According to one embodiment of the present invention, a transfer release film and a lithium electrode using the same and a manufacturing method thereof can manufacture a lithium electrode by first forming a release layer and a lithium deposition layer on a separate substrate instead of forming a lithium deposition layer directly on a current collector when manufacturing a lithium electrode, and then transferring the release layer and the lithium deposition layer together to a current collector, thereby minimizing the situation in which lithium is exposed to the air during the electrode manufacturing process and preventing the growth of lithium dendrites, etc.

[0042] In addition, according to the present invention, since the lithium deposition layer and the release layer are transferred simultaneously in the process of transferring the lithium deposition layer to the current collector, there is an effect such that the release layer can perform the function of a protective layer for the lithium deposition layer and the current collector surface.

[0043] In addition, according to the present invention, there is an effect such as improving the lifespan of a secondary battery by controlling the thickness of the lithium deposition layer.

[0044] However, the effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description below.

[0045] FIG. 1 is a cross-sectional view of a transfer film according to one embodiment of the present invention in which a lithium deposition layer is not formed.

[0046] Figure 2 is a cross-sectional view of a transfer film according to one embodiment of the present invention.

[0047] Hereinafter, with reference to the attached drawings, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. The present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0048] In order to clearly explain the present invention in the drawings, parts that are not related to the description are omitted, and the same reference numerals are added to the same or similar components throughout the specification. In addition, the thickness is shown in the drawings to clearly express various layers and regions. In addition, when it is mentioned in this specification that an element is disposed "on" or "over" another element, the element may be disposed directly on the other element, or there may be elements interposed between the elements. On the other hand, when it is mentioned that an element is disposed "directly on" or "directly above" another element, there may not be interposed elements.

[0049] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In the event of a conflict, the present specification, including its definitions, will govern. Furthermore, although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

[0050] The term "including" in this specification means that other components may be included rather than excluding other components unless specifically stated to the contrary.

[0051] The term "combination of these" in this specification means a mixture or combination of one or more of the described components.

[0052] As used herein, the term "and / or" is meant to include any and all combinations of one or more of the items described herein. As used herein, the term "or" means "and / or." The expressions "at least one" or "one or more" preceding elements herein may supplement the entire list of elements and do not imply that they supplement individual elements described above.

[0053] Unless otherwise stated herein, all percentages, parts, ratios, etc. are by weight. Additionally, whenever an amount, concentration, or other value or parameter is given as a range, a preferred range, or a list of upper preferred values ​​and lower preferred values, this should be understood to specifically disclose all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed.

[0054] When a range of numerical values ​​is mentioned in this specification, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range. The scope of the present invention is not intended to be limited to the specific values ​​mentioned when defining the range.

[0055] In this specification, each component is a concept that includes both singular and plural.

[0056] Hereinafter, the present invention will be described in detail with reference to the attached drawings.

[0057] FIG. 1 is a cross-sectional view of a transfer release film according to one embodiment of the present invention in which a lithium deposition layer is not formed, and FIG. 2 is a cross-sectional view of a transfer release film according to one embodiment of the present invention.

[0058] Referring to FIG. 2, a transfer release film according to one embodiment of the present invention includes a substrate (120), a release layer (110) formed by being applied to one surface of the substrate (120), and a lithium deposition layer (140) formed by being deposited on the upper surface of the release layer (110), and may further include a coating layer (130) formed on the other surface of the substrate.

[0059] In general, lithium secondary batteries have several limitations in the manufacturing process due to their high reactivity, and contact with oxygen and moisture in the atmosphere is inevitable during battery assembly, which reduces the lifespan and performance of the battery, and there is a problem that the charge / discharge efficiency of the lithium electrode is reduced due to the growth of lithium dendrites. Accordingly, the inventors of the present invention have conducted various studies and confirmed that, when manufacturing a lithium electrode, instead of forming a lithium deposition layer directly on a current collector, a lithium deposition layer is formed on a separate substrate and then transferred to a current collector to manufacture a lithium electrode, thereby minimizing the exposure of lithium to the atmosphere during the electrode manufacturing process and preventing the growth of lithium dendrites, and thus completing the present invention. At this time, since a general release film cannot control the reactivity with lithium metal and the reactivity with heat and moisture, the lithium deposition layer cannot be transferred, and therefore, a transfer release film that implements a release layer that is non-reactive with lithium can be provided, thereby ensuring the processing processability of the lithium deposition layer and ensuring transferability that allows easy transfer to a current collector.

[0060] 1. Description (120)

[0061] According to one embodiment of the present invention, the substrate (120) of the transfer release film is preferably at least one selected from the group consisting of polyethylene terephthalate (PET), polyimide (PI), poly(methylmethacrylate) (PMMA), cellulose triacetate (TAC), polypropylene, polyethylene, and polycarbonate.

[0062] In one embodiment, the arithmetic mean roughness (Ra) of the substrate (120) is preferably 10 to 2,000 nm, and more preferably 10 to 100 nm. When the arithmetic mean roughness (Ra) of the substrate (120) is less than 10 nm, the adhesion between the release layer (110) and the surface of the substrate (120) is improved, and thus, transferability in which the release layer (110) and the lithium deposition layer (140) are transferred together cannot be obtained. When it exceeds 2,000 nm, the adhesion between the substrate (120) and the deposition drum is reduced during the formation of the lithium deposition layer (140), and thus, the deposition processability cannot be secured.

[0063] 2. Heterogeneous layer (110)

[0064] The release layer (110) is formed by applying a release composition to one surface of the substrate (120). Here, the release layer (110) is formed by coating one surface of the substrate (120), and is characterized in that there is no change in physical properties over time due to heat and moisture environments, and even when the lithium deposition layer (140) is formed on the release layer (110), the reaction with the lithium deposition layer (140) is controlled.

[0065] In one embodiment, the heterogeneous composition forming the heterogeneous layer (110) includes an ion conductive polymer resin and a solvent.

[0066] In the present invention, the ion-conductive polymer resin contained in the release composition forming the release layer (110) exhibits hydrophobic properties with low affinity for water and has excellent moisture barrier properties for the lithium deposition layer (140). In addition, in the present invention, the ion-conductive polymer resin can simultaneously function as a release agent and a binder.

[0067] In one embodiment, the ion conductive polymer resin preferably includes at least one selected from cyclic olefin copolymer (COC), polymethylmethacrylate (PMMA), polyacrylate, polycarbonate, polystyrene, polyurethane, polyimide, and polyethylene naphthalate.

[0068] In addition, the glass transition temperature (Tg) of the ion conductive polymer resin is preferably 80 to 150°C, and more preferably 100 to 130°C. When the glass transition temperature of the ion conductive polymer resin is less than 80°C, the hardness of the release layer (110) is low, so that when the release layer (110) and the lithium deposition layer (140) are laminated and peeled off together on the transfer body (current collector), the release layer (110) and the substrate (120) do not separate from each other, and thus transferability cannot be exhibited. When the glass transition temperature exceeds 150°C, the hardness of the release layer (110) becomes excessively high, so that when wound in a roll shape, the flexural elastic modulus of the release layer (110) decreases, causing cracks to occur in the release layer (110) and separation from the substrate (120).

[0069] In addition, the solvent included in the release composition is a solvent that can easily dissolve the ion conductive polymer resin, and preferably includes at least one solvent selected from among ethyl acetate (EA), methyl acetate (MA), methyl ethyl ketone (MEK), toluene, tetrahydrofolic acid (THFA), and cyclohexane. In addition, it is preferable to configure one or more mixed solvents so as to secure an excellent appearance in the process of applying the release composition on the substrate (120).

[0070] In one embodiment, the release composition preferably contains 3 to 50 parts by weight of the ion-conductive polymer resin based on the total 100 parts by weight, more preferably more than 10 parts by weight and less than 30 parts by weight. If the ion-conductive polymer resin is less than 3 parts by weight, sufficient coating coverage cannot be secured, so that the unique properties of the release layer (110) cannot be expressed and transfer characteristics cannot be achieved. If the ion-conductive polymer resin is more than 50 parts by weight, the viscosity of the release composition increases, so that a large amount of coating stains such as living, rainbow, or cloud patterns occur, resulting in a poor appearance.

[0071] In one embodiment, the water contact angle of the surface of the release layer (110) is preferably 65 to 90°. At this time, if the water contact angle of the surface of the release layer (110) is less than 65°, the surface may be easily contaminated due to high surface energy, and the surface may become vulnerable to blocking as the force of contact with the coating layer (130) on the other side increases during winding. On the other hand, if the water contact angle of the surface of the release layer (110) exceeds 90°, the slipperiness may become strong after winding in a roll state or depositing a lithium deposition layer (140), which may cause the winding section to come off and the appearance of scratches to be poor.

[0072] In one embodiment, the moisture permeability of the release layer (110) is preferably 200 g / m2·day or less, more preferably 180 g / m2·day or less, and even more preferably 150 g / m2·day or less. The release layer (110) can achieve the above-described moisture permeability through an ion conductive polymer resin having low moisture permeability and thus serve as a protective layer for the lithium deposition layer (140). If the moisture permeability of the release layer (110) exceeds 200 g / m2·day, the moisture permeability is excessive, which causes a problem in that the lithium deposition layer (140) cannot be protected from moisture.

[0073] In one embodiment, the ionic conductivity of the heterolayer (110) is 10 -6 10 inland -1 S / cm is preferable, 10 -5 10 inland -2 S / cm is more preferable, 10 -4 10 inland -3 It is even more preferable that it is S / cm. When the ionic conductivity of the heterogeneous layer (110) satisfies the above range, the rate performance for driving the secondary battery can be satisfied. Conversely, when the ionic conductivity of the heterogeneous layer (110) does not satisfy the above range, the rate performance cannot be satisfied.

[0074] In addition, the release layer (110) is preferably formed by at least one coating method selected from dip coating, spray coating, spin coating, die coating, roll coating, slot-die coating, bar coating, gravure coating, comma coating, curtain coating, and micro-gravure coating, but is not limited thereto, and various coating methods that can be used to form a coating layer in the art can be used.

[0075] In one embodiment, the thickness of the release layer (110) is preferably 0.2 to 2 μm, and more preferably 0.3 to 1.5 μm. If the thickness of the release layer (110) is less than 0.2 μm, a reverse peeling problem may occur during the transfer process, and if the thickness of the release layer (110) exceeds 2 μm, it becomes difficult to proceed with the process when the film is peeled after the transfer process.

[0076] Additionally, it is preferable that the surface pencil hardness of the heterogeneous layer (110) be 3H or higher.

[0077] In addition, the ion conductive polymer resin included in the heterogeneous composition is easily dissolved in an electrolyte solution, and thus does not cause a side reaction during or after battery assembly. In particular, the ion conductive polymer resin is dissolved by the electrolyte provided in the electrode assembly during the process of transferring the heterogeneous layer (110) and the lithium deposition layer (140) together to the electrode assembly, and thus does not cause a side reaction during or after battery assembly. At this time, the electrolyte solution that dissolves the ion conductive polymer resin may include at least one mixture selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate, vinylethylene carbonate, and halogenides thereof, and the halogenides thereof may include, but are not limited to, fluoroethylene carbonate (FEC).

[0078] As described above, the release layer (110) is peeled off from the substrate (120) together with the lithium deposition layer (140) and transferred to a transfer target (current collector, etc.), and in this process, the release layer (110) is dissolved and removed by the electrolyte provided in the electrode assembly. That is, the release layer (110) plays a role in protecting the lithium deposition layer (140) during the process of being transferred to the transfer target together with the lithium deposition layer (140), and during this process, the release layer (110) is dissolved by the electrolyte and removed without an additional process.

[0079] In addition, although the release layer (110) is formed only on one side of the substrate (120) in FIGS. 1 and 2, the release layer (110) may be formed on both sides of the substrate (120). Due to the release layer (110), the reverse delamination problem in which the lithium deposition layer (140) is transferred to another adjacent substrate (120) rather than the current collector during the winding process for transferring the lithium deposition layer (140) to the current collector can be prevented, and the substrate can be easily separated after the lithium deposition layer (140) is transferred onto the current collector. In addition, since the release layer (110) is formed on both sides of the substrate (120), outgassing caused by a reaction with the substrate (120) due to heat and moisture that may occur during the lithium deposition process for forming the lithium deposition layer (140) can be prevented.

[0080] Additionally, the release layer (110) may additionally include a protective layer between it and the lithium deposition layer (140). The protective layer between the release layer (110) and the lithium deposition layer (140) protects the lithium deposition layer (140) from heat and moisture in addition to the release layer (110).

[0081] 3. Lithium deposition layer (140)

[0082] A transfer release film according to one embodiment of the present invention includes a lithium deposition layer (140) formed by depositing on the upper surface of a release layer (110). More specifically, the lithium deposition layer (140) can be formed as a single layer of a lithium layer deposited (evaporated) on the release layer (110), and, if necessary, a lithium alloy layer can be formed on the surface of the deposited (evaporated) lithium metal layer through a gas treatment method. As an example, a lithium metal layer can be formed on the release layer (110) through deposition of gaseous lithium metal particles in a vacuum state, and a lithium alloy layer composed of Li2CO3 can be formed by injecting CO2 gas onto the lithium metal layer, thereby forming the lithium deposition layer (140). In this way, by additionally forming a lithium alloy layer on the surface of the deposited (evaporated) lithium metal layer through a gas treatment method, the lithium dendrite suppression effect can be enhanced.

[0083] In addition, the thickness of the lithium deposition layer is preferably 1.5 to 10 μm. Such a lithium deposition layer (140) acts as a diffusion barrier for lithium ions, thereby preventing the growth of lithium dendrites.

[0084] In addition, it is preferable that the lithium alloy layer is formed by depositing at least one lithium alloy selected from Li2CO3, Li2O3, Li3N, LiOH, and LiH, among which lithium carbonate (Li2CO3) is more preferable in terms of stability. However, the lithium alloy is not limited to the materials described above, and lithium alloys generally used in current collectors of secondary batteries can be used without limitation.

[0085] In addition, the thickness of the lithium alloy layer is preferably 1 nm to 1 μm. If the thickness of the lithium alloy layer is less than 1 nm, the lithium dendrite suppression effect is minimal, and if it exceeds 1 μm, the density difference with the lithium (Li) metal is large, so the surface and interface of the lithium metal may peel off.

[0086] In addition, the total thickness of the lithium deposition layer (140) including the lithium metal layer and the lithium alloy layer is preferably 1.5 to 10 μm, and more preferably 4 to 8 μm. In this case, if the total thickness is less than 1.5 μm, the charging and discharging performance of the secondary battery deteriorates, and if it exceeds 10 μm, the electrode thickness becomes excessively thick.

[0087] 4. Transmission type film (100)

[0088] According to one embodiment of the present invention, it is preferable that the transfer film has a peeling force that satisfies Equation 1.

[0089] (Formula 1)

[0090] 1 < TR < 100

[0091] In Equation 1, TR is the peeling force between the release layer (110) and the substrate (120) when the acrylic adhesive tape, Nitto-31B tape, is adhered to the surface of the release layer (110) at room temperature (23°C), the substrate (120) is attached so that it touches the floor, and the acrylic adhesive tape is held and peeled at a speed of 0.3 mpm (the peeling force when peeling the release layer from the substrate). The unit of peeling force is gf / inch.

[0092] If the value of equation 1 is 1 or less, the release layer (110) is too easily peeled off from the substrate (120), which causes a problem in that a separation occurs at the interface between the substrate (120) and the release layer (110) before the transfer process. If the value is 100 or more, a strong force is required for peeling, which causes a problem in that the film is torn or the transfer and peeling are not performed.

[0093] According to one embodiment of the present invention, it is preferable that the transfer film has a peeling force that satisfies Equation 2.

[0094] (Formula 2)

[0095] 1 < FR < 20

[0096] In Equation 2, FR is the peeling force between the release layer (110) and the substrate (120) when Nitto-31B tape, an acrylic adhesive tape, is adhered to the surface of the release layer (110) at room temperature (23°C), the adhesive tape is adhered so that it touches the floor, and then a substrate other than the acrylic adhesive tape is held and peeled at a speed of 0.3 mpm (the peeling force when peeling the substrate from the release layer). The unit of peeling force is gf / inch.

[0097] If the value of equation 2 is 1 or less, the substrate (120) is too easily peeled off from the release layer (110), which causes a problem in that a separation occurs at the interface between the substrate (120) and the release layer (110) before the transfer process. If the value is 20 or more, a strong force is required for peeling, which causes a problem in that the film is torn or the transfer and peeling are not performed.

[0098] As described above, both Equations 1 and 2 represent the peeling force between the release layer (110) and the substrate (120), and exhibit different peeling forces as described above due to the difference in the peeling method. This is related to the mechanism by which the release layer (110) is peeled from the substrate (120). When the release layer (110), which has relatively higher strength and lower elasticity than the substrate (120), is bent and peeled while the substrate (120) and the adhesive tape are laminated together, a crack occurs in the release layer (110) due to the difference in the bending rigidity of the PET forming the substrate (110) and the bending rigidity of the release layer (110), and the release layer is separated (transferred). In this process, when peeling off the release layer (110) with the adhesive tape, the release layer (110) has a strong tendency to stick to the substrate (120), and conversely, when peeling off the substrate (120) from the release layer (110) attached to the adhesive tape by turning it over, the release layer (110) has a strong tendency to stick to the adhesive tape, resulting in a difference in the peeling force values ​​of Equations 1 and 2.

[0099] According to one embodiment of the present invention, when a Nitto-31B tape is adhered to the surface of a release layer (110) and then peeled at a speed of 0.3 mpm, it is preferable that the peeling force between the release layer (110) and the substrate (120) satisfies the following equation 3.

[0100] (Formula 3)

[0101] 1 < TR1 / TR0 < 5

[0102] In Equation 3, TR0 is the peeling force of the release layer before heat treatment, TR1 is the peeling force of the release layer after heat treatment at 80℃ for 5 hours, and the unit of peeling force is gf / inch.

[0103] By satisfying the value of Equation 3, the change in peeling force under high temperature conditions can be suppressed, thereby solving the peeling problem at high temperatures.

[0104] According to one embodiment of the present invention, the transfer release film preferably satisfies the following Equation 4 when the Nitto-31B tape is adhered to the surface of the lithium deposition layer (140) and then peeled at a speed of 0.3 mpm, the peeling force of the interface between the release layer (110) and the substrate (120), that is, when the lithium deposition layer (140) is formed on the release layer (110) and the release layer (110) and the lithium deposition layer (140) are peeled together from the interface of the substrate (120).

[0105] (Formula 4)

[0106] 1 ≤ LR ≤ 200

[0107] In Equation 4, LR is the peeling force of the release layer that is peeled together with the lithium deposition layer, and the unit of peeling force is gf / inch.

[0108] If the value of Equation 4 is less than 1, there is a problem that the layer is easily peeled off and separated at the interface between the release layer (110) and the substrate (120) before the transfer process, and if it is more than 200, there is a problem that the lithium deposition layer (140) is not transferred.

[0109] According to one embodiment of the present invention, the release film for transfer preferably has a peeling force between the release layer (110) and the substrate (120) when the lithium deposition layer (140) is transferred to the current collector, which is 1 to 100 gf / inch. If the peeling force is less than 1 gf / inch, a separation defect occurs in which the lithium deposition layer (140) is first separated from the substrate (120) together with the release layer (110) in the transfer release film state, and if it exceeds 100 gf / inch, a peeling defect occurs in which the substrate (120) is not peeled after the lithium deposition layer (140) is transferred to the current collector.

[0110] In addition, in the transfer release film according to one embodiment of the present invention, after the lithium deposition layer (140) is cross-cut into 100 pieces and Nitto-31B tape is attached to the surface and removed, it is preferable that the lithium deposition layer (140) remaining on the tape has a residual ratio of 10 or less. If the residual ratio of the release layer exceeds 10, the release layer (110) does not separate from the substrate (120) together with the lithium deposition layer (140) but remains on the substrate (120), thereby reducing the transferability of the lithium layer.

[0111] 5. Coating layer (130)

[0112] In a transfer release film according to one embodiment of the present invention, the substrate (120) may further include a coating layer (130) formed on the other surface (the surface opposite the release layer). In this case, the coating layer (130) may have the same configuration as the release layer (110). Through such a coating layer (130), a blocking phenomenon can be prevented when the transfer release film is wound, and outgassing caused by a reaction with the substrate (120) due to heat and moisture that may occur during the lithium deposition process can be prevented.

[0113] 6. Lithium electrode and method for manufacturing the same

[0114] According to one embodiment of the present invention, a transfer release film is used in a transfer process in which a release layer (110) and a lithium deposition layer (140) are peeled off together from a substrate (120) and transferred, and the release layer (110) acts as a protective layer (barrier) for the lithium deposition layer (140) during a manufacturing process of a lithium electrode, thereby preventing the formation of a native layer of a lithium metal oxide film.

[0115] According to one embodiment of the present invention, a lithium electrode comprises a current collector, a lithium deposition layer formed on at least one surface of the current collector, and a protective layer formed on the lithium deposition layer, wherein the lithium deposition layer and the protective layer may be formed of a lithium deposition layer and a release layer transferred from the above-described transfer release film.

[0116] In addition, a method for manufacturing a lithium electrode according to one embodiment of the present invention includes a step (S101) of forming a release layer by coating a release composition on at least one surface of a substrate, a step (S102) of forming a lithium deposition layer by depositing lithium metal on the release layer, and a step (S103) of attaching the surface of the lithium deposition layer to a current collector and then transferring the release layer and the lithium deposition layer to the current collector.

[0117] In the step (S101) of forming a release layer by coating a release composition on at least one side of the substrate, the release composition has the same composition as the release composition of the transfer release film described above, and a duplicate description thereof is omitted.

[0118] After the step (S101) of forming a release layer by coating a release composition on at least one surface of a substrate, and before performing the step (S102) of forming a lithium deposition layer on the release layer, a step of forming a protective layer on the release layer may be further included. In this case, as an example, the protective layer may include Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and in addition, a general protective material capable of protecting lithium metal in a lithium battery or secondary battery may be used.

[0119] Next, the step (S102) of forming a lithium deposition layer on the release layer is a step of forming a lithium deposition layer composed of a single layer of lithium metal layers by depositing lithium metal on the release layer. In addition, if necessary, a step of forming a lithium alloy layer on the lithium deposition layer may be further included after the step (S102) of forming the lithium deposition layer. In this case, the lithium deposition layer may be formed through a deposition process, and the lithium alloy layer may be formed through a gas treatment method. As an example, a lithium metal layer may be formed on the release layer (140) by depositing gaseous lithium metal particles in a vacuum state, and a lithium alloy layer composed of Li2CO3 may be formed by injecting CO2 gas onto the lithium metal layer, thereby forming the lithium deposition layer (140).

[0120] If a protective layer is formed after step (S101), a lithium deposition layer (140) can be formed on the protective layer in step (S102) of forming a lithium deposition layer on the heterostructure.

[0121] Next, in the step (S103) of transferring the release layer and the lithium deposition layer to the current collector, the release layer (110) and the lithium deposition layer (140) are transferred to not only one side of the current collector but also both sides of the current collector, thereby forming a lithium deposition layer (140) on both sides of the current collector, thereby enabling the formation of a thin and uniform lithium deposition layer (140).

[0122] Hereinafter, the composition and resulting effects of the present invention will be described in more detail through examples and comparative examples. However, these examples are intended to more specifically illustrate the present invention, and the scope of the present invention is not limited to these examples.

[0123] [Example]

[0124] 1. Confirmation of transferability by type of heterogeneous layer resin

[0125] In order to determine the suitability for lithium deposition and transfer to the collector, the transferability according to the type of resin of the release layer was first confirmed.

[0126] A release film having a 0.5 ㎛ thick release layer was manufactured by coating silicone, fluorine, melamine, urethane, acrylic, and olefin resins onto a polyester base film (Toray Advanced Materials, Excell-25 ㎛, arithmetic mean roughness Ra: 20 nm), respectively. After leaving each manufactured film at room temperature (23 ℃) for one day, 100 crosscuts were made on the surface of the release layer by crossing lines of 10 x 10 (mm) with a cross hatch cutter, and then Nitto-31B tape was attached, rubbed off with a uniform force, and the film pieces that were separated from the release layer on the tape were counted to check the residual rate.

[0127] As a result, it was confirmed that there was no transferability in the case of silicone, fluorine, melamine, and urethane resins, with a residual rate of 100 (all release layers remaining on the tape), and that acrylic and olefin resins had a residual rate of 0, with a transferability.

[0128] In addition, as a result of proceeding with the same method except that the above-mentioned heterogeneous layer was manufactured to a thickness of 1 ㎛, it was confirmed that silicone, fluorine, melamine, and urethane resins had a residual rate of 100, indicating no transferability, and acrylic and olefin resins had a residual rate of 0, indicating transferability.

[0129] 2. Confirmation of moisture barrier properties of heterogeneous layer coating resin

[0130] In order to determine the suitability as a material for a protective layer for lithium electrodes, the water vapor transmission rate (WVTR) of the release layer was measured to confirm the moisture barrier property. Here, the water vapor transmission rate (g / m 2 ·day) refers to the amount of moisture [g] that passes through a film with an area of ​​1㎡ in one day, and the lower the moisture permeability, the better the moisture blocking property.

[0131] First, water was filled in each of three cups, and each was covered with a film of PVdF-HFP coated on triacetyl cellulose film (TAC) (TAC / PVdF-HFP), a film of PMMA resin coated on TAC (TAC / PMMA), and a film of COC resin coated on TAC (TAC / COC). After one day, the moisture permeability of each of the above films was measured using a moisture permeability measuring device (TSY-T3, Labthink).

[0132] As a result of the measurement, the moisture permeability of TAC, TAC / PVdF-HFP, TAC / PMMA, and TAC / COC was measured to be 327g, 319g, 157g, and 146g, respectively, indicating that TAC / PMMA and TAC / COC have excellent moisture barrier properties, and thus are confirmed to be suitable coating resins for transferring a protective layer for lithium electrodes.

[0133] [Example 1]

[0134] (1) Preparation of heterogeneous composition and coating layer composition

[0135] A release composition was prepared by mixing 20 parts by weight of polymethyl methacrylate (PMMA) (IH830HT from LX MMA), an ion-conducting polymer resin, 40 parts by weight of EA (Ethyl Acetate), and 40 parts by weight of toluene to have a solid content of 20% by weight.

[0136] In addition, a coating layer composition was prepared by mixing 5 parts by weight of ion conductive polymer resin (LX MMA; IH830HT), 47.5 parts by weight of EA (Ethyl Acetate), and 47.5 parts by weight of toluene so that the solid content was 20% by weight.

[0137] (2) Manufacturing of a film with a release layer and a coating layer formed

[0138] A release composition was applied to one side of a polyester base film (Toray Advanced Materials, Excell-25㎛, arithmetic mean roughness Ra: 20nm) and a coating layer composition was applied to the other side using a Micro-Gravure coater, and then dried at 140°C for 30 seconds to manufacture a film with a release layer coating thickness of 800nm ​​and a coating layer thickness of 200nm on the other side.

[0139] (3) Manufacturing of a release film with a lithium deposition layer formed

[0140] Using the evaporation deposition method, lithium metal was deposited on the release layer at 600°C, and a transfer release film having a lithium deposition layer having a thickness of 6 μm was manufactured.

[0141] [Example 2]

[0142] A transfer release film was manufactured in the same manner as in Example 1, except that polymethyl methacrylate (PMMA) (HP101 from LX MMA) was used as the ion-conducting polymer resin in the release composition.

[0143] [Example 3]

[0144] A transfer release film was manufactured in the same manner as in Example 1, except that a cyclic olefin copolymer (COC) (6013 Grade from Topas) was used as the ion-conducting polymer resin in the heterogeneous composition.

[0145] [Example 4]

[0146] A transfer release film was manufactured in the same manner as in Example 1, except that the arithmetic mean roughness Ra of the base film was 10 nm.

[0147] [Example 5]

[0148] A transfer release film was manufactured in the same manner as in Example 1, except that the arithmetic mean roughness Ra of the base film was 50 nm.

[0149] [Example 6]

[0150] A transfer release film was manufactured in the same manner as in Example 1, except that the arithmetic mean roughness Ra of the base film was 2,000 nm.

[0151] [Example 7]

[0152] A transfer release film was manufactured in the same manner as in Example 1, except that the coating thickness of the release layer was set to 200 nm.

[0153] [Example 8]

[0154] A transfer release film was manufactured in the same manner as in Example 1, except that the coating thickness of the release layer was set to 400 nm.

[0155] [Example 9]

[0156] A transfer release film was manufactured in the same manner as in Example 1, except that the coating thickness of the release layer was set to 1,000 nm.

[0157] [Example 10]

[0158] A transfer release film was manufactured in the same manner as in Example 1, except that the coating thickness of the release layer was set to 2,000 nm.

[0159] [Comparative example]

[0160] [Comparative Example 1]

[0161] A transfer release film was manufactured in the same manner as in Example 1, except that an aqueous acrylic resin (GS0131 from NIPPON CARBIDE) was used as the ion-conducting polymer resin in the release composition.

[0162] [Comparative Example 2]

[0163] A transfer release film was manufactured in the same manner as in Example 1, except that an aqueous acrylic resin (FT9542 from NIPPON CARBIDE) was used as the ion-conducting polymer resin in the release composition.

[0164] [Comparative Example 3]

[0165] A transfer release film was manufactured in the same manner as in Example 1, except that polymethyl methacrylate (PMMA) (HP05B from LX MMA) was used as the ion-conducting polymer resin in the release composition.

[0166] [Comparative Example 4]

[0167] A transfer release film was manufactured in the same manner as in Example 1, except that the arithmetic mean roughness Ra of the base film was 2 nm.

[0168] [Comparative Example 5]

[0169] A transfer release film was manufactured in the same manner as in Example 1, except that the arithmetic mean roughness Ra of the base film was 8 nm.

[0170] [Comparative Example 6]

[0171] A transfer release film was manufactured in the same manner as in Example 1, except that the coating thickness of the release layer was set to 50 nm.

[0172] [Comparative Example 7]

[0173] A transfer release film was manufactured in the same manner as in Example 1, except that the coating thickness of the release layer was set to 100 nm.

[0174] [Comparative Example 8]

[0175] A transfer release film was manufactured in the same manner as in Example 1, except that the coating thickness of the release layer was set to 190 nm.

[0176] The properties of the transfer-use release films manufactured in Examples 1 to 10 and Comparative Examples 1 to 8 were evaluated through the following experimental examples, and the results are shown in Table 1. Meanwhile, the glass transition temperature (Tg) of the ion-conductive polymer resin used in each Example and Comparative Example is separately shown in Table 1 below.

[0177] [Experimental Example]

[0178] (1) Measurement of transcription

[0179] Acrylic adhesive tape Nitto-31B was attached to the surface of the lithium deposition layer of the manufactured examples and comparative examples, and was rubbed off with a force of 2 kg to check whether the release layer and lithium deposition layer were transferred onto the tape and peeled off.

[0180] ○: Transcribed

[0181] X: Not transcribed

[0182] (2) Measurement of the peel strength of the heteromorphic layer (TR, TR1)

[0183] For the examples and comparative examples, before forming the lithium deposition layer, the substrate was attached to a cold-rolled stainless steel plate with a double-sided adhesive tape, then the adhesive tape Nitto-31B was placed on the release layer and pressed with a 2 kg press roller, and left at room temperature (23°C) for 5 hours. Then, the adhesive tape Nitto-31B was held and the release layer was peeled from the substrate, and the peeling force (TR, TR0) of the release layer and the substrate was measured. After leaving it at 80°C for 5 hours, the peeling force (TR1) when peeling the release layer from the substrate was measured using the same method.

[0184] Peel strength was measured using an AR-1000 (Chem-Instrument) at a peel angle of 180° and a peel speed of 0.3 mpm. The average value (g / inch) was calculated by measuring five times, and the value was rounded to the nearest tenth. In addition, Equation 3 was calculated based on the measured value, and the value was rounded to the nearest tenth.

[0185] (3) Measurement of the peel strength (FR) of the heteromorphic layer

[0186] For the examples and comparative examples, before forming the lithium deposition layer, the adhesive tape Nitto-31B was attached to a cold-rolled stainless steel plate with a double-sided adhesive tape with the adhesive side facing upward, and then a film was placed on the adhesive side of the adhesive tape Nitto-31B so that the release layer was in contact with it, and then pressed with a 2 kg press roller, and left at room temperature (23°C) for 5 hours, and the substrate was peeled from the release layer, and the peeling force (FR) when the substrate was peeled from the release layer was measured.

[0187] Peeling force was measured using AR-1000 (Chem-Instrument) at a peeling angle of 180° and a peeling speed of 0.3 mpm. The measurement was performed 5 times and the average value (g / inch) was calculated, rounded to the first decimal place.

[0188] (4) Measurement of lithium deposition layer peeling force (LR)

[0189] For the transfer release films of the examples and comparative examples, a substrate was attached to a cold-rolled stainless steel plate with a double-sided adhesive tape, and then the adhesive tape Nitto-31B was placed on the lithium deposition layer and pressed with a 2 kg pressing roller, and left at room temperature (23°C) for 5 hours. Then, the lithium deposition layer (lithium layer) and the release layer were peeled off from the substrate together as in Experimental Example 2, and the peel strength (LR) was measured.

[0190] (5) Measurement of crosscut survival rate

[0191] In the transfer release film of the examples and comparative examples, 10x10 (mm) lines were cut crosswise on the surface of the lithium deposition layer (lithium layer) using a cross hatch cutter, and then Nitto-31B tape was attached, rubbed off with uniform force, and the film pieces that were separated from the coating surface on the tape were counted to express the residual rate as a number (ASTM D3359, KS M ISO 2409).

[0192] (6) Measurement of coating thickness (dry thickness)

[0193] The transfer release films of the examples and comparative examples were cut into samples measuring 5 cm X 5 cm, and the dry thickness of the release layer was measured. The thickness was measured using an ellipsometer (Elli-SE, Ellipso Technology), and the average value was calculated by measuring three times.

[0194] (7) Measurement of arithmetic mean roughness (Ra)

[0195] The Ra of the substrate film surface was measured using a contact-type 3D roughness measuring instrument (Kosaka SE3300 product), and the average value was calculated by repeating the measurement 5 times with a standard measurement length of 0.08 cm.

[0196] ClassificationRelease layer Resin roughnessThicknessPeel strength(gf / inch)TransferabilityResidual rateBase materialRelease layerTR1TR(TR0)LRFRTR1 / TR0Release layer and lithium layerLithium layer typeTg(℃)Ra(㎚)(㎚)80℃23℃23℃23℃--(%)Example 1PMMA1202080010030554.33.3○0Example 2PMMA80208001328814212.11.5○0Example 3COC13820800381 8382.02.1○0Example 4PMMA12010800182881585.12.1○0Example 5PMMA120508005526412.82.1○0Example 6PMMA1202,00080010532653.13.3○0Example 7PMMA12020200210981827.62.1○8Example 8PMMA12020400162781685.72.1○1Example 9PMMA120201,0003921322.21.9○0Example 10PMMA120202,0002515282.11.7○0Comparative Example 1Water-based acrylic7020800920929108.810.0○100Comparative Example 2Water-based acrylic10720800280659508.24.3○100Comparative Example 3PMMA702080022210824014.22.1X12Comparative Example 4PMM A12028001,1208209208151.4X100Comparative Example 5 PMMA 12088001,1508309008311.4X100Comparative Example 6 PMMA 12020501,1009209109081.2X100Comparative Example 7 PMMA 120201001,1209108909051.2X100Comparative Example 8 PMMA 120201901,1108502628701.3X15

[0197] As described in Table 1 above, the transfer release films according to Examples 1 to 10 of the present invention have excellent transfer properties and peeling strength, and it can be confirmed that the transfer properties and peeling properties are excellent and have appropriate values ​​within an appropriate range even when lithium is deposited in a high-temperature atmosphere and a high-temperature vacuum atmosphere.

[0198] More specifically, when comparing the transfer release films according to Examples 2 and 3 of the present invention and Comparative Examples 1 to 3, it can be confirmed that the transferability and peel strength properties of the release layer change in a correlation depending on the type of release composition resin and the glass transition temperature (Tg).

[0199] In addition, when comparing the transfer release films according to Examples 4 to 6 of the present invention and Comparative Examples 4 and 5, it can be confirmed that the arithmetic average roughness (Ra) of the substrate has a large correlation with the transferability and peeling force of the release layer, and that the transferability and peeling force of the release layer change depending on the arithmetic average roughness of the substrate.

[0200] In addition, when comparing the transfer release films of Examples 7 to 10 of the present invention and Comparative Examples 6 to 8, it can be confirmed that the coating thickness of the release layer has a large correlation with the transferability and peeling force, and that the transferability and peeling force change depending on the coating thickness of the release layer. More specifically, it can be confirmed that the thicker the release layer, the better the transferability and easy peeling properties, and it can be confirmed that implementing a thickness above a certain level is necessary to secure the transferability.

[0201] As described above, the transfer release film according to the present invention can be appropriately applied to a desired purpose, but is not limited thereto. In addition, the present invention can provide a high-quality transfer release film for use in the field of secondary battery materials, which has excellent transfer properties and an appropriate range of peeling strength, thereby reducing damage to electrode active materials during transfer to a current collector, and can be used for a desired purpose without degrading the function of the battery.

[0202] Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept of the present invention defined in the following claims also fall within the scope of the present invention.

Claims

1. Description; A release layer formed by applying a release composition containing an ion conductive polymer resin and a solvent to one surface of the substrate; and A lithium deposition layer formed by deposition on the upper surface of the above heterogeneous layer; A transfer film containing a transfer agent.

2. In paragraph 1, A transfer release film in which the above-mentioned release layer is detached from the above-mentioned substrate and transferred to an electrode together with the above-mentioned lithium deposition layer.

3. In paragraph 1, A transfer release film further comprising a coating layer formed on the other side of the above-mentioned substrate and containing an ion-conductive polymer resin.

4. In paragraph 1, The above ion conductive polymer resin is a transfer release film that is dissolved by an electrolyte provided in an electrode assembly.

5. In paragraph 1, The above transfer release film has a peeling force satisfying the following equations 1 and 2: (Formula 1) 1 < TR < 100 (Formula 2) 1 < FR < 20 The above TR is the peeling force when the release layer is peeled off from the substrate at a speed of 0.3 mpm while holding the Nitto-31B tape in a state where the substrate is fixed after the Nitto-31B tape is adhered to the surface of the release layer at room temperature (23°C) before forming a lithium deposition layer on the release layer, and the above FR is the peeling force when the substrate is peeled off from the release layer at a speed of 0.3 mpm while holding the Nitto-31B tape in a state where the Nitto-31B tape is adhered to the surface of the release layer at room temperature (23°C) before forming a lithium deposition layer on the release layer, and the unit of peeling force is gf / inch.

6. In paragraph 1, The above transfer release film is a transfer release film that satisfies the following formula 3 when Nitto-31B tape is adhered to the surface of the release layer and then peeled at a speed of 0.3 mpm: (Formula 3) 1 < TR1 / TR0 < 5 The above TR0 is the peeling force of the release layer before heat treatment, and TR1 is the peeling force of the release layer after heat treatment at 80°C for 5 hours, and the unit of peeling force is gf / inch.

7. In paragraph 1, The above transfer release film is a transfer release film in which, when Nitto-31B tape is adhered to the surface of a lithium deposition layer and then peeled at a speed of 0.3 mpm, the peeling force of the release layer peeled together with the lithium deposition layer from the substrate interface satisfies the following equation 4. (Formula 4) 1 ≤ LR ≤ 200 The above LR is the peeling force of the release layer that is peeled together with the lithium deposition layer, and the unit of peeling force is gf / inch.

8. In paragraph 1, A transfer release film, wherein the ion conductive polymer resin comprises at least one selected from among cyclic olefin copolymer, polymethylmethacrylate, polyacrylate, polycarbonate, polystyrene, polyurethane, polyimide, and polyethylene naphthalate.

9. In paragraph 1, A transfer release film with improved transfer efficiency, wherein the glass transition temperature (Tg) of the above ion conductive polymer resin is 80 to 150°C.

10. In paragraph 1, A transfer release film, wherein the above-mentioned heterogeneous composition comprises 3 to 50 parts by weight of an ion-conductive polymer resin for a total of 100 parts by weight.

11. In paragraph 1, A transfer release film, wherein the solvent is at least one selected from ethyl acetate, methyl acetate, methyl ethyl ketone, toluene, tetrahydrofolic acid, and cyclohexane.

12. In paragraph 1, A transfer release film having a water contact angle of 65 to 90° on the surface of the release layer.

13. In paragraph 1, A transfer release film having a moisture permeability of the above release layer of 200 g / ㎡·day or less.

14. In paragraph 1, The ionic conductivity of the above heterogeneous layer is 10 -6 10 inland -1 S / cm, transfer-type release film.

15. In paragraph 1, A transfer release film having a surface pencil hardness of 3H or higher.

16. In paragraph 1, A transfer film having an arithmetic mean roughness (Ra) of 10 to 2,000 nm.

17. In paragraph 1, A transfer release film having a thickness of the above release layer of 0.2 to 2㎛.

18. In paragraph 1, A transfer release film having a thickness of the lithium deposition layer of 1.5 to 10 μm.

19. In paragraph 1, A transfer release film in which the lithium deposition layer is cross-cut into 100 pieces, Nitto-31B tape is attached to the surface, and then removed, and the remaining lithium deposition layer remains on the tape at a rate of 10 or less.

20. The whole house, A lithium deposition layer formed on at least one surface of the above collector; and Including a protective layer formed on the above lithium deposition layer, A lithium electrode, wherein the lithium deposition layer and the protective layer are formed from the lithium deposition layer and the release layer transferred from a transfer release film according to any one of claims 1 to 19.

21. A step of forming a release layer by coating a release composition containing an ion conductive polymer resin and a solvent on at least one surface of a substrate; A step of forming a lithium deposition layer by depositing lithium metal on the hetero layer; and A step of attaching the surface of the lithium deposition layer to a current collector and then transferring the release layer and the lithium deposition layer to the current collector; A method for manufacturing a lithium electrode, comprising:

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