JP2009266526A - Method of forming inorganic thin-film pattern on metal base plate, and method of manufacturing electrode for lithium secondary battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve a problem such that, an exposed part of a current collector foil (metal plate) is required for joining a terminal to an electrode in forming an active material layer (inorganic thin film) on the current collector foil, and so there is the risk of active material layer (inorganic thin film) contamination by oil or water in forming the exposed part by a method in a prior art. <P>SOLUTION: The method of forming an inorganic thin-film pattern on a metal plate includes the steps of: (a) preparing a base plate having a first region where an organic thin film containing one compound selected from phthalic ester and paraffine is formed on the metal base plate and a second region where the organic thin film is not formed; (b) forming an inorganic thin film on the first and second regions of the base plate; and (c) removing the inorganic thin film formed on the first region of the base plate. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for forming an inorganic thin film pattern on a metal substrate and a method for producing an electrode for a lithium secondary battery.

  In recent years, the miniaturization and multi-functionalization of portable devices have progressed, and accordingly, the capacity of a battery as a power source for portable devices has been demanded.

  As a high-capacity negative electrode active material in a lithium secondary battery, a material containing silicon (Si) is promising because it has a large amount of occlusion of lithium, and in particular, SiOx (0 <x <2), which is a compound of Si and oxygen (O). Many have been studied. As a method for forming SiOx on a current collector, there are a vacuum deposition method, a method in which SiOx particles are mixed with a binder and a solvent, and a paste is applied, dried, and rolled.

  Among these methods, the vacuum evaporation method is a dry process that can obtain an active material film that does not contain a binder and is advantageous for increasing the energy density.

  As a method of forming SiOx by a vacuum deposition method, there is a reactive deposition method in which Si is used as an evaporation source and oxygen (O) is introduced into a vacuum chamber. In order to increase productivity, it is effective to increase the evaporation rate of Si, and there is a method of heating Si as an evaporation source to about 2000 ° C. above the melting point. In this case, since the vicinity of the place where the film is formed becomes high temperature, it is difficult to introduce a complicated mechanism.

  By the way, there are various types of lithium secondary batteries. In lithium secondary batteries such as a wound type and a laminated type, cutting is performed according to the battery size, and a tab (terminal) is joined to the current collector exposed portion. Positive and negative electrodes are required. When joining a terminal to an electrode in which the active material is formed on both sides of the current collector, it may be difficult to join the terminal, or even if it can be joined, there will be defects such as insufficient electrical contact and high electrical resistance. Or other problems may occur. Therefore, the electrode needs a current collector exposed portion.

  In the vacuum deposition method, the current collector exposed part is formed by forming a film while covering a part of the current collector with a mask during film formation. There is a way to do it. However, in the roll-to-roll method that forms a film continuously on a long current collector with high productivity, a mask of a method that moves according to the movement of the current collector is required. Has the problem of becoming complicated.

  There is an oil margin method (also called an oil mask method) as a method for forming a non-deposition portion with a simple configuration in the roll-to-roll method. (See Patent Document 1) In the oil margin method, when a metal film is formed on a polymer film, the oil application part becomes a non-film formation part by applying oil on the film in advance.

Moreover, there exists a method of forming a film exposure part by forming water-soluble resin partially on a film, vapor-depositing a metal film, and washing with water. (See Patent Document 2)
Japanese Patent Publication No. 3-59981 JP-A-3-134154

  As shown in FIG. 4, the exposed portion of the current collector foil 2 is necessary to join the terminal 38 to the electrode 37 during the manufacture of the lithium ion secondary battery. When the active material film 39 is formed by forming oil on the current collector foil, part of the oil is taken into the active material film 39. When the water-soluble resin is formed on the current collector foil and the active material film 39 is formed, there is a step of immersing the active material film 39 in water, and there is adsorbed water or the like and water remains. An active material incorporating impurities such as oil, or an active material in which water remains may have an adverse effect on cycle characteristics and the like in a lithium secondary battery.

  More specifically, in Patent Document 1, since the oil formed on the substrate on which the film is formed is volatilized, a part of the volatilized oil is taken into the formed film. Therefore, there are concerns about adverse effects such as an increase in impurities made up of oil and oil breakdown products, and deterioration of the cycle characteristics of the lithium secondary battery.

  In Patent Document 2, a water washing step is necessary after film formation, and the formed film comes into contact with water. A certain amount of water can be removed by high temperature drying or vacuum drying, but it is difficult to remove completely due to adsorbed water. In the lithium secondary battery, residual water adversely affects cycle characteristics and the like.

  Moreover, such a problem is a problem that may occur not only in the manufacturing process of a lithium secondary battery, but generally when a patterned inorganic thin film is formed on a metal substrate.

  The present invention solves the above-described problems, and an object of the present invention is to provide a method for manufacturing an electrode in which a terminal is attached to a current collector foil by a method that does not contaminate an active material film.

In order to solve the above problems, a method of forming an inorganic thin film pattern on a metal substrate of the present invention is as follows.
(A) The substrate having a first region in which an organic thin film containing one compound selected from phthalate ester and paraffin is formed on the substrate, and a second region in which the organic thin film is not formed The process of preparing
(B) forming an inorganic thin film on the first region and the second region of the substrate; and (c) removing the inorganic thin film formed on the first region of the substrate;
Have

  Here, the inorganic substance is a metal, a semiconductor, an oxide or a nitride thereof. Desirably, it is a semiconductor or an oxide thereof. More preferably, it is Si or Si oxide.

  Examples of the phthalic acid ester include DEHP, DIDP, DINP, DBP and the like.

Moreover, the method for producing the electrode for a lithium ion battery of the present invention comprises:
(A) having a first region where an organic thin film containing one compound selected from phthalate ester and paraffin is formed on a current collector substrate, and a second region where the organic thin film is not formed Preparing the substrate;
(B) forming an active material thin film on the first region and the second region of the substrate; and (c) removing the active material thin film formed on the first region of the substrate;
Have

  According to the method for forming an inorganic thin film pattern on the metal substrate of the present invention, the inorganic thin film pattern can be formed without contaminating the inorganic thin film.

  According to the method for manufacturing an electrode for a lithium secondary battery of the present invention, it is possible to form an active material film patterned by a method that does not contaminate the active material film. Therefore, it is possible to provide an electrode having a current collector exposed portion (terminal junction portion) used for a wound type or stacked type lithium secondary battery without adversely affecting the cycle characteristics of the lithium secondary battery.

  Embodiments of the present invention will be described below with reference to the drawings.

  In the following, as an example of a method for producing an inorganic thin film pattern, a case where a current collector substrate is used as a metal substrate and an active material thin film is used as an inorganic thin film to produce an electrode for a lithium secondary battery will be described.

(Embodiment 1)
FIG. 1 is a manufacturing process flow diagram of an electrode for a lithium secondary battery of the present invention. Each step will be described below with reference to FIG.

<Organic coating process 1>
As a method for coating the current collector foil 2 with an organic substance, there are a vacuum evaporation method and a method by exposure to an organic vapor under atmospheric pressure. The internal structure of the chamber 1 shown in FIG. 2A is a schematic diagram of an apparatus for coating an organic substance by a vacuum deposition method. As shown in FIG. 2A, an unwinding roll 3 in which a current collector foil 2 is wound, a plurality of auxiliary rolls 4, 5, 6, a mask 7, and an evaporation source are arranged in a chamber 1. A vacuum pipe 8 is connected below the chamber 1 and evacuated to a vacuum degree of 1E-2 Pa by an oil diffusion pump 9 and an oil rotary pump 10. The evaporation source is configured by putting an organic substance 12 in a boat 11 made of molybdenum, and the boat 11 is heated by a resistance heating method. The evaporation source heating condition is controlled while measuring the evaporation rate with a quartz oscillator film thickness meter (not shown). The organic substance 12 is preferably a phthalate ester. Here, DEHP (Diethylhexyl Phthalate) was used among the phthalates. DEHP is an organic substance having a boiling point of 370 ° C. at atmospheric pressure (about 1.0E + 5 Pa) and a boiling point of 100 ° C. or less at a vacuum degree of 1.0E-2 Pa. The current collector foil 2 is unwound from the unwinding roll 3 at a speed of 1 cm / min, moves along the auxiliary roll 4, and forms an organic substance when passing through the opening region of the stainless steel mask 7. 5 and 6 to move to the portion shown in FIG.

  The presence of the organic substance 12 on the current collector foil 2 can be detected by generated gas analysis (EGA-MS). As a result of analysis, it was confirmed that the organic substance 12 coated on the current collector foil 2 could exist stably even after a long time in vacuum. On the other hand, when the current collector foil 2 coated with the organic substance 12 was analyzed by a thermobalance (TG) that heated and measured the weight change, the weight change was below the detection limit. From these results, it is presumed that the organic substance 12 is a monomolecular film or a state close thereto and is adsorbed on the surface by physical or chemical bonding.

  It is estimated that the film thickness of the organic substance 12 is preferably a monomolecular film or a thickness close thereto. The reason is that the active material film can be sufficiently removed with this film thickness, and if the organic material film thickness is thick, there is a concern that the organic material will re-adhere to the surrounding organic material removal part in the active material forming process, which is a subsequent process, and the adhesion will be reduced. Because there is.

<Heating step 1>
As a method of heating the current collector foil 2, there are heating with a halogen lamp or heating with an infrared heater. The internal structure of the chamber 1 shown in FIG. 2B is a schematic diagram of an apparatus for heating the current collector foil 2 with a halogen lamp 18. As shown in FIG. 2B, a plurality of auxiliary rolls 13, 14, 15, 16, a mask 17, a halogen lamp 18, a mask driving roll 91, and mask auxiliary rolls 92, 93, 94 are arranged in the chamber 1. To do. A vacuum pipe 19 is connected to the lower side of the chamber 1 (B), and vacuum exhaust is performed by the oil diffusion pump 20 and the oil rotary pump 21. A halogen lamp 18 is disposed at a location facing the current collector foil 2 below the chamber 1 (B), and the current collector foil 2 is heated.

  The current collector foil 2 moves along the auxiliary rolls 13, 14, 15, and 16 at a speed of 1 cm / min and moves to the chamber (C) in FIG. The mask 17 moves along the mask driving roll 91 and the mask auxiliary rolls 92, 93, 94 at a speed of 1 cm / min. By making the movement speeds of the current collector foil 2 and the mask 17 the same, the specific position of the current collector foil 2 can be continuously shielded by the mask 17. FIG. 6 is a schematic diagram of the mask 17. The mask 17 has a structure having a rectangular opening on a long plate. When the current collector foil 2 is between the auxiliary rolls 14 and 15, it is heated by the light of the halogen lamp 18 that is transmitted without being shielded by the mask 17, and organic substances are removed except for a predetermined portion. In order to remove the organic material covering the current collector foil 2, the heating temperature is required to be 300 ° C. or higher. Organic substances that have volatilized by heating are quickly exhausted.

  In the case where the current collector foil 2 is a foil having a surface oxidation preventing layer such as a chromate treatment such as a copper foil, the current collector foil 2 is oxidized and the surface oxidized layer when the current collector foil 2 is heated at a temperature of 500 ° C. or higher. Therefore, the heating temperature is preferably 500 ° C. or lower.

  The mask 17 may be fixed. When the mask 17 is fixed, a mechanism for stopping the movement of the current collector foil 2 may be provided. FIG. 3 is a schematic view of an apparatus for heating the current collector foil 2 having a mechanism for fixing the mask 17 and stopping the movement of the current collector foil 2. As shown in FIG. 3, the current collector foil 2 that has entered the chamber 1 (B) at a speed of 1 cm / min is the auxiliary rolls 101, 102, 103, 104, 105, 106, 107, 14, 15, 108, It moves along 109,110,111,112,113,114. Each of the auxiliary rolls 101 to 114 moves in the left and right directions shown in FIG.

  The current collector foil 2 that has entered at a speed of 1 cm / min moves (feeds) the current collector foil 2 by moving the auxiliary rolls 101, 103, 105 to the right and moving the 102, 104, 106 to the left. The current collector foil 2 that accumulates and moves between the auxiliary rolls 14 to 15 stops. At this time, the auxiliary rolls 109, 111, 113 move to the left side, and the 110, 112, 114 move to the right side to release the movement (feed) of the accumulated current collector foil 2, and the current collector foil 2 is 1 cm / Exit from chamber 1 (B) at a rate of minutes.

  The current collector foil 2 that has entered at a speed of 1 cm / min moves (feeds) the accumulated current collector foil 2 as the auxiliary rolls 101, 103, 105 move to the left and the 102, 104, 106 move to the right. ) And move between the auxiliary rolls 14 to 15 at a speed of 25 cm / min. At this time, the auxiliary rolls 109, 111, and 113 move to the right side, and the movements (feeds) of the current collector foil 2 are accumulated by moving the 110, 112, and 114 to the left side, and the current collector foil 2 is 1 cm / min. Exit from chamber 1 (B) at speed.

<Active material formation process 1>
As a method of forming the active material film 39 on the current collector foil 2, there are a vacuum deposition method and a sputtering method. The internal structure of the chamber 1 shown in FIG. 2C is a schematic view of an apparatus for forming an active material film 39 by a vacuum deposition method. As shown in FIG. 2C, a plurality of auxiliary rolls 22, 23, 24, 27, a can roll 25, a mask 26, an evaporation source, a take-up roll 27,
An oxygen nozzle 28 is disposed. The evaporation source is configured by putting an evaporation material 30 in a carbon crucible 29 and is disposed in a water-cooled copper hearth 31. The evaporation source is heated by an electron beam (not shown), and it is desirable to use Si as the evaporation material 30. A vacuum pipe 32 is connected below the chamber 1 (C) and evacuated by an oil diffusion pump 33 and an oil rotary pump 34. The current collector foil 2 moves along the auxiliary rolls 22 and 23 and the can roll 25, and an active material film 39 is formed on the current collector foil 2 while the current collector foil 2 moves through the opening of the mask 26. To do. When vapor deposition is performed, the flow rate is controlled by the mass flow controller 36 from the oxygen gas cylinder 35 and the O 2 gas is introduced into the chamber 1 from the oxygen nozzle 28 according to the electrode design requirements. SiOx is formed as the material film 39. The current collector foil 2 on which the active material film 39 is formed moves along the auxiliary roll 24 and is finally wound on the winding roll 27.

  Note that Sn may be used as the evaporation material, and SnOx may be formed as the active material film 39.

<Organic substance coating process 2, heating process 2, active material formation process 2>
In order to form the active material film 39 on both sides of the current collector foil 2, the current collector foil 2 having the active material film 39 formed on one side is opened and taken out of the chamber 1, and the inside and outside of the winding are rewinded and unwound. Mount on roll 3. Thereafter, the organic material covering step 1, the heating step 1, and the active material forming step 1 are performed in the same manner.

<Active material removal process>
As an example of a method for removing the active material film 39 on the current collector foil 2, there is a method in which a tape is applied and peeled off. As shown in FIG. 4A, the current collector foil 2 on which the active material film 39 is formed is cut into a size of 200 mm × 50 mm to form an electrode 37. In the heating step and the heating step 2, an organic substance is left, and a tape of 50 mm × 10 mm is attached to a portion where the active material film 39 is formed (right side 50 mm × 10 mm shown in FIG. 4A). When the pressing tape is peeled off around the attached area, as shown in FIG. 4B, an electrode 37 from which the active material film 39 has been removed is obtained. Tapes such as silicone adhesives and acrylic adhesives can be used as the tape.

<Terminal joining process>
As a method for joining the terminal 38 to the electrode 37, there are an ultrasonic welding method and a spot welding method. In the case of the ultrasonic welding method, the electrode 37 and the terminal 38 can be joined by superimposing the terminal 38 on the part where the active material film 39 of the electrode 37 is peeled off and applying ultrasonic vibration by pressing with the head of the ultrasonic welding apparatus. In the case of the spot welding method, the terminal 38 is overlapped on the part where the active material film 39 of the electrode 37 is peeled off, inserted between the electrodes of the spot welding apparatus, and the electrode 37 and the terminal 38 are joined by flowing current while being sandwiched between the electrodes. it can.

(Process after terminal joining process)
When the electrode 37 with the terminal 38 obtained by the above process is a negative electrode, the electrode 37 is wound or laminated so as to face the positive electrode 40 with the separator 42 interposed therebetween. The electrode group 50 can be configured. The electrode group 50 is accommodated in the battery can 47 together with the electrolyte.

  The electrolyte includes a solvent and a solute that dissolves in the solvent. For example, in the electrolyte of a lithium secondary battery, a mixed solvent of a cyclic carbonate such as ethylene carbonate and a chain carbonate such as dimethyl carbonate is preferably used as a solvent, and lithium hexafluorophosphate, 4 fluorine as a solute. Lithium borate and the like are preferably used. The positive electrode 40 of the lithium secondary battery preferably contains LiCoO 2, LiNiO 2, LiMn 2 O 4 or the like as an active material.

  An example of the structure of a wound lithium secondary battery will be described with reference to the drawings.

  FIG. 5 is a schematic cross-sectional view of a wound lithium secondary battery according to the present invention. In FIG. 6, a strip-shaped positive electrode 40 and a negative electrode 41 composed of an electrode 37 are wound together with a strip-shaped separator 42 disposed between them and wider than both electrodes, thereby forming an electrode group 50. A positive electrode terminal 43 made of aluminum or the like is connected to the positive electrode 40, and one end thereof is connected to a sealing plate 48 in which an insulating packing 49 made of polypropylene or the like is arranged at the periphery. A negative electrode terminal 44 made of nickel or the like is connected to the negative electrode 41, and one end thereof is connected to a battery can 47 that houses the electrode group 50. An upper insulating ring 45 and a lower insulating ring 46 are disposed above and below the electrode group 50, respectively. The electrode group 50 is impregnated with an electrolyte (not shown) having lithium ion conductivity. The opening of the battery can 47 is closed with a sealing plate 48.

  In addition, batteries having various shapes such as a flat type and a square can be manufactured, and an excellent battery having a high capacity can be obtained.

  The organic substance used in the first embodiment of the present invention is a material that remains on the current collector foil 2 at 25 ° C. and a vacuum degree of 1E-2 Pa and inhibits the adhesion between the current collector foil 2 and the active material. In addition to the DEHP, DIDP (Diisodecyl Phthalate), DINP (Diisononyl Phthalate), and DBP (Dibutyl Phthalate) can be used. In addition, paraffin (alkane having 15 or more carbon atoms (chain saturated hydrocarbon represented by CnH2n + 2)) such as mineral oil can be used.

  The current collector foil 2 used in Embodiment 1 of the present invention has a surface roughness Ra of 0.5 μm or more and 3.0 μm or less in order to improve the adhesion with the active material film 39. Further, it is preferably 1.5 μm or more and 2.5 μm or less, and within this range, high adhesion can be obtained.

  EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited to a following example.

(Example)
Hereinafter, the manufacturing method of the electrode for lithium secondary batteries is demonstrated concretely.

  The inside of the chamber 1 (A) is evacuated to a vacuum degree of 1E-2 Pa, and on the roughened copper foil (surface roughness Ra = 2 μm, thickness 35 μm) manufactured by Furukawa Circuit Foil Co., Ltd. as the current collector foil 2, Organic coating was performed by vacuum deposition of DEHP as an organic material by a resistance heating method.

  The current collector foil 2 coated with organic matter was heated by a halogen lamp 18. Separately, the heating conditions were fixed by attaching a thermocouple to the current collector foil 2 and finding the output conditions of the halogen lamp 18 at a heating temperature of 350 ° C. During the heating, a stainless steel mask 17 was disposed so as to shield a part of the current collector foil 2 and heated with a halogen lamp 18.

  The detection of the presence or absence of DEHP on the roughened copper foil was separately performed using a heat extraction gas chromatography mass spectrometry method. A sample obtained by heating a roughened copper foil coated with DEHP at a vacuum degree of 1E-2 Pa at different temperatures was prepared, cut out, and subjected to thermal extraction gas chromatography mass spectrometry. As a result, DEHP was detected at 100 ° C. and 200 ° C., but not detected at 300 ° C. or higher. The boiling point of DEHP is 100 ° C. or less at a degree of vacuum of 1E-2 Pa, but could not be removed by heating at the boiling point. Presumably, it is physically or chemically adsorbed on the surface of the copper foil, and it is presumed that it can hardly be desorbed by heating at the boiling point. It is thought that it is necessary to heat until it exceeds the energy of adsorption.

  In the chamber (C) shown in FIG. 2, the current collector foil 2 moved along the auxiliary rolls 22 and 23, the can roll 25, and the auxiliary roll 24 at a speed of 1 cm / min, and was wound around the take-up roll 27. Si (purity 6N) manufactured by High-Purity Chemical Co., Ltd. is used as the evaporation material 30 and is placed in a carbon crucible 29. The crucible 29 is placed in the copper hearth 31 while being cooled, and an electron beam (not shown) ). The electron beam was output under the conditions of an acceleration voltage of -13 kV and an emission current of 1A. Oxygen was introduced in such a direction as to blow from the 100 sccm oxygen nozzle 28 onto the final conductor foil 2. When the current collector foil 2 passed through the opening of the mask 26, Si and O came on the current collector foil 2, and an SiOx film was formed as the active material film 39.

  The obtained SiOx film thickness was about 20 μm. The SiOx film formed on the current collector foil 2 was analyzed by ICP emission spectroscopic analysis for the amount of Si, and the amount of O was analyzed by the JIS Z2613 infrared absorption method. As a result, the molar ratio of O / Si representing x was 0.6. Met.

  The current collector foil 2 on which the SiOx film was formed was cut into a size of 50 mm × 200 mm as shown in FIG. Nomex adhesive tape No. made by Nitto Denko Co., Ltd. was formed on the end of the electrode plate 37 where the SiOx film was formed in advance leaving DEHP. 403FP (silicone adhesive) was pasted. After sufficiently adhering, the periphery of the tape was pressed and peeled off, and the SiOx film was peeled off. The opposite surface of the electrode plate 37 was similarly peeled off the SiOx film.

  As a result of observing the part of the electrode 37 where the SiOx film was peeled off and the part of the SiOx film which was peeled off with the tape attached thereto by SEM, it was found that the peeled place was the interface between the collector foil 2 and the SiOx film. Although there is a possibility that DEHP remains at the interface portion, the detection is difficult because the thickness is originally about a monomolecular film and the amount is small.

  Adhesiveness of the interface between the collector foil 2 and the SiOx film using a sample cut out from the place where the SiOx film was formed leaving DEHP and a sample cut out from the place where the SiOx film was formed after removing the DEHP Evaluated. A probe having an epoxy adhesive applied to a φ2 mm metal cylinder was bonded onto the SiOx film of the sample in which the DEHP was left to form the SiOx film and the sample in which the DEHP was removed and then the SiOx film was formed. From then on, it was pulled until it broke with a tensile testing machine. As a result, the sample in which the SiOx film was formed leaving DEHP was peeled off at the interface between the copper foil and the SiOx film at 10 kgf / cm2, and the epoxy adhesive was broken at 35 kgf / cm2 in the sample in which the SiOx film was formed after removing the DEHP. . Therefore, the adhesion strength between the copper foil and the SiOx film interface was 10 kgf / cm 2 for the sample in which the SiOx film was formed while leaving DEHP, and the sample in which the SiOx film was formed after the DEHP was removed was 35 kgf / cm 2 or more.

  As a result of attempting to join the electrode plate 37 and the terminal 38 by an ultrasonic welding method by superimposing the nickel-made terminal 38 on the exposed portion of the current collector foil 2 of the electrode plate 37, the electrode plate 37 was easily joined. As a result of measuring the bonding strength between the electrode plate 37 and the terminal 38 by pulling the terminal, the average tensile strength was 12N. Therefore, the bonding strength was sufficient.

  The method for producing an electrode for a lithium secondary battery of the present invention is particularly useful as a method for producing an electrode for a lithium secondary battery using an active material having a high capacity. The shape is not particularly limited, and can be applied to a lithium secondary battery using terminals such as a wound type and a laminated type.

Manufacturing process flow diagram of electrode for lithium secondary battery in Embodiment 1 of the present invention Schematic diagram of a lithium secondary battery electrode manufacturing apparatus according to Embodiment 1 of the present invention. Schematic diagram of a heating device with a mask fixed to a lithium secondary battery electrode manufacturing apparatus according to Embodiment 1 of the present invention. (A) Top view of lithium secondary battery electrode according to Embodiment 1 of the present invention, (b) Cross-sectional view Cross-sectional schematic diagram of a cylindrical lithium secondary battery according to Embodiment 1 of the present invention Outline diagram of mask 17

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Vacuum chamber 2 Current collector foil 3 Unwinding roll 4 Auxiliary roll 5 Auxiliary roll 6 Auxiliary roll 7 Mask 8 Vacuum piping 9 Oil diffusion pump 10 Oil rotary pump 11 Boat 12 Organic substance 13 Auxiliary roll 14 Auxiliary roll 15 Auxiliary roll 16 Auxiliary roll DESCRIPTION OF SYMBOLS 17 Mask 18 Halogen lamp 19 Vacuum piping 20 Oil diffusion pump 21 Oil rotary pump 22 Auxiliary roll 23 Auxiliary roll 24 Auxiliary roll 25 Can roll 26 Mask 27 Winding roll 28 Oxygen nozzle 29 Crucible 30 Evaporating material 31 Copper hearth 32 Vacuum piping 33 Oil Diffusion pump 34 Oil rotary pump 35 Oxygen gas cylinder 36 Mass flow controller 37 Electrode 38 Terminal 39 Active material film 40 Positive electrode 41 Negative electrode 42 Separator 43 Positive electrode terminal 44 Negative electrode terminal 45 Upper insulating ring 46 Lower insulating ring Ring 47 Battery can 48 Sealing plate 49 Insulating packing 50 Electrode group 91 Mask drive roll 92 Mask auxiliary roll 93 Mask auxiliary roll 94 Mask auxiliary roll 101 Auxiliary roll 102 Auxiliary roll 103 Auxiliary roll 104 Auxiliary roll 105 Auxiliary roll 106 Auxiliary roll 107 Auxiliary roll 108 Auxiliary roll 109 Auxiliary roll 110 Auxiliary roll 111 Auxiliary roll 112 Auxiliary roll 113 Auxiliary roll 114 Auxiliary roll

Claims (12)

A method of forming an inorganic thin film pattern on a metal substrate,
(A) The substrate having a first region in which an organic thin film containing one compound selected from phthalate ester and paraffin is formed on the substrate, and a second region in which the organic thin film is not formed The process of preparing
(B) forming an inorganic thin film on the first region and the second region of the substrate; and (c) removing the inorganic thin film formed on the first region of the substrate;
Forming an inorganic thin film pattern on a metal substrate having The step (a)
(A1) forming the organic thin film in the first region and the second region on the substrate;
(A2) A method of forming an inorganic thin film pattern on a metal substrate comprising: a step of removing the organic thin film by heating a second region on the substrate. The method for forming an inorganic thin film pattern on a metal substrate according to claim 2, wherein the heating temperature in the step (a2) is 300 ° C or higher. 2. The method of forming an inorganic thin film pattern on a metal substrate according to claim 1, wherein the step of forming the inorganic thin film in the step (b) is a vacuum deposition method. 2. The method for forming an inorganic thin film pattern on a metal substrate according to claim 1, wherein the step (b) is performed by a roll-to-roll method. 2. The method for forming an inorganic thin film pattern on a metal substrate according to claim 1, wherein the inorganic thin film does not contain a binder. The method for forming an inorganic thin film pattern on a metal substrate according to claim 1, wherein the metal substrate is a copper foil having a surface roughness Ra of 0.5 μm to 3.0 μm. The method of forming an inorganic thin film pattern on a metal substrate according to claim 1, wherein the organic thin film is a phthalate ester. 9. The method of forming an inorganic thin film pattern on a metal substrate according to claim 8, wherein the phthalate ester is DEHP. The method of forming an inorganic thin film pattern on a metal substrate according to claim 1, wherein the organic substance is paraffin. A method for producing an electrode for a lithium secondary battery, comprising:
(A) having a first region where an organic thin film containing one compound selected from phthalate ester and paraffin is formed on a current collector substrate, and a second region where the organic thin film is not formed Preparing the substrate;
(B) forming an active material thin film on the first region and the second region of the substrate; and (c) removing the active material thin film formed on the first region of the substrate;
The manufacturing method of the electrode for lithium secondary batteries which has this. 12. The method for producing an electrode for a lithium secondary battery according to claim 11, wherein the active material thin film contains SiOx (0 <x <2) as a main component.

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