KR102159294B1 - Processing method of secondary battery separator using line-beam - Google Patents

Abstract

The present invention relates to a technique for processing a separator for a secondary battery to change the mechanical strength and thermal deformation characteristics of a separator by irradiating a beam to have a direction angle to a separator material of a porous polymer material in a vacuum environment and crosslinking a certain portion of a separator. A method for processing a separator for a secondary batter using a line beam according to the present invention comprises: a first step of generating processing control information for controlling electron beams emitted from first and second electron beam generators so that a separator material is disposed between the first electron beam generator and the second electron beam generator provided in a chamber and the beam generator corresponds to the material of the separator material and a position of a processing layer; and a second step of forming an electron beam density higher than an electron beam density of a surrounding area in a processing layer area since a beam control device controls the first and second electron beam generators based on the processing control information to irradiate first and second electron beams generated from the first and second electron beam generators to an inner layer of the separator material, respectively, and the first and second electron beams are irradiated to overlap each other in the processing layer area while focal positions of the first and second electron beams penetrate a processing layer set in the separator material and are located in the inner layer of the separator material.

Description

Processing method of secondary battery separator using line-beam}

The present invention relates to a separator processing technology for a secondary battery, by irradiating a concentrated line beam so as to have a direction angle to a separator material of a porous polymer material in a vacuum environment to crosslink a certain portion of the separator, thereby providing mechanical strength and thermal deformation characteristics of the separator. It's about technology that changes things.

As the 21st century enters, the market demand for secondary batteries is rapidly increasing due to the rapid high performance of wireless home appliances and information and communication equipment, and the development of large-capacity secondary batteries that can be applied to electric vehicles and power storage is actively progressing worldwide.

The characteristics generally required for a secondary battery are: First, since the battery must be installed in a limited space due to miniaturization, the energy density per volume must be large, and second, it must show excellent reversibility in terms of high power and charge/discharge. In addition, stability problems and shortening of lifespan at high temperatures must be solved.

In particular, lithium secondary batteries have a long charge/discharge life, high energy density, and low self-discharge rate, leading the market of small-sized secondary electricity, overtaking nickel hydride batteries, which were the mainstream of secondary batteries.

As shown in FIG. 1, the secondary battery is composed of an anode (1), a cathode (2), and a separator (3), and the inside is filled with an electrolyte (4).

This secondary battery can be used semi-permanently by repeating charging and discharging using an electrochemical reaction, and the separator 3 isolates the two electrodes in the secondary battery to block electrical short-circuit caused by physical contact, and A passage through which ions move between the two electrodes is provided through the electrolyte carried therein.

In addition, the separator 3 is required to have excellent mechanical strength to ensure durability of the secondary battery and high thermal stability to ensure the safety of the battery during abnormal driving such as overcharge or internal short circuit.

In general, the separator 3 is a porous membrane having pores of 1 μm or less, and in particular, a separator for lithium-ion batteries requires a thickness of 10-30 μm, a porosity of 30-60%, and a tensile strength of 100 MPa level.

In addition, a polyolefin polymer membrane is used as the material for the separator 3, and the separator is made of polyethylene (PE) to perform a shutdown function that prevents the movement of ions when the temperature rises rapidly in the secondary battery, and is made of polypropylene (PP). It is required to have high heat resistance.

Accordingly, the product 2325 of Cell Gard in the United States is composed of multi-layers of PP/PE/PP structure, so that mechanical strength is imparted to PP and the shut down temperature is controlled using PE.

In addition, in this regard, in Prior Document 1 (Korean Patent Publication No. 10-2017-0045438), a heat-resistant coating layer containing a heat-resistant inorganic filler and an organic polymer for heat sealing for adhesion between the electrode and the heat-resistant inorganic filler was additionally formed on a polyolefin-based porous substrate. And a separator for a secondary battery having an improved electrode adhesion function is disclosed.

In addition, in Prior Document 2 (Korean Patent No. 10-1027120), an organic/inorganic slurry containing inorganic particles, a polymer electrolyte, and a crosslinking agent is coated on a porous separator, and a porous organic/inorganic coating layer and a porous separator are used by irradiation with radiation. There is disclosed a configuration for providing an organic/inorganic composite membrane having an improved ionic conductivity of an electrolyte by increasing the chemical bonding strength with and improving peeling resistance and thermal stability, and forming appropriate pores in the organic/inorganic composite membrane.

That is, the product 2325 of cell gard in the United States, and Prior Document 1 and Prior Document 2 are all configured to have a multi-layered structure to provide different functions.

However, in the case of combining different layers or forming a coating layer to impart a function as described above, a high-temperature process must be performed to adhere to different materials, which may cause thermal deformation of the separator material.

Accordingly, efforts are being made to change the physical properties of electronic materials by using the existing electron beam accelerator.

However, conventional electron beam accelerators use hot filament to emit electron beams into the atmosphere through a 30-50 μm-thick titanium window, thereby processing the separation membrane, which has an acceleration energy of 30-50 μm titanium. It must have more than a certain amount of energy (electron acceleration energy) to emit it through the window and into the atmosphere. As a result, fine thickness control by voltage control is not possible, making it impossible to partially process a 10-50 μm thin separator, and thus shut down temperature control is not possible, so safe operation of the secondary battery is not guaranteed. In addition, since this process is carried out at atmospheric pressure, oxidation may occur on the surface of the polymer, and since the electron beam has a certain energy (electron density), it causes a decomposition action rather than a crosslinking action on the polymer, thereby lowering the thermal and mechanical properties. There is a problem that provides dysfunction.

1. Korean Patent Laid-Open Patent No. 10-2017-0045438 (Name: electrode adhesive coating separator for secondary battery and its manufacturing method) 2. Korean Patent Registration No. 10-1027120 (Name: manufacturing method of organic/inorganic composite membrane using irradiation and organic/inorganic composite membrane manufactured accordingly)

Accordingly, the present invention was created in view of the above circumstances, and by irradiating an electron beam so as to have a direction angle to the separator material of a porous polymer material in a vacuum environment to crosslink a certain part in the separator, thereby improving the mechanical strength in that part. In addition to the sikim, there is a technical purpose to provide a method for processing a separator for a secondary battery using a line beam that enables the shutdown function to be improved.

According to an aspect of the present invention for achieving the above object, a line beam for forming a processed layer having different ionization properties on the inner layer of the separator material by irradiating an electron beam to a separator material of a porous material having a thickness of several tens of μm in a chamber in a vacuum environment In the method of processing a separator for a secondary battery using, a separator material is disposed between a first electron beam generator and a second electron beam generator provided in a chamber, and the beam generator is prepared to correspond to the material of the separator material and the position of the processed layer. A first step of generating processing control information for controlling electron beams emitted from the first and second electron beam generating devices, and controlling the first and second electron beam generating devices based on the processing control information in the beam control device And irradiating the first and second electron beams generated by the second electron beam generating device to the inner layer of the separation membrane material, respectively, wherein the focal positions of the first and second electron beams penetrate the processed layer set in the separation membrane material and are positioned in the inner layer of the separation membrane material, Processing a separator for a secondary battery using a line beam, characterized in that it comprises a second step of forming an electron beam density higher than the surrounding area in the processed layer area by irradiating the first and second electron beams to overlap in the processed layer area A method is provided.

In addition, in the first step, there is provided a method of processing a separator for a secondary battery using a line beam, characterized in that the processed layer is set to an inner center or one side region of the separator material.

In addition, in a method of processing a separator for a secondary battery using a line beam in which an electron beam is irradiated to a separator material of a porous material having a thickness of several tens of μm in a chamber in a vacuum environment to form a processed layer having different ionization properties on the inner layer of the separator material, A separator material is disposed between the provided first electron beam generator and the second electron beam generator, and electron beams emitted from the first and second electron beam generators are transmitted from the beam generator to correspond to the material of the separator material and the position of the processed layer. A first step of generating processing control information for controlling, and first and second electron beam generating devices generated by the first and second electron beam generating devices by controlling the first and second electron beam generating devices based on the processing control information in the beam control device. The second electron beam is irradiated to the inner layers of both surfaces of the separator material, respectively, but the focal positions of the first and second electron beams penetrate the processed layer set in the separator material and are irradiated to be located in the inner layer of the separator material. 1 The processed layer is crosslinked in response to the first electron beam density, and the second processed layer set on the other side of the separator material is crosslinked in response to the second electron beam density. A method of processing a separator for a battery is provided.

In addition, at least two first electron beam generators are disposed on one side of the chamber, and at least two second electron beam generators are disposed on opposite sides of the first electron beam generator, and in the first step, the processed layer is It is set as a first region and a second region on both sides of the separator material, and in the second step, the beam control device controls two or more first electron beam generators to obtain two or more regions having different direction angles in the first region of the separator material. A line beam, characterized in that irradiation so that the first electron beams overlap, and by controlling two or more second electron beam generating devices to irradiate two or more second electron beams having different direction angles in a second region of the separator material to overlap each other. A method of processing a separator for a secondary battery is provided.

In addition, the first step includes an eleventh step of determining a dose corresponding to a crosslinking condition for a change in mechanical strength of a separator material, and a voltage level for generating an electron beam corresponding to the dose determined in the eleventh step. Step 12, Step 13 of obtaining an electron beam focal length corresponding to the voltage level set in Step 12, The focal position of the electron beam according to the focal length of the electron beam obtained in Step 13 passes through the processed layer area There is provided a method for processing a separator for a secondary battery using a line beam, characterized in that it comprises a fourteenth step of setting a direction angle of an electron beam so as to be positioned on an inner layer of a material.

In addition, there is provided a method for processing a separator for a secondary battery using a line beam, wherein the electron beam is irradiated with a separator material such that a central axis thereof has a direction angle of 45° or less with the surface of the separator.

In addition, the electron beam is irradiated with a separator material such that its central axis has a direction angle of 45° or less with the surface of the separator, and the direction angle is set smaller as the thickness of the separator material decreases. A method of processing a separator for a battery is provided.

In addition, it is configured to further include the step of forming a wetting layer on the surface of the separation membrane material by irradiating a first electron beam to the inner surface layer of one side of the separation membrane material, and the part where the wetting layer is formed is the electrolyte solution of the secondary battery and There is provided a method for processing a separator for a secondary battery using a line beam, characterized in that the contact is made.

In addition, it is configured to further include the step of forming a nano layer by depositing nanoparticles including TiO ₂ , Al ₂ O ₃ , and SiO ₂ on the surface of one side of the separator material in an aerosol method, and the nano layer is formed. There is provided a method of processing a separator for a secondary battery using a line beam, characterized in that it is connected to a silver negative electrode material to prevent the formation of dentrite on the surface of the negative electrode material.

In addition, a line beam, characterized in that it further comprises the step of forming an inorganic material including Al ₂ O ₃ and SiO ₂ using an ALD deposition using an electron beam or an aerosol method on both surfaces of the separator material. A method for processing a separator for a secondary battery using is provided.

In addition, in the interior of the chamber, first and second ion beam generators are additionally disposed on both sides of the separation membrane material, and the beam control device controls the first and second ion beam generators to control the first and second ion beam generators. There is provided a method of processing a separator for a secondary battery using a line beam, characterized in that it further comprises forming a roughness layer on both surfaces of the separator material by irradiating an ion beam to both surfaces of the separator material. .

According to the present invention, by irradiating an electron beam so as to have an directional angle on the separator material of a porous polymer material to crosslink a certain part in the separator, it is possible to improve the stability and efficiency of the secondary battery by improving the mechanical strength characteristics in the part.

In addition, by performing the separation membrane processing process in a chamber in a vacuum environment, it is possible to lower the heat shrinkage rate according to the separation membrane process.

In addition, by performing a wetting treatment on the surface in contact with the electrode, hydrophilicity and hydrophobicity can be improved, as well as forming a nano layer on the surface in contact with the negative electrode material to prevent the formation of dentrite from the surface of the negative electrode material. I can.

In addition, roughness may be formed on the surface of the separator to improve adhesion between the positive electrode material and the negative electrode material.

1 is a view schematically showing the internal configuration of a secondary battery.
2 is a view for explaining the configuration of a separator processing system for a secondary battery using a line beam according to the first embodiment applied to the present invention.
3 is a view for explaining the configuration of the first electron beam generating apparatus 100 shown in FIG.
4 is a view for explaining a method of processing a separator for a secondary battery using a line beam according to the present invention.
5 is a view for explaining in more detail the process control information generation process (ST200) shown in FIG.
6 to 9 are views for explaining in more detail the separation membrane processing process (ST300) shown in FIG.
10 and 11 are diagrams for explaining the configuration of a separator processing system for a secondary battery using a line beam according to a second embodiment applied to the present invention.

Since the embodiments described in the present invention and the configurations shown in the drawings are only preferred embodiments of the present invention, and do not represent all the technical spirit of the present invention, the scope of the present invention is limited to the embodiments and drawings described in the text. Should not be construed as limited by That is, since the embodiments can be variously changed and have various forms, the scope of the present invention should be understood to include equivalents capable of realizing the technical idea. In addition, since the object or effect presented in the present invention does not mean that a specific embodiment should include all of them or only those effects, the scope of the present invention should not be understood as being limited thereto.

All terms used herein have the same meaning as commonly understood by one of ordinary skill in the field to which the present invention belongs, unless otherwise defined. Terms defined in a commonly used dictionary should be construed as having the meaning of the related technology in context, and cannot be interpreted as having an ideal or excessively formal meaning that is not clearly defined in the present invention.

2 is a view for explaining the configuration of a separator processing system for a secondary battery using a line beam according to a first embodiment applied to the present invention. FIG. 2 is a separator for a secondary battery using a beam for processing the inner layer of the secondary battery separator. The configuration of the main parts of the processing system is schematically shown.

Referring to FIG. 2, the separation membrane processing system for secondary batteries using a beam applied to the present invention is disposed at a certain distance apart from one side of the separation membrane 10 for secondary batteries to be processed, and has directionality toward one side of the separation membrane 10 for secondary batteries. A first electron beam generator 100 for irradiating a line-shaped first electron beam, and a predetermined distance from the separator 10 for secondary batteries while facing the first electron beam generator 100 on the other side of the separator 10 for secondary batteries. A second electron beam generator 200 that is disposed to be spaced apart and irradiates a second electron beam in a line shape toward the separator 10 for a secondary battery, and a separator for a secondary battery in the first and second electron beam generators 100 and 200 ( 10) The first and second electron beam generators 100 and 200 are provided so that the focal positions of the first and second electron beams E1 and E2 irradiated to the side are located in the inner processed layer region without penetrating the separator 10 for secondary batteries. It is configured to include a line beam control device 300 to control.

The first and second electron beam generators 100 and 200 irradiate an electron beam to the separator 10 for secondary batteries to perform crosslinking in a certain area inside the separator 10 for secondary batteries, thereby changing physical properties in the corresponding region. Carry out processing.

At this time, the first and second electron beam generators 100 and 200 and the separator 10 for secondary batteries are installed in the chamber C in a vacuum state to perform processing on the separator 10 for secondary batteries, and the chamber C has A gas injection pipe for injecting gas and a gas exhaust pipe for exhausting the gas are provided. In addition, the first and second electron beam generators 100 and 200 may be configured in separate electron beam chambers, and the electron beam chamber is connected to a hole formed in the chamber C to inject or exhaust a process gas. An exhaust pipe may be provided.

In addition, the first and second electron beam generators 100 and 200 have the same configuration, and the first and second electron beam generators shown in FIG. 2 are shown in FIG. 2 by using the main configuration of the first electron beam generator 100 shown in FIG. The configuration of the electron beam generators 100 and 200 will be described.

Referring to FIG. 3A, the first electron beam generator 100 includes a cathode 110 and an anode 120, a cathode power supply unit 130 supplying power to the cathode 110, and an anode 120. It is configured to include an anode power supply unit 140 for supplying power, and the anode 120 is disposed below the cathode 110 to be separated by a predetermined distance.

At this time, the process gas is ionized by the voltage difference between the cathode 110 and the anode 120 while the process gas is introduced to form a plasma between the cathode 110 and the anode 120 or collide with the cathode 110 Generates electrons by For example, the cathode power supply 130 may apply a first negative voltage to the cathode 110, and the anode power supply 140 may apply a second negative voltage lower than the first negative voltage to the anode 120. In addition, the cathode power supply unit 130 may apply RF power to the cathode 110, and the anode power supply unit 140 may apply positive power to the anode 120.

In addition, electrons formed in the space between the cathode 110 and the anode 120 are emitted downward through the hole H of the anode 120, and the anode 120 has a plate shape in which a plurality of holes H are formed. The central line is configured to have a certain radius of curvature so that the focal position toward the electronic material 10 is formed, and the intensity of the electric field is configured such that the intensity of the electric field is highest in the center and the intensity of the electric field decreases from the center to the outside based on the center line of the plate . That is, as shown in Fig. 3D, an electron beam E1 having a line shape of a certain length is emitted toward the electronic material 10 side.

In this case, as a method of configuring the electric field strength of the anode 120 differently depending on the location, as shown in Fig. 3(B), the size of the hole H of the center line is made smaller, and as it goes outward from the center line, The size of the hole H can be set to be larger. In addition, various types of anode structures implemented in patent application No. 10-2018-019875 (line-type electron beam emission device) for which the inventors applied for a patent on October 8, 2018 may be applied, and detailed descriptions thereof will be omitted. .

That is, the gas ions ionized by the high voltage of the cathode 110 are distributed in a relatively wide space under the anode 120, and a smaller hole H is formed along the center line, thereby widening the electrode area. , As it passes through the hole (H) of the anode 120 according to the strength of the electric field, the direction is directed toward the center line having a large electric field strength, so that when secondary electrons are generated in the cathode 110, electrons can be more concentrated to the center line. have.

In addition, although not shown in FIG. 3(A), a grid electrode for speeding up the first electron beam E1 emitted from the anode 120 and a grid for supplying voltage to the grid electrode under the anode 120 A voltage supply may be additionally provided.

In addition, a heat medium such as an IR lamp may be provided on one side of the chamber C to promote polymer decomposition.

Next, a method of processing a separator for a secondary battery using a line beam having the above configuration will be described.

4 is a view for explaining a method of processing a separator for a secondary battery using a line beam according to the present invention.

Referring to FIG. 4, a separator material 11 having a thickness of 50 μm or less, for example 10 to 30 μm thick, is positioned between the first and second electron beam generators 100 and 200 disposed in the chamber C. In addition, the line beam control apparatus 300 receives basic information of the separation membrane including the material and thickness of the separation membrane material 11 and the processed layer region (position and thickness) (ST100). The basic information of the separation membrane may be input through an administrator or may be provided to the line beam control device 300 through an external terminal. Information on the processed layer area is processed based on the depth from one surface of the separation membrane material 11 applied from the outside to the surface of the processed layer area and the depth from the other surface of the separation membrane material 12 to the other surface of the processed layer area. It can be obtained by calculating the location and thickness of the layer.

The line beam control device 300 controls electron beams emitted from the first and second electron beam generators 100 and 200 to correspond to the material of the separator material 11 and the position of the processed layer 12 based on the basic information of the separator. For generating processing control information (ST200).

As shown in FIG. 5, the process control information generation process (ST200) corresponds to the material of the separation membrane material 11 and corresponds to the crosslinking condition required for the processed layer 12 of the separation membrane material 11. Determining a dose (ST210), setting a voltage level for emitting an electron beam corresponding to the dose (ST220), acquiring a focal length of an electron beam corresponding to the voltage level (ST230), and an electron beam And setting the direction angle of the electron beam so that the focal position of is properly dosed to the inner layer of the separation membrane material 11 while passing through the processed layer 12 in the separation membrane material 11 (ST240).

In this case, processing control information may be stored in advance in the line beam control device 300 in correspondence with basic information of different separation membranes. For example, an electron beam intensity (voltage level) corresponding to a dose amount for each separator material constituting the separator material 11 may be set.

In addition, the line beam control device 300 controls the first and second electron beam generators 100 and 200 based on the processing control information set in the ST200 step, thereby forming the processed layer 12 set in the separator material 11. By irradiating the first and second electron beams E1 and E2, the characteristics of the processed layer 12 inside the separation membrane material 11 are processed to be different from the material properties of the original separation material 1 (ST300).

That is, the line beam control device 300 is configured such that the central axes of the first and second electron beams generated by the first and second electron beam generators 100 and 200 have a direction angle of 45° or less with the surface of the separator material. And control to irradiate the second electron beam, wherein the focal positions of the first and second electron beams pass through the processed layer 12 set in the separation membrane material 11 and are set to be located in the inner layer of the separation membrane material. 12) Crosslink the area.

At this time, the separator material 11 may be made of polyolefin-based polyethylene (PE) or polypropylene (PP), which is a polymer material having a porous structure, and the first and second electron beams E1 and E2 are applied to the processed layer 12. By irradiating and crosslinking the processed layer 12 in response to the dose amount, the thermal and mechanical strength of the area of the processed layer 12 is enhanced.

In addition, in order to increase the dose, the intensity of the electron beam must be increased, and in order to increase the intensity of the electron beam, the voltage level for generating the electron beam must be set higher.

Next, the separation membrane processing process (ST300) shown in FIG. 4 will be described in more detail with reference to FIGS. 6 to 9.

In this embodiment, a process of forming the processed layer 12 in the center of the inner layer of the separator material 11 as shown in Fig. 6C to complete the separator 10 for a secondary battery will be described. For example, 20 to 100 KGY electron beams are superimposed on the separator material 11 having a thickness of 20 to 50 μm in the central 5 μm region of the separator material 11.

Referring to FIG. 6, the first and second electron beams E1 and E2 generated from the first electron beam generator 100 and the second electron beam generator 200 overlap in the processed layer 12 area. Crosslinking proceeds in response to the electron beam density. Accordingly, the central region in the separator is crosslinked, thereby enhancing mechanical and thermal properties.

At this time, the first and second electron beam generating apparatuses 100 and 200 correspond to the material and thickness of the separator material 11 and the processing type, and the characteristics of the process gas and the electron beam (beam direction angle, dose, focus position, voltage level, etc. ) Can be set differently. For example, depending on the position (depth) of the processed layer 12 in the separation membrane material 11, the beam voltage may be set in the range of 10 kV to 200 kV, and the beam current may be set in the range of 10 mA to 300 mA. In addition, the process gas may be used with one of CF ₄ , SF ₆ , O ₂ and Cl ₂ .

Here, the electron beam (E1/E2) is the depth from the surface of the separator material 11 for secondary batteries as shown in (D) of FIG. 6, with the focal position (F) set on the inner layer of the separator material 11 As a result, a difference occurs in the electron beam density, that is, the amount of dose (DOSE) that affects the material of the separator, and has the largest dose at the focal position (F) of the electron beam. In other words, the closer to the focal position (F) of the electron beam, the greater the dose. Since the dose of the first electron beam and the dose of the second electron beam are overlapped in the processed layer 12, which is an overlapping region, the dose is larger than that of the surrounding layer. Distribution. For example, when the maximum dose at the focal position of the first and second electron beams E1 and E2 generated by the first and second electron beam emitting devices 100 and 200 in FIG. 6C is "10", the processed layer as an overlapping portion In (12), a dose amount of about "18", which is approximately the sum of the dose amounts of the first and second electron beams, may be distributed, and a dose amount of approximately "3 to 4" may be distributed on both surfaces of the processed layer 12, respectively. Accordingly, a high dose is distributed only in the processed layer 12 of the separation membrane material 11 to modify the chemical chain structure of the processed layer 12, thereby changing the physical properties differently from the surrounding layers. In addition, it is possible to maintain or change the shut down temperature characteristic of the material itself because the dose amount lower than that of the processed layer 12 is distributed in the peripheral layer where the electron beam does not overlap according to the dose distributed around the processed layer 12. Do.

In addition, when the first and second electron beams are superimposed on the processed layer 12 and overdosed, a swell phenomenon occurs due to a reaction with the electrolyte in the secondary battery cell, and the gel ( GEL) state.

In addition, in the present invention, as shown in Fig. 6C, the electron beam is injected with the central axes C1 and C2 of the electron beam with a predetermined direction angle θ with respect to the surface of the separation membrane material 11.

Due to the characteristics of the electron beam, the intensity of the electron beam must be increased for a large dose, and the voltage for generating the electron beam must be set high in order to increase the intensity of the electron beam, and when the voltage is increased, the focal length of the electron beam is lengthened. ), the depth of penetration is increased, and in the present invention, the electron beam is transferred to the inner layer of the separation membrane material 11 so that the separation membrane material 11 has a beam direction angle θ of 45° or less, preferably in the range of 30° to 45°. By injecting, it makes it possible to allow longer focal length electron beams. Therefore, it is possible to process the separation membrane material 11 using an electron beam having a larger dose under the same conditions.

In addition, by setting a longer penetration range of the electron beam distributed in the processed layer 12 existing inside the separation membrane material 11 having a thickness of 10 to 20 μm, it is possible to easily set the focal position for the desired processed layer 12. have. In this case, as the thickness of the separator material 11 decreases, the beam direction angle θ of the electron beam injected into the separator material 11 for secondary batteries is set to be smaller.

In addition, as shown in Fig. 7 (E), when the electron beam having the same focal position penetrates perpendicularly to the separation membrane material 11, the electron beam region in the processed layer 12 corresponds to D1, but Fig. 7 ( As shown in F), when an electron beam penetrates with a certain beam direction angle to the separation membrane material 12, as the beam direction angle is lower, the electron beam region in the processed layer 12 becomes D2, which is wider than D1. Accordingly, in processing a thin film of 50 μm or less, preferably 20 μm or less, it is possible to more efficiently irradiate the thin film with an electron beam with a low thickness. In order to increase the electron beam scanning density, the voltage must be increased at the same time. However, it is difficult to precisely control the electron beam transmission depth when the electron beam is vertically incident on a thin surface of less than 5-10 um when the separator is crosslinked. In particular, in the cold cathode method using secondary electrons, it is particularly difficult to control the transmission depth of the electron beam, but this problem can be solved in the present invention.

In addition, when the processed layer 12 of the separation membrane material 11 needs to be processed with a high dose, it may be divided into multiple times to minimize thermal deformation, and the processing may be repeatedly performed. That is, the line beam control device 300 divides the intensity of the beam required for processing the separation membrane material 11 by a predetermined number, and controls the voltage level of the electron beam generators 100 and 200 to irradiate it by dividing it into a plurality of beam intensities. do. For example, when a 100KGY electron beam is required for processing, 50KGY electron beam processing may be performed twice, or 3 times processing may be performed with an electron beam of 30KGR, 30KGY, and 40KGY. In addition, the line line beam control device 300 sets the irradiation angle of the electron beam differently so that the focal position of the electron beam is the same every time the electron beam is irradiated. This solves the problem that the size of the chamber must be increased as the length to the focal position of the electron beam increases in response to the voltage level, and the length to the focal position increases as the separator 10 for secondary batteries has a thickness of 50 μm or less. I can.

At this time, by additionally providing a moving means for moving the positions of the first and second electron beam generators 100, 200 up, down, left, and right or moving the separator material 11 up, down, left and right, the focal position and irradiation angle of the electron beam are automatically adjusted. By changing, it is possible to perform a processing treatment on the region of the desired processing layer 12 in the separation membrane material 11.

FIG. 8 is a diagram illustrating a method of processing a separator for a secondary battery using a line beam according to the first embodiment of the present invention, and illustrates a method of processing the processed layer 12 using first and second electron beams.

Referring to FIG. 8, the processed layer 12 is formed on the central inner layer of the separator material 11 made of a porous material (G), or is formed in one region of the inner layer of the separator material 11 (H), or the separator material It may be formed on both sides of the inner layer of (11) (I,J).

In this case, (G) and (H) in FIG. 8 show that the first and second electron beams E1 and E2 are overlapped in one processed layer 12 area to form an electron beam density higher than that of the surrounding area, It increases the material properties, temperature properties, and mechanical strength of the processed layer 12.

That is, in the case of processing the separator material 11 having a thickness of 10 to 50 μm made of a polyolefin-based polyethylene (PE) and polypropylene (PP) material, which is a polymer material that is a molecular porous material in the structure (G) in FIG. 8, for example, By overlapping the 20~100KGY electron beam in the 5μm area of the center of the separator material 11, the density (dosage) of the electron beam is increased so that crosslinking is carried out intensively only at the center, thereby imparting tensile strength to the center of the separator and at the same time thermal By increasing the deformation temperature and minimizing the deformation on the surface layer of the separator, it is possible to prevent a short circuit by shutting down the secondary battery in the event of an external shock and excessive current and a sudden temperature increase inside the secondary battery.

In addition, (I) and (J) in FIG. 8 are processed layers (12-1, 12-2) formed on the inner layers of both sides of the separation membrane material 11, improving the mechanical strength of both sides of the separation membrane 10 It is the structure that I made. This may simultaneously process different processed layers 12-1 and 12-2 using the first and second electron beams E1 and E2.

In FIG. 8, (I) shows a first processed layer region set on one side of the separator material 11 by irradiating the first electron beam E1 and the second electron beam E2 to the inner layers of both surfaces of the separator material 11 respectively. 12-1) may be crosslinked corresponding to the first electron beam density, and the second processed layer region 12-2 set on the other side of the separator material 11 may be crosslinked corresponding to the second electron beam density. At this time, the first and second electron beams E1 and E2 are irradiated to satisfy different crosslinking conditions to form different heat resistance and mechanical strength characteristics of the first and second processed layer regions 12-1 and 12-2. It is possible.

In Fig. 8, (J) is a first processed layer in which a plurality of, for example, two first electron beams E1-1 and E1-2 having different directional angles are simultaneously overlapped in the area of the first processed layer 12-1. In addition to forming the electron beam density of the region 12-1 higher than that of the peripheral layer 11, a plurality of, for example, two second electron beams E2-1 and E2-2 having different directional angles are simultaneously second By overlapping in the processed layer 12-2 region, the electron beam density of the second processed layer 12-2 may be formed higher than that of the peripheral layer 11. At this time, in the chamber (C), at least two or more first electron beam generators are disposed on one side of the separator material 11 to be spaced apart by a predetermined distance, and at least two or more second electron beam generators are disposed on the other side of the separator material 11 They are arranged spaced apart.

Meanwhile, in the present invention, as shown in FIG. 8, an additional process for improving the characteristics of the separator may be performed using an electron beam in the separator structure for a secondary battery in which the processed layer 12 is processed.

9 illustrates an additional process for the separator 10 for a secondary battery in which the processed layer 12 is formed. 9 illustrates a separator 10 for a secondary battery having a structure in which a processed layer 12 is formed in the middle of the separator material 11, but as shown in (H), (I) and (J) of FIG. As a matter of course, the same can be performed for the structure of the separator 10 for a secondary battery in which the processed layers 12 are formed on one or both sides of the separator material 11.

In Figure 9 (K), a secondary wetting layer 13 is formed by modifying the surface to have hydrophilic and hydrophobic properties by using an electron beam on the inner layer of one surface of the separator material 11 in contact with the cathode material. A separator 10 for a battery is shown.

For example, the hydrophilic reforming treatment may be performed to improve the transfer efficiency of hydrogen ions on one surface of a hydrogen fuel cell, and a separation membrane material made of a fluorine-based resin by irradiating an electron beam in the range of 20 to 100 KGy to have a predetermined beam direction angle (11 ) By inducing a molecular change in a certain portion of the surface of one side of the), the corresponding region can be modified to be hydrophilic/hydrophobic. As a result of performing a hydrophilicity test on a separator for secondary batteries made of a fluorine resin, the present inventors found that the contact angle was improved from 82 degrees to 55 degrees by cutting of the CF system of the fluorine resin, thereby increasing the hydrophilicity. In particular, in the case of performing hydrophilic reforming treatment using O ₂ as a process gas in a vacuum, the carbon component on the surface of the separation membrane material 11 and O ₂ react to form a "CO-" group (chain), thereby hydrophilic modification It is easier than this. This increases the conductivity of ions by facilitating absorption and passage of ions in the electrolyte solution through the separator, thereby improving the efficiency of the secondary battery.

9(L) shows a separator 10 for a secondary battery in which inorganic layers 14 are additionally formed on both surfaces of the separator material 11.

The inorganic layer 14 is formed by coating an inorganic material of a ceramic component including Al ₂ O ₃ or SiO ₂ , and using an ALD (atomic layer deposition) deposition method using an electron beam or an aerosol method is used to form ceramics, especially Al ₂ O _3. Can be deposited.

Here, the ALD deposition method decomposes a process gas such as TMA or H ₂ O using an electron beam, and the deposition process proceeds at a low temperature, thereby eliminating a thermal burden on the surface of the separator. That is, the ALD deposition method can secure a thickness of 1 to 2 μm by repeatedly performing a number of deposition and purging processes using TMA or H ₂ O.

This requires a high temperature environment for TMA or H ₂ O decomposition in the case of depositing a few nano (nm) to tens of nano (nm) Al ₂ O ₃ on both surfaces of a separator material using a plasma or heat source in a conventional vacuum environment. As a result, there is a problem of thermal deformation of the separator material, but in the present invention, it is possible to deposit Al ₂ O ₃ having a thickness of several tens of nm at a low temperature by decomposing gas molecules of the process gas using an electron beam. Accordingly, Al ₂ O ₃ ALD deposition without a thermal burden on the surface of the separation membrane is possible, and by simultaneously irradiating an electron beam to the separation membrane, the bonding strength between the thin film and the separation membrane can be increased.

In the aerosol method, a fine ceramic film of 100 nm or less is applied in the vacuum chamber C by applying vacuum pressure to coat ceramic on the surface of the separator. When the inorganic layer 14 is coated, it may be TMA, H ₂ O, SnO ₂ , TiO ₂ or the like, and at least one of these materials may be used.

In addition, in the present invention, the electron beam is irradiated toward the separator 10 for secondary batteries to increase the adhesion between the ceramic and the precursor (PRECUSOR) and the separator, and a trace amount of polyvinylidene fluoride, styrene butadiene rubber (SBR), etc. An organic layer may be further deposited by adding a binder.

At this time, it is possible to simultaneously perform the crosslinking process and the bonding process at a low temperature by simultaneously irradiating the processed layer and the surface layer of the separation membrane using different electron beams having different focal positions.

9(M) shows a separator 10 for a secondary battery in which roughness layers 15 are additionally formed on both surfaces of the separator material 11.

In general, since the separator 10 for a secondary battery is disposed between a positive electrode material and a negative electrode material, roughness processing may be additionally performed on surfaces in contact with the positive electrode material and the negative electrode material.

That is, by increasing the contact area by making the surface of the separator 10 for a secondary battery rough, it is possible to increase adhesion and reduce contact resistance when bonding the positive electrode material and the negative electrode material to both sides of the separator.

FIG. 10(N) shows a separator 10 for a secondary battery in which a nano-layer 16 is additionally formed on a side of the separator material 11 in contact with the negative electrode material.

That is, nanoparticles such as titanium oxide (TiO ₂ ) or Al ₂ O ₃ , SiO ₂ are coated on one surface of the separator material 11 in a vacuum chamber in an aerosol method. By arranging the nano-layer 16 on which nanoparticles such as TiO ₂ , Al ₂ O _{3 and} SiO ₂ are deposited to face the cathode layer of lithium metal, the formation of dentrite on the surface of the anode layer is prevented and secondary battery The efficiency and stability of the product can be secured. In addition, Mg nanoparticles are deposited on one surface of the separator material 11 to change to a lithiophilic state, thereby forming an ionic redistribution layer of lithium metal, thereby reducing the distribution of litum ions at the electrode. It may interfere with the formation of the resulting dentrite.

At this time, by applying a solid ceramic electrolyte to glassy and garnet-shaped inorganic materials, it is located before or after the electrolyte to prevent dendrite from growing in the solid electrolyte, and the galvanized separator part is filled. It is possible to increase contact resistance and ion conductivity by ensuring contact with an electrode that contracts and expands during discharge.

Here, the roughness layer 15 may be additionally applied to the structure of the separator 10 for a secondary battery such as (K) or (L) or (N) of FIG. 9, and also, the wetting layer 13 and the inorganic The roughness layer 15 may also be applied to the separator 10 for secondary batteries in which at least two or more layers of the layer 14 and the nano layer 16 are formed.

In addition, the roughness layer 15 process described above in the present invention is not limited to using an electron beam, and may be performed using an ion beam, as a process on the surface of the separator 10 for a secondary battery.

That is, since the ion beam cannot be injected into the inner layer of the separator material 11 because its size is larger than that of the electron beam, it can be used in a process for the surface layer of the separator material 11.

In addition, in the present invention, the separator surface is coated with a polymer polymer such as polyvinylidene fluoride, polyethylene oxide (PEO), polypropylene oxide (PPO), polymethyl grate (PMMA), etc. After the electron beam treatment, a process of increasing the intensity may be added.

FIG. 10 is a view for explaining the configuration of a separation membrane processing system for a secondary battery using an ion beam that performs surface layer processing of the separation membrane material 11, and the same reference numerals are assigned to configurations that perform the same functions as in FIG. Description is omitted. Preferably, the first and second ion beam generators 500 and 600 are provided in the chamber C in which the first and second electron beam generators 100 and 200 shown in FIG. 2 are provided, and one line beam control device 300 ) Through the electron beam and ion beam generation can be controlled.

Referring to FIG. 10, a system for processing a separator for a secondary battery using an ion beam includes a first ion beam generator 500 for irradiating a first ion beam I1 toward the separator 10 for a secondary battery, and the first ion beam generator 500. ) And irradiating a second ion beam (I2) in the form of a line toward the separator 10 for a secondary battery while facing the second ion beam generator 600, and a separator for a secondary battery ( It is configured to include a line beam control device 300 for controlling the first and second ion beams (I1, I2) irradiated to the side 10).

In addition, the first and second ion beam generators 500 and 600 have the same configuration, and by using the main configuration of the first ion beam generator 500 shown in FIG. Describe the configuration.

Referring to FIG. 11(O), the first ion beam generator 500 supplies power to the cathode 510 and the anode 520 and cathode 510 disposed at a predetermined distance from the lower side of the cathode 510 A cathode power supply unit 530 and an anode power supply unit 540 supplying power to the anode 520 are included.

The cathode power supply 530 applies RF power to the cathode 510, and the anode power supply 540 applies a negative voltage to the anode 520. For example, the cathode power supply unit 530 applies 0.5 to 20 kW of RF power to the cathode 510, and the anode power supply unit 540 applies a negative voltage of 100 to 1,000 kV to the anode 520.

That is, when the first ion beam generator 500 is supplied with a certain level of RF power to the cathode 510 in a state in which the process gas is introduced, and when a negative voltage is applied to the anode 520, the cathode 510 and the anode The process gas is ionized between 520 to form a plasma, and ions on the plasma are drawn by the anode 520 due to the voltage difference between the cathode 510 and the anode 520, and an anode hole H formed in the anode 520 It is emitted to the electronic material 10 side through.

At this time, the anode 520 is an insulating layer having a predetermined thickness between the first and second metal layers 521 and 522 in a plate shape having a size corresponding to the cathode 510, as shown in FIG. 11P. While being configured to form 523, the central line is configured to have a predetermined radius of curvature so that the focal position toward the electronic material 10 is formed, so that ions on the plasma are concentrated and released in a line shape corresponding to the center line. In addition to the anode 520, various types of anode structures implemented in Patent Application No. 10-2018-0161915 (line type ion beam emission device) for which the inventor applied for a patent on December 14, 2018 may be applied. Detailed description of this will be omitted.

In addition, although not shown in FIG. 11(O), a grid electrode for speeding up the first ion beam I1 emitted from the anode 520 and a grid for supplying a voltage to the grid electrode under the anode 520 A voltage supply may be additionally provided.

On the other hand, in the present invention, it is also possible to include at least two or more line beam generating devices on both sides of the separator 10 for secondary batteries.

For example, first and second electron beam generators are provided on one side of the separator 10 for secondary batteries, and third and fourth electron beam generators are provided on the other side of the separator 10 to have different beam direction angles at different positions. By generating an electron beam, it can be configured to simultaneously perform a crosslinking process and an additional process (see Fig. 9) for the processed layer 12.

In addition, based on the separator 10 for a secondary battery, a first electron beam generator and a first ion beam generator are provided on one side, and a second electron beam generator and a second ion beam generator are provided on the other side, and the processed layer 12 It may be configured to simultaneously perform a crosslinking process and a roughness process for.

100, 200: electron beam generator, 500, 600: ion beam generator,
300: line beam control device,
10: separator for secondary battery, 11: separator material,
12: processed layer, 13: wetting layer,
14: inorganic layer, 15: roughness layer,
16: nano layer,
C: chamber, E: electron beam,
I: ion beam, F: focal position,
θ: direction angle.

Claims (11)

In a method for processing a separator for a secondary battery using a line beam in which an electron beam is irradiated to a separator material of a porous material having a thickness of several tens of μm in a chamber in a vacuum environment to form a processed layer having different ionizing properties on the inner layer of the separator material,
A separator material is disposed between the first electron beam generator and the second electron beam generator provided in the chamber, and the beam generator is emitted from the first and second electron beam generators so as to correspond to the position of the material and the processed layer of the separator material. A first step of generating processing control information for controlling the electron beam,
The beam control device controls the first and second electron beam generators based on the processing control information to irradiate the first and second electron beams generated by the first and second electron beam generators to the inner layer of the separation membrane material, respectively, And an electron beam density higher in the processed layer area than in the surrounding area by irradiating the first and second electron beams to overlap in the processed layer area while the focal position of the second electron beam penetrates the processed layer set in the separation material and is located in the inner layer of the separation material. Method for processing a separator for a secondary battery using a line beam, characterized in that it comprises a second step to form a.
The method of claim 1,
In the first step, the processing layer is set to an inner center or one side region of the separator material. A method of processing a separator for a secondary battery using a line beam.
In a method for processing a separator for a secondary battery using a line beam in which an electron beam is irradiated to a separator material of a porous material having a thickness of several tens of μm in a chamber in a vacuum environment to form a processed layer having different ionizing properties on the inner layer of the separator material,
A separator material is disposed between the first electron beam generator and the second electron beam generator provided in the chamber, and the beam generator is emitted from the first and second electron beam generators so as to correspond to the position of the material and the processed layer of the separator material. A first step of generating processing control information for controlling the electron beam,
The beam control device controls the first and second electron beam generators based on the processing control information to irradiate the first and second electron beams generated from the first and second electron beam generators to the inner layers of both surfaces of the separation membrane material, respectively. , By irradiating so that the focal positions of the first and second electron beams penetrate the processed layer set in the separation membrane material and are located in the inner layer of the separation membrane material, the first processed layer set on one side of the separation membrane material is crosslinked corresponding to the first electron beam density, and the separation membrane A method of processing a separator for a secondary battery using a line beam, characterized in that the second processed layer set on the other side of the material comprises a second step of crosslinking in response to a second electron beam density.
The method of claim 3,
At least two first electron beam generators are disposed on one side of the chamber, and at least two second electron beam generators are disposed on opposite sides of the first electron beam generator,
In the first step, the processed layer is set as a first region and a second region on both sides of the separator material,
In the second step, the beam control device controls two or more first electron beam generators to irradiate two or more first electron beams having different directional angles to overlap each other in the first region of the separation membrane material, and at least two second electron beams. A method for processing a separator for a secondary battery using a line beam, characterized in that by controlling a generator to irradiate two or more second electron beams having different direction angles to overlap in a second region of the separator material.
The method according to any one of claims 1 to 4,
The first step includes an eleventh step of determining a dose corresponding to a crosslinking condition for a change in mechanical strength of the separator material,
A twelfth step of setting a voltage level for generating an electron beam corresponding to the dose determined in the eleventh step,
A thirteenth step of obtaining an electron beam focal length corresponding to the voltage level set in the 12th step,
And a 14th step of setting the direction angle of the electron beam so that the focal position of the electron beam according to the focal length of the electron beam obtained in the 13th step passes through the processed layer region and is positioned in the inner layer of the separation membrane material. Separator processing method for secondary batteries using.
The method according to any one of claims 1 to 4,
The electron beam is irradiated with a separator material such that a central axis thereof has a direction angle of 45° or less with the surface of the separator. A method of processing a separator for a secondary battery using a line beam.
The method according to any one of claims 1 to 4,
The electron beam is irradiated with a separator material so that its central axis has a direction angle of 45° or less with the surface of the separator,
The direction angle is a method of processing a separator for a secondary battery using a line beam, characterized in that the smaller the thickness of the separator material is set to be smaller.
The method according to any one of claims 1 to 4,
And forming a wetting layer on the surface of the separator material by irradiating a first electron beam to the inner surface layer of one side of the separator material,
A method of processing a separator for a secondary battery using a line beam, characterized in that the part where the wetting layer is formed is in contact with the electrolyte solution of the secondary battery.
The method according to any one of claims 1 to 4,
And depositing nanoparticles including TiO ₂ , Al ₂ O ₃ , and SiO ₂ on the surface of one side of the separator material in an aerosol method to form a nano layer,
A method of processing a separator for a secondary battery using a line beam, characterized in that the portion where the nano-layer is formed is connected to the negative electrode material to prevent the formation of dentrite on the surface of the negative electrode material.
The method according to any one of claims 1 to 4,
Secondary using a line beam, characterized in that it further comprises the step of forming an inorganic material including Al ₂ O ₃ and SiO ₂ using an ALD deposition using an electron beam or an aerosol method on both surfaces of the separator material. Battery separator processing method.
The method according to any one of claims 1 to 4,
Inside the chamber, first and second ion beam generators are additionally disposed on both sides of the separation membrane material,
The beam control device controls the first and second ion beam generators to irradiate the first and second ion beams to both surfaces of the separation membrane material, thereby forming a roughness layer on both surfaces of the separation membrane material. Method for processing a separator for a secondary battery using a line beam, characterized in that it is configured to further include.

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