KR102138273B1 - Electrode Repair Apparatus and Repair Method for All Solid Thin Film Batteries and Method for Manufacturing All Solid Thin Film Batteries - Google Patents

Abstract

An apparatus for repairing a product for an all-solid thin film battery according to an embodiment of the present invention includes a support for supporting a laminated structure including an electrode active material layer; An image inspecting unit that identifies an abnormal growth body formed on the electrode active material layer through an image of the surface of the electrode active material layer; And a laser irradiation unit to planarize the electrode active material layer by selectively removing the abnormal growth material identified by using a laser beam.

Description

Electrode Repair Apparatus and Repair Method for All Solid Thin Film Batteries and Method for Manufacturing All Solid Thin Film Batteries}

The present invention relates to an all-solid thin film electrode repair device and a repair method, and more specifically, an all-solid thin film electrode repair device for selectively removing and flattening abnormal growth formed on the electrode active material layer, a repair method using the same, and an all solid film It relates to a battery manufacturing method.

The all-solid thin film lithium secondary battery is a battery in which all the constituent materials are made of a solid material, and each constituent layer is made thin and thin. The all-solid thin film lithium secondary battery is composed of a positive electrode, an electrolyte, and a negative electrode, and is manufactured in a thickness of a micro unit on a thin substrate through deposition methods such as PVD and CVD. The all-solid thin film lithium secondary battery is a battery in which all the constituent materials are made of a solid material, and each constituent layer is made thin and thin. The positive electrode, electrolyte, and negative electrode of the all-solid thin film lithium secondary battery are manufactured to a thickness of micro units on a thin substrate through various deposition methods such as PVD and CVD. In particular, the positive electrode active material layer may be deposited by a PVD method such as sputtering. However, during the process of depositing the positive electrode active material layer, abnormal growth bodies are often formed, and these may generate a peeling phenomenon due to stress during a subsequent process such as a heat treatment process or an electrolyte deposition process. In addition, the thin electrolyte made thin and thin electrolytes, etc., suffer from a problem of yield reduction caused by the abnormal growth body, and the abnormal growth body that appears when the solid anode layer is formed is larger in size as the subsequent process progresses and solids on the anode. When depositing the electrolyte, a large abnormal growth body prevents the solid electrolyte layer from properly covering it, thereby causing short circuits, or even after fabrication, current concentration is deepened in the area to accelerate performance degradation. Can occur.

Patent Publication No. 10-2016-0095381

The present invention provides an all-solid thin film electrode repair device and repair method for flattening the electrode active material layer by selectively removing the identified abnormal growth material by checking the abnormal growth material formed on the electrode active material layer by an image-based inspection method.

The present invention provides a method of forming an all-solid thin film battery that is manufactured flat without an abnormal growth body by providing a repaired electrode active material layer.

Electrode repair apparatus for an all-solid thin film battery according to an embodiment of the present invention is a support for supporting a laminated structure including an electrode active material layer; An image inspecting unit that identifies an abnormal growth body formed on the electrode active material layer through an image of the surface of the electrode active material layer; And a laser irradiation unit to planarize the electrode active material layer by selectively removing the abnormal growth material identified by using a laser beam.

The laser irradiation unit may include a beam size adjusting unit for adjusting the size of the laser beam according to the size of the abnormal growth body.

The laser irradiation unit may further include a focus change optical unit provided on an optical path of the laser beam to focus out of the laser beam so as to deviate from the surface of the electrode active material layer.

The laser irradiation unit may further include a beam forming unit that shapes the laser beam into a rectangular laser beam.

The laser beam has a discontinuity in energy over time and may be irradiated to the abnormal growth body.

The image inspecting unit includes: an imaging unit that acquires an image of the surface of the electrode active material layer; A reference image storage unit that stores an image of an electrode active material layer made of uniform grain as a reference image; By comparing the picked-up image with the reference image, it is determined that the growth body included in the picked-up image is larger than the average grain size of the reference image or different from the average shape of the grain pattern appearing on the reference image to determine an abnormal growth body. It may include; a judgment unit.

The image inspection unit may further include an information acquisition unit that acquires at least one of location and size information of the abnormal growth body.

The electrode active material layer may be a positive electrode active material layer of lithium-based metal oxide.

The wavelength of the laser beam may be 300nm to 1500nm.

Electrode repair method for an all-solid thin film battery according to an embodiment of the present invention is to provide an electrode active material layer formed on the current collector; Identifying an abnormal growth body formed on the electrode active material layer; And a process of planarizing the electrode active material layer by selectively removing the identified abnormal growth material using a laser beam.

The flattening may include adjusting the size of the laser beam according to the identified size of the abnormal growth body; And irradiating the laser beam whose size has been adjusted to the abnormal growth body.

The planarizing process may include a process of out-focusing and irradiating the focus of the laser beam out of the electrode active material layer through a focus changing optical unit provided on the optical path of the laser beam.

The planarizing process may include forming the laser beam into a rectangular laser beam.

The process of checking the abnormal growth body may include: obtaining an image of a surface of the electrode active material layer; Setting an image of an electrode active material layer made of uniform grain as a reference image; Comparing the reference image and the captured image; And determining whether the growth body included in the captured image is larger than the average grain size of the reference image or different from the average shape of the grain pattern appearing on the reference image to determine the abnormal growth body.

The method may further include acquiring at least one of the identified location and size information of the abnormal growth body.

The electrode active material layer may be a positive electrode active material layer of lithium-based metal oxide.

A method of forming an all-solid thin film battery according to an embodiment of the present invention includes providing a positive electrode active material layer repaired by the repair method; Forming a positive electrode by heat-treating the positive electrode active material layer; Forming a solid electrolyte on the anode through a vapor deposition method; And forming a negative electrode on the solid electrolyte.

The electrode repair apparatus and repair method for an all-solid thin film battery according to an embodiment of the present invention can improve performance of an all-solid thin film battery by selectively removing an abnormal growth body formed on the electrode active material layer to planarize the electrode active material layer.

That is, the image of the electrode active material layer made of uniform grain is selected as a reference image and compared with the surface image of the electrode active material layer captured by the imaging unit, the growth body included in the captured image is larger than the average grain size of the reference image or By checking whether the difference in the average shape of the grain pattern appearing on the reference image is determined as the abnormal growth body, the location coordinates are determined, and the laser beam is irradiated to remove the abnormal growth body from the electrode active material layer to remove the electrode active material. The layer can be leveled.

In addition, by adjusting the size of the laser beam so that only the area with the identified abnormal growth body can be removed, only the abnormal growth body can be removed without affecting the electrode active material layer around the abnormal growth body, and the energy over time of the laser beam It is possible to remove the abnormal growth body by allowing the laser to be irradiated only to the abnormal growth body without affecting the surface of the electrode active material layer by irradiating the abnormal growth body for a short time by having a discontinuity.

In addition, by forming the shape of the laser beam into a square beam of a rectangular shape, the deposition surface on which the electrode active material layer is deposited minimizes the effect of the laser beam and prevents the difference in removal degree due to the energy difference of the irradiated laser beam. Even growth can be removed evenly. In addition, by providing a focus change optical unit on the optical path of the laser beam, the focus of the laser beam is out-focused so as to deviate from the surface of the electrode active material layer, and thus the energy of the laser beam affects only the abnormal growth body, thereby removing the abnormal growth body.

The method for manufacturing an all-solid thin film battery according to the present invention does not generate electrical short, peeling phenomenon, or decrease in yield of the battery due to the abnormal growth body by forming a solid electrolyte or the like on the repaired and flattened positive electrode active material layer, thereby improving the performance of the battery. It is possible to manufacture an improved all-solid thin film battery.

1 is a block diagram showing an electrode repair device for a solid thin film battery according to an embodiment of the present invention.
Figure 2 is an image showing an abnormal growth body of the electrode active material layer according to an embodiment of the present invention.
Figure 3 is an image showing the deposition of the electrode active material layer according to an embodiment of the present invention.
Figure 4 is a flow chart showing the electrode repair method for a solid thin film battery according to an embodiment of the present invention.
5 is a flow chart showing a method of manufacturing a solid thin film battery according to an embodiment of the present invention.
6 is an image showing a state in which a solid electrolyte is deposited on an abnormal growth structure according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various different forms, and only the present embodiments allow the disclosure of the present invention to be complete, and the scope of the invention to those skilled in the art is completely It is provided to inform you. In the description, the same reference numerals are assigned to the same components, and the drawings may be exaggerated in size in order to accurately describe the embodiments of the present invention, and the same reference numerals in the drawings refer to the same elements.

1 is a block diagram showing an electrode repair device for a solid thin film battery according to an embodiment of the present invention.

Referring to Figure 1, the electrode repair device for an all-solid thin film battery according to an embodiment of the present invention is a support 500 for supporting the stacked structure 100 including the electrode active material layer 130; An image inspection unit 200 for confirming an abnormal growth body 131 formed on the electrode active material layer 130 through an image of the surface of the electrode active material layer 130; And a laser irradiation unit 400 to planarize the electrode active material layer 130 by selectively removing the abnormal growth body 131 identified by using a laser beam L.

The support 500 serves to fix the stacked structure 100 including the electrode active material layer 130 so that it does not move, and the coordinates of the stacked structure 100 supported on the support 500 by moving the support 500 It can be placed on the image.

Here, the laminated structure 100 may be formed of a substrate 110, a current collector 120, and an electrode active material layer 130. The substrate 110 according to an embodiment of the present invention may be a mica sheet, a polyimide sheet, glass, a silicon wafer, etc., depending on its use. Among them, an mica sheet, a mica substrate 110 or a substrate 110 formed of a material containing mica may be used while being environmentally friendly and having excellent heat resistance and ductility. Mica may be applied with natural mica, and artificial mica may also be applied. Mica may be applied with natural mica, and artificial mica may also be applied. Mica, muscovite, lithium mica, light mica, etc. can be used. The current collector 120 serves to collect current generated from the electrodes of the all-solid thin film battery. The electrode active material layer 130 may be a positive electrode active material layer, and may be formed of various lithium metal oxides of several hundred nm to several tens of μm. LiCoO ₂ may be applied to the positive electrode active material layer according to the embodiment of the present invention.

The image inspecting unit 200 may check whether or not the abnormal growth body 131 formed on the electrode active material layer 130 is present. Specifically, the electrode active material layer (that is, the grain forming the electrode active material layer 130 is uniform) 130) Compare the reference image and the surface of the electrode active material layer 130 and the captured image captured by capturing the surface of the reference image and determine whether it is different from a preset condition, and whether the abnormal growth body 131 exists. In addition, it is possible to determine the location and size information of the region of the abnormal growth body 131 of the difference.

Here, the abnormal growth body 131 may be a grain having a shape larger than or equal to an average grain size among the grains forming the electrode active material layer 130. When depositing the electrode active material layer 130 on the current collector 120, the raw material can be converted into a vapor phase and deposited. The cause of the abnormal growth body 131 is the substrate constituting the stacked structure 100. When the foreign material 132 is present due to poor cleaning of the 110, the foreign material 132 acts as a growth nucleus so that an abnormal growth body can be grown around the foreign material 132. In addition, when the electrode active material layer 130 is deposited, it can be deposited through a PVD (physical vapor deposition method) or a CVD (chemical vapor deposition method). Particles generated from various shields in the chamber forming the electrode active material layer 130 An abnormal growth body 131 may be formed along the back, and a ceramic for deposition of the electrode active material layer 130 when deposited on the current collector 120 by sputtering to deposit the electrode active material layer 130 Under the influence of the foreign material 132 generated at the target, the abnormal growth body 131 may be generated when the electrode active material layer 130 is formed around the foreign material 132. The region in which the abnormal growth body 131 is generated may be convex upward or pointed in shape above the electrode active material layer 130, thereby convex than the electrode active material layer 130 formed when the solid electrolyte 140 or the like is deposited. Or by being formed on the pointed abnormal growth body 131, it may not be able to completely cover the abnormal growth body 131, or there may be a problem in that the all-solid thin film battery has a defect or a yield decreases due to its thin thickness. An all-solid thin film battery according to an embodiment of the present invention may be affected by small particles or foreign substances 132 as the all-solid electrode is formed in a thin film form. When a solid thin film electrode is formed on the abnormal growth body 131 grown around this particle or foreign material 132, the all-solid electrolyte 140 is not deposited flat and abnormal growth protruding more convex than the electrode active material layer 130 As the all-solid electrolyte 140 is not completely connected by the sieve 131 and is not deposited, it is deposited in a broken form, or as the deposited part becomes very thin, the stress is concentrated on the part after the heat treatment process or the subsequent process. As a result, peeling may occur, or the thin film electrolyte layer may not completely cover the abnormal growth body 131, resulting in electrical shorts and deterioration of the battery starting from the shorts.

The controller 300 checks the coordinates of the abnormal growth body 131 by analyzing the location and size information of the abnormal growth body 131 received from the image inspection unit 200, and the laser irradiation unit according to the size of the abnormal growth body 131 A signal capable of driving the 400 may be generated.

The laser irradiation unit 400 may flatten the electrode active material layer 130 by receiving a signal from the control unit 300 and irradiating and removing the laser beam L on the abnormal growth body 131 formed on the electrode active material layer 130. .

Here, when the planarization is performed by removing the laser beam L to the abnormal growth body 131, the region where the abnormal growth body 131 is removed based on the electrode active material layer 130 is similar to the electrode active material layer 130. The area that is removed in parallel or the abnormal growth body 131 is removed in the direction of the substrate 110 included in the stacked structure 100 so as to be completely flat without a height difference, and thus the electrode active material in the direction of the substrate 110 The height difference of the layer 130 may be caused. In addition, even if the abnormal growth body 131 is not completely removed and has a convex shape than the electrode cargo layer 130, when the solid electrolyte 140 is deposited, the solid electrolyte 140 cannot cover the abnormal growth body 131. Alternatively, the abnormal growth body 131 may be smoothly removed so that the thickness is not too thin. Even by depositing the solid electrolyte 140 on the electrode active material layer 130 by flattening in this way, the step is lowered to an aspect ratio when depositing the solid electrolyte 140 even if it is at least not convex or convex than the electrode active material layer 130. Step coverage can be deposited to produce an all-solid thin film battery to achieve even performance. Based on the surface of the electrode active material layer 130, it is removed so that it does not exist at a higher position than the surface of the electrode active material layer 130, or the abnormal growth body 131 is formed so that the abnormal growth body 131 is smoothly close to the surface of the electrode active material layer 130. The reason for the removal is that as described above, by shortening the aspect ratio, short-circuiting or peeling may occur when depositing the solid electrolyte 140 in the region where the abnormal growth body 131 is appropriately suitable for manufacturing an all-solid thin film battery having step coverage. This is to improve the performance of the all-solid thin film battery by solving the above problems by preventing it from occurring.

The laser irradiation unit 400 may include a beam size adjusting unit 410 for adjusting the size of the laser beam L according to the size of the abnormal growth body 131.

The beam size adjusting unit may adjust the size of the laser beam L according to the abnormal growth body 131. The size and shape of the abnormal growth body 131 may be different. In order to minimize the influence on the peripheral region of the different abnormal growth body 131, while irradiating the laser beam L only to the abnormal growth body 131 to remove it There is a need to adjust the size of the laser beam L. Here, since minimizing the influence on the surrounding area, since only the abnormal growth body 131 cannot be accurately removed when the abnormal growth body 131 is removed, the electrode active material layer 130 around the abnormal growth body 131 is laser beam. This is to prevent it from being removed when irradiating (L). For this purpose, various methods are used. Among them, one axis and the other axis intersect each other, and the size of the laser beam L is adjusted to control the size of the laser beam L by adjusting the size of the slit due to the adjustment of the intervals of the plurality of gap control parts provided on the one axis and the other axis, respectively. It can minimize that 130 is removed. The gap adjusting unit may be formed in multiple stages, and each gap adjusting unit may be moved to adjust the shape and size of the laser beam L according to the size or shape of the abnormal growth body 131. The method for minimizing the influence on the area around the ideal growth body 131 will be described below.

The laser irradiation unit 400 is provided on the optical path of the laser beam L, and the focus change optical unit for focusing the laser beam L out of focus so as to escape the surface of the electrode active material layer 130 ( 420); may be further included.

The focus change optical unit 420 may be provided on the optical path of the laser beam L to adjust the focus of the laser beam L. For example, the focus changing optical unit 420 may be a focus lens, and the focus of the laser beam L may be changed by moving the focus lens. In addition, the focus changing optical unit 420 includes a first lens (not shown) that corrects the size of the laser beam L, a second lens (not shown) that corrects a focus position, and a lens that can move the above lens A moving part (not shown) may be included, and in addition, an F-Theta lens may be further included. The F-Theta lens can generate an energy difference between the outer and middle regions due to the optical distortion phenomenon, which can be used to irradiate different energy depending on the distance. In addition, the surface of the electrode active material layer 130 is controlled by adjusting the focus of the laser beam L through the focus change optical unit 420 so that the focus of the laser beam L is not formed on the surface of the electrode active material layer 130. The damage of the laser beam L is irradiated only to the abnormal growth body 131 by allowing the focus of the laser beam L to be formed on the abnormal growth body 131 because it is not affected by the beam L. It is possible to remove the abnormal growth body 131.

The laser irradiation unit 400 may further include a beam forming unit 430 for forming the shape of the laser beam L into a rectangular shape laser beam L.

The beam forming unit 430 generally has an oscillated laser beam L having a Gaussian shape. The laser beam L of the Gaussian shape can be formed into a square beam having a flat upper square shape. By forming the Gaussian-shaped laser beam L into a square beam, the energy distribution of the square beam irradiated is formed into a square-shaped energy distribution having a flat shape, so that the energy of the laser beam L is not concentrated in one place but a certain area. By irradiating the energy of the laser beam (L), the difference in the degree of removal of the abnormal growth body 131 due to the energy difference can be reduced, and the surface of the electrode active material layer 130 can be prevented from being damaged. The square shape laser beam L may have a circular flat-top beam, a linear flat-top beam, or a square flat-top beam shape.

The laser beam L may be irradiated to the abnormal growth body 131 with energy discontinuity over time.

When the laser beam L is irradiated to the abnormal growth body 131 with energy discontinuity over time, high energy is irradiated to the abnormal growth body 131 in a relatively short time, thereby not affecting the surface of the electrode active material layer 130. Without being irradiated, only the abnormal growth body 131 is irradiated with energy, so that the abnormal growth body 131 can be removed. When the energy of the laser beam L is continuously irradiated in this way, when the laser beam L is irradiated to the abnormal growth body 131, the high energy of the laser beam L is reached only in a very thin thickness range. Since heat is not conducted around, energy can be irradiated only to the desired part, and energy may not be accumulated because energy is irradiated periodically for a short period of time. On the other hand, when the energy of the laser beam L is irradiated continuously, rather than discontinuously, the irradiated energy is continuously conducted to the surroundings, and heat can be removed to the part that is not desired to be removed. Therefore, a laser beam in which the energy of the laser beam L is discontinuously irradiated can be used. For example, the laser used in the electrode repair device for an all-solid-state thin film battery is a pulse laser, and the above-described effect can be obtained if the laser beam L has a pulse width and is output. The pulse width may range from nanoseconds to femtoseconds, and the shorter the pulse width, the more energy is not conducted around the electrode active material layer 130, and thus does not affect the energy of the laser beam L. ) Can be removed by irradiating the energy of the laser beam (L), and the smaller the pulse width, the more finely the laser beam (L) can be irradiated. As another example, a laser beam L is applied to the abnormal growth body 131 by blocking or passing the laser beam L by opening and closing the shutter by providing a shutter at a portion where the continuously emitted laser beam L is irradiated. When irradiated, energy can be irradiated with discontinuities. The laser beam L irradiated by opening and closing the shutter is irradiated with a wider pulse width than the pulse laser, and a laser beam L of a pulse shape similar to the pulse laser can be irradiated.

2 is an image showing the abnormal growth body 131 of the electrode active material layer 130 according to the embodiment of the present invention, and FIG. 3 is an image showing the deposition of the electrode active material layer 130 according to the embodiment of the present invention to be.

2 and 3, the image inspection unit 200 includes: an imaging unit 210 that acquires an image of a surface of the electrode active material layer 130; A reference image storage unit 220 that stores the image of the electrode active material layer 130 made of uniform grain as a reference image; By comparing the picked-up image with the reference image, it is determined whether the growth body included in the picked-up image is larger than the average grain size of the reference image or different from the average shape of the grain pattern appearing on the reference image. 131), the determination unit 230; may include.

The imaging unit 210 may acquire a surface image of the electrode active material layer 130 by imaging the surface of the electrode active material layer 130. The imaging unit 210 may be an image taken on the surface of the electrode active material layer 130 or may be an image captured at any moment in the image. In addition, the surface of the electrode active material layer 130 may be imaged in real time. The imaging unit 210 may entirely photograph the surface of the electrode active material layer 130, or may capture at least a portion of a plurality of divided shots in which the captured image is divided.

The reference image storage unit 220 may store an image of the electrode active material layer 130 made of uniform grain as a reference image. The uniform grain may be a grain having an average shape and size among grains formed when the electrode active material layer 130 is formed. At least a portion of the electrode active material layer 130 formed of a uniform grain may be picked up and selected as a reference image. Meanwhile, as a reference image, an image obtained by previously photographing the electrode active material layer 130 made of uniform grain may be selected as a reference image, and at least a part made of uniform grain among the portions where the electrode active material layer 130 is formed is a reference image. You can choose with.

The determination unit 230 compares the captured image with the reference image to determine whether the growth body included in the captured image is larger than the average grain size of the reference image or different from the average shape of the grain pattern shown in the reference image. A portion larger than the size or different from the average grain pattern may be determined as the abnormal growth body 131.

For example, the captured image is an image showing the entire electrode active material layer 130, and thus the abnormal growth body 131 can be identified by comparing the same area as the reference image. In addition, the abnormal growth body 131 may be identified by dividing the captured image into a plurality of shots and sequentially comparing the plurality of shots with a reference image. By comparing each of these, it is possible to check the abnormal growth body 131 formed on the electrode active material layer 130 over the entire area.

Referring to FIG. 2, it can be seen that the normal electrode active material layer 130 on the current collector 120 is formed in a columnar structure. On the other hand, the abnormal growth body 131 used the foreign material 132 as a growth nucleus to grow the growth nucleus direction in a preferential growth direction, and formed a columnar structure, but the angle formed with the electrode current collector 120 did not form a vertical growth. The abnormal growth body 131 grown in this way may be a major cause of reducing the performance of the battery when manufacturing an all-solid thin film battery.

Referring to Figure 3, the electrode active material layer 130 shows a top view grown with a columnar (Columnar) structure. The reference image can be selected based on the average grain size and shape shown in this top view. A portion different from the average grain size and shape can be judged as an abnormal growth body formed in the electrode active material layer.

The image inspecting unit 200 may further include an information acquiring unit 240 acquiring at least one of position and size information of the abnormal growth body.

The information acquisition unit 240 may acquire at least one of the location and size information of the abnormal growth body 131 identified by the determination unit 230. The acquired information is transmitted to the control unit 300, and the control unit 300 analyzes the transmitted information to control the support 500, the image inspection unit 200, and the laser irradiation unit 400 to control the abnormal growth body 131. The support 500 may be moved and positioned under the laser irradiation unit 400, and the size and intensity of the laser beam L may be controlled according to the size or shape of the abnormal growth body 131.

The electrode active material layer 130 may be a positive electrode active material layer of lithium-based metal oxide.

The lithium-based metal oxide according to an embodiment of the present invention may be LiCoO ₂ , Li[NiCoAl]O ₂ ,Li[NiCoMn]O ₂ , LiMn ₂ O ₄ , LifePO ₄ /C, or the like. The thickness of the deposited thin film can range from hundreds of nm to several tens of μm. The positive electrode active material oxide layer such as LCO may be first grown in a specific crystal direction among the crystal directions of the unit grid made of metal and oxygen. The presence or absence of the foreign material 132 on the current collector 120 as a base layer, the lower layer The abnormal growth body 131 can be relatively easily grown due to the crystal structure characteristics or process conditions of. In the positive electrode active material oxide layer, the abnormal growth body 131 may grow by using the above foreign substances as the growth nuclei, and accordingly, the positive active material layer has relatively more abnormal growth bodies 131 compared to other electrode constituent layers. There is a possibility to be. Therefore, the lithium-based metal oxide as described above can be repaired by an electrode repair device for an all-solid thin film battery according to an embodiment of the present invention to improve performance of the all-solid thin film battery. Meanwhile, the positive electrode active material layer may be formed of NCA, NCM, LMO, and LFP series positive electrode active material layers.

The wavelength of the laser beam L may be 300 nm to 1500 nm.

In the case of the positive electrode active material layer made of LCO or the like, when the wavelength of the laser beam L is 300 nm to 1500 nm, the absorption rate for the laser beam L is high, which may be advantageous when removing the abnormal growth body 131. When the wavelength is 300 nm or less, there is a possibility that the energy is relatively high and thus affects the electrode active material layer 130, not only the ideal growth body 131. When the wavelength is 1500 nm or more, the energy is too low to cause the abnormal growth body 131 to be laser. The beam L may not be absorbed and may not be removed.

4 is a flow chart showing a method for repairing an electrode for a solid thin film battery according to an embodiment of the present invention. Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the accompanying drawings, but the same or corresponding elements are assigned the same reference numbers regardless of the reference numerals, and overlapping descriptions thereof can be omitted or simply described. have.

Referring to Figure 4, the electrode repair method for an all-solid thin film battery according to an embodiment of the present invention is a process of providing an electrode active material layer 130 formed on the current collector 120 (S10); Checking the abnormal growth body 131 formed on the electrode active material layer 130 (S20); And selectively removing the abnormal growth body 131 identified using a laser beam L to planarize the electrode active material layer 130 (S30 ).

First, a process of providing the electrode active material layer 130 formed on the current collector 120 is performed (S10). The current collector 120 may be formed on the substrate 110, and the electrode active material layer 130 may be formed thereon. As an embodiment of the present invention, the electrode active material layer 130 may be a positive electrode active material layer, may be vapor-deposited, and may be formed by chemical vapor deposition or PVD using sputtering. At this time, in the process of providing the electrode active material layer 130, the abnormal growth body 131 may be formed on the electrode active material layer 130.

Next, a process of checking the abnormal growth body 131 formed on the electrode active material layer 130 is performed (S20).

The abnormal growth body 131 formed on the electrode active material layer 130 is compared with a reference image to determine whether a portion having a difference deviates from a preset condition and checks whether the abnormal growth body 131 is. The process of checking the abnormal growth body 131 may compare the image taken with the electrode active material layer 130 and the reference image as above, or compare the real-time image with the reference image to check the abnormal growth body 131.

Next, a process of planarizing the electrode active material layer 130 by selectively removing the abnormal growth body 131 identified using a laser beam L is performed (S30).

The abnormal growth body 131 is confirmed by checking the abnormal growth body 131 formed on the electrode active material layer 130 and removing the identified abnormal growth body 131 from the electrode active material layer 130 using a laser beam L. ) May flatten the electrode active material layer 130 in the region. As described above, planarization may be performed in parallel with the electrode active material layer 130 or flattened so that a height difference is formed with the electrode active material layer 130 in the direction of the current collector 120. In addition, the abnormal growth body 131 may be smoothly removed to convex upward so that a large difference in height from the surface of the electrode active material layer 130 does not occur. By flattening and repairing the electrode active material layer 130 in this way, it is possible to solve a problem occurring in the process of forming the solid electrolyte 140 to be described later on the electrode active material layer 130.

The flattening process may include adjusting the size of the laser beam L according to the identified size of the abnormal growth body 131; And irradiating the laser beam (L) whose size has been adjusted to the abnormal growth body (131).

The ideal growth body 131 is not the same size and may be formed in various shapes and sizes. Accordingly, when irradiating the laser beam L, it is necessary to adjust the shape and size of the laser beam L according to the abnormal growth body 131. The energy of the laser beam L is applied to the abnormal growth body 131 by irradiating the laser beam L whose shape and size is adjusted to the identified abnormal growth body 131 by adjusting the shape and size of the laser beam L. Can be concentrated and removed, and the electrode active material layer 130 can be reduced from being affected by the energy of the laser beam L.

In the planarization process, the focus of the laser beam L is out of the electrode active material layer 130 through the focus change optical unit 420 provided on the optical path of the laser beam L, and then irradiated. Process.

For example, the focus change optical unit 420 may include a focus lens, and as the focus lens is moved, the focus position of the laser beam L can be adjusted. Also, a first lens, a second lens, a lens shift unit, and an F-Theta lens may be included. Thus, the focus of the laser beam L is formed on the identified abnormal growth body 131 rather than on the surface of the electrode active material layer 130 so that the focus is not formed on the electrode active material layer 130. When focusing out, the focus of the laser beam L is formed on the abnormal growth body 131 so that the energy of the laser beam L is concentrated and the energy of the laser beam L reaches the surface of the electrode active material layer 130. The amount is reduced so that only the abnormal growth body 131 can be removed while minimizing the influence on the electrode active material layer 130.

The planarization process may include forming the laser beam L into a rectangular laser beam L.

As described above, a beam beam forming unit 430 is provided on a path of a laser beam L that is generally oscillated in a Gaussian shape, and a square beam irradiated by shaping the shape of the laser beam L into a square beam having a flat upper square shape The energy of the laser beam L is irradiated to a certain region rather than a form in which the energy of the laser beam L is concentrated in one place by forming an energy distribution in a square shape having a flat shape of the upper surface of the energy distribution of the laser beam L ) To reduce the difference in the degree of removal of the abnormal growth body 131 due to the energy difference, and to prevent the surface of the electrode active material layer 130 from being damaged. The square shape laser beam L may have a circular flat-top beam, a linear flat-top beam, or a square flat-top beam shape.

The process of checking the abnormal growth body 131 may include: obtaining an image of the surface of the electrode active material layer 130; Setting an image of the electrode active material layer 130 made of uniform grain as a reference image; Comparing the reference image and the captured image; And determining whether the growth body included in the captured image is larger than the average grain size of the reference image or different from the average shape of the grain pattern appearing on the reference image to determine the abnormal growth body 131. have.

In the process of acquiring an image of the surface of the electrode active material layer 130, an image is obtained by imaging the surface of the electrode active material layer 130 using the imaging unit 210. The captured image may be an image of the entire surface of the electrode active material layer 130 or may be composed of a plurality of shots obtained by dividing the entire surface of the electrode active material layer 130. This captured image may represent a collection of a plurality of grains constituting the electrode active material layer 130.

In the process of setting the image of the electrode active material layer 130 made of uniform grain as a reference image, the electrode active material layer 130 made of uniform grain can be found and the image is captured and set as a reference image. The uniform grain may be a grain having an average shape and size among grains formed when the electrode active material layer 130 is provided on the current collector. At least a portion of the electrode active material layer 130 formed of a uniform grain may be picked up and selected as a reference image. On the other hand, the reference image may be selected as an image in which the image of the surface of the electrode active material layer 130 made of a uniform grain in advance is selected as a reference image, or at least made of a uniform grain among portions of the image taken of the electrode active material layer 130 You can also select a portion of it as a reference image. Also, the electrode active material layer 130 may be compared with a real-time image and a reference image.

The process of determining whether the growth body included in the captured image is larger than the average grain size of the reference image or different from the average shape of the grain pattern shown on the reference image is determined as the abnormal growth body 131. By comparing the reference image, it is determined whether the growth body included in the captured image is larger than the average grain size of the reference image or different from the average shape of the grain pattern shown in the reference image, and is larger than the average grain size or different from the average grain pattern. The portion may be determined as the abnormal growth body 131. The average shape and size of the grain may be pre-determined. For example, the captured image is an image of the entire electrode active material layer 130, and thus the abnormal growth body 131 can be identified by comparing the same area with the reference image capturing a relatively partial area multiple times. Can. Also, the abnormal growth body 131 may be identified by dividing an image of the entire electrode active material layer 130 into a plurality of shots and sequentially comparing the plurality of shots with a reference image. By comparing the captured image and the reference image, the abnormal growth body 131 formed on the electrode active material layer 130 can be checked over the entire area.

The electrode repair method for an all-solid thin film battery may further include obtaining at least one of the identified location and size information of the abnormal growth body 131.

The location of the abnormal growth body 131 can be determined to obtain coordinate information, and after grasping the size of the abnormal growth body 131, the laser is irradiated with an abnormal growth body during the process of flattening the electrode active material layer 130 ( According to the size of 131), it is possible to obtain information capable of adjusting the size of the laser beam L. The obtained information may be transmitted to the control unit 300, and the control unit 300 analyzes the transmitted abnormal growth body 131 based on the information to transmit the laser irradiation unit 400, the image inspection unit 200, or the support 500. Control. In order to accurately remove the abnormal growth body 131, the support 500 is controlled so that the electrode active material layer 130 on which the abnormal growth body 131 is formed can be provided under the laser irradiation unit 400 to which the laser is irradiated, and received When the laser beam L is irradiated to the abnormal growth body 131 by controlling the size of the laser beam L according to the size information of the abnormal growth body 131, only the abnormal growth body 131 is exposed from the electrode active material layer 130. It can be controlled to be removed.

The electrode active material layer 130 may be a positive electrode active material layer of lithium-based metal oxide.

The lithium-based metal oxide according to an embodiment of the present invention may be LiCoO ₂ , Li[NiCoAl]O ₂ ,Li[NiCoMn]O ₂ , LiMn ₂ O ₄ , LifePO ₄ /C, or the like. The thickness of the deposited thin film can range from hundreds of nm to several tens of μm. The anode active material oxide layer such as LCO may be first grown in a specific crystal direction among the crystal directions of the unit grid made of metal and oxygen. The presence or absence of the foreign material 132 on the current collector 120 as a base layer, the lower layer The abnormal growth body 131 can be relatively easily grown due to the crystal structure characteristics or process conditions of. In the positive electrode active material oxide layer, the abnormal growth body 131 may grow by using the foreign material as the growth nucleus as described above, and accordingly, the positive active material layer may have a relatively large number of abnormal growth bodies 131 compared to other electrode constituent layers. There is a possibility. Therefore, the lithium-based metal oxide as described above can be repaired by an electrode repair method for an all-solid thin film battery according to an embodiment of the present invention to improve the performance of the all-solid thin film battery. Meanwhile, the positive electrode active material layer may be formed of NCA, NCM, LMO, and LFP series positive electrode active material layers.

5 is a flowchart illustrating a method of manufacturing a solid thin film battery according to an embodiment of the present invention. 6 is an image showing a state in which the solid electrolyte 140 is deposited on the abnormal growth structure according to the embodiment of the present invention. Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the accompanying drawings, but the same or corresponding elements are assigned the same reference numbers regardless of the reference numerals, and overlapping descriptions thereof can be omitted or simply described. have.

5 and 6, a method for forming an all-solid thin film battery according to an embodiment of the present invention includes providing a positive electrode active material layer repaired by the repair method (S100); Forming a positive electrode by heat-treating the positive electrode active material layer (S200); Forming a solid electrolyte 140 through vapor deposition on the anode (S300); And forming a negative electrode on the solid electrolyte 140 (S400).

First, a process of providing a positive electrode active material layer repaired by the repair method is performed (S100). The stacked structure 100 may form a current collector 120 on the substrate 110 and a positive electrode active material layer thereon. The abnormal growth material 131 formed on the positive electrode active material layer may be repaired by the electrode repair method for an all-solid thin film battery described above to provide a flat positive active material layer without the abnormal growth material 131.

On the other hand, the substrate 110 according to an embodiment of the present invention may be a mica sheet or the like according to its use. Among them, an mica sheet, a mica substrate 110 or a substrate 110 formed of a material containing mica may be used, which is eco-friendly and has excellent heat resistance and ductility. Mica, muscovite, lithium mica, light mica, etc. can be used. In order to minimize the occurrence of the abnormal growth body 131 when forming the positive electrode active material layer, it can be removed using dry cleaning using plasma and wet cleaning using chemicals to remove various impurities present in the substrate 110. have. In addition, an anode current collector may be formed on the cleaned substrate 110. Silver (Ag), gold (Au), platinum (Pt), palladium (Pd), aluminum (Al), nickel (Ni), copper ( Cu), titanium (Ti), chromium (Cr), iron (Fe), stainless steel, and Inconel may be used to form an anode current collector.

In addition, the positive electrode active material layer may be formed of various lithium metal oxides of several hundred nm to several tens of μm. The positive electrode active material layer according to an embodiment of the present invention may be LiCoO ₂ ,[NiCoAl]O ₂ ,Li[NiCoMn]O ₂ , LiMn ₂ O ₄ , LifePO ₄ /C, or the like.

Next, a process of forming a positive electrode by heat-treating the positive electrode active material layer is performed (S200).

The positive electrode active material layer can be vapor-deposited, and can be formed by a PVD method such as chemical vapor deposition or sputtering. The positive electrode active material layer thus formed has an amorphous phase. When the positive electrode active material layer has a crystalline phase rather than an amorphous phase, it may have excellent characteristics of an all-solid thin film battery. For this reason, a process of forming a positive electrode by converting the positive electrode active material layer having a non-cutting phase into a crystalline phase by heat treatment may be performed. Here, the heat treatment may be performed in a temperature range of about 400°C to 800°C. By performing the heat treatment, the area where the abnormal growth body 131 flattened by the electrode repair method for the all-solid thin film battery may grow to some extent, and thus, it is not restored in parallel with the positive electrode active material layer, but is restored to some extent to obtain a more flat anode. Can provide. In the process of forming the positive electrode according to the embodiment of the present invention, a heat treatment process may be performed such that the non-slicing positive electrode active material layer becomes a crystalline positive electrode, and after the heat treatment process, the above-described electrode repair method for an all-solid thin film battery is secondarily performed. Thereafter, the generated abnormal growth body 131 may be removed.

A process of forming the solid electrolyte 140 through the vapor deposition method is performed on the anode (S300).

The solid electrolyte 140 may be formed on the anode that has been repaired by an electrode repair method for an all-solid thin film battery and subjected to a heat treatment process through a vapor deposition method. The positive electrode repaired by the electrode repair method for an all-solid thin film battery and subjected to a heat treatment process is flattened by removing the abnormal growth body 131, and depositing a solid electrolyte 140 on the flattened positive electrode to form a thin solid electrolyte 140. The abnormal growth body 131 may not be connected, or the abnormal growth body 131 may not be completely covered, so that deposition can be performed without breaking. If a positive electrode is formed by heat treatment without removing the abnormal growth body 131 formed on the positive electrode active material layer by the electrode repair method for the all-solid thin film battery, the solid electrolyte 140 is formed on the positive electrode where the abnormal growth body 131 is not removed. When the solid electrolyte 140 in the region where the growth body 131 is present is very thin or does not completely cover the abnormal growth body 131, the abnormal growth body 131 is present when an all-solid thin film battery is manufactured by utilizing it later. An electrical short may occur from the region to be started or deterioration may occur around the point, which may cause a decrease in yield and performance of the all-solid thin film battery. In addition, when a heat treatment process or a subsequent process is performed, a stress may be concentrated in a region where the abnormal growth body 131 is present, such that the solid electrolyte 140 may be peeled off. Meanwhile, the chemical vapor deposition method according to the embodiment of the present invention may be PVD or CVD using sputtering, and the solid electrolyte 140 according to the embodiment of the present invention may be a LiPON thin film. It can be Li ₃ PO ₄ to be exact. Li ₃ PO ₄ may be deposited in an N ₂ atmosphere by high-frequency magnetron sputtering at room temperature, and the thickness may be greater than 0 μm to 5 μm.

Referring to FIG. 6, it can be seen that the solid electrolyte 140 is deposited on the abnormal growth body 131. The abnormal growth is achieved by depositing the solid electrolyte 140 on the anode where the abnormal growth body 131 is not removed. The solid electrolyte 140 in the region where the body 131 is located may be very thin or fail to completely cover the abnormal growth body 131, thereby deteriorating the performance of the all-solid thin film battery. As described above, when performing a heat treatment process or a subsequent process A stress may be concentrated on a portion of the abnormal growth body 131, and thus a phenomenon in which the solid electrolyte 140 is peeled off may appear.

Next, a process of forming a cathode on the solid electrolyte 140 is performed (S400).

In the process of forming the negative electrode on the solid electrolyte 140 according to the embodiment of the present invention, the negative active material layer is formed on the solid electrolyte 140 and is formed on the negative electrode active material layer using the electrode repair method for the all-solid thin film battery described above. The abnormal growth body 131 may be identified and removed. In addition, an amorphous anode active material layer may be formed as a crystalline anode through a heat treatment process.

The all-solid thin film battery manufactured by the above-described method for manufacturing the all-solid thin film battery has the abnormal growth body 131 formed on the positive electrode active material layer removed, thereby flattening the surface of the positive electrode active material layer, thereby causing the abnormal growth body 131 to undergo heat treatment or post-processing. Due to the peeling phenomenon, the yield of the battery and the concentration of the current in the abnormal growth body 131 is deepened, it is possible to solve problems such as deterioration of the performance of the battery and occurrence of defects in the battery. In addition, the abnormal growth body 131 is removed and planarized, thereby contributing to the large area of the all-solid thin film battery.

As described above, although specific embodiments have been described in the description of the present invention, various modifications are possible without departing from the scope of the present invention. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined not only by the claims described below, but also by the claims and equivalents.

100: laminated structure 110: substrate
120: current collector 130: electrode active material layer
131: abnormal growth body 132: foreign matter
140: solid electrolyte 200: image inspection unit
210: imaging unit 220: reference image storage unit
230: judgment unit 240: information acquisition unit
300: control unit 400: laser irradiation unit
410: beam size adjustment unit 420: focus change optics
430: beam forming unit 500: support
L: laser beam

Claims (17)

A support for supporting a laminated structure including an electrode active material layer;
An image inspecting unit that identifies an abnormal growth body formed on the electrode active material layer through an image of the surface of the electrode active material layer; And
It includes; a laser irradiation unit to planarize the electrode active material layer by selectively removing the abnormal growth material identified by using a laser beam;
The electrode active material layer is a positive electrode active material layer of lithium-based metal oxide,
The abnormal growth body is a grain having a different growth direction from other grains among the grains forming the electrode active material layer,
The laser irradiation unit,
A beam size adjusting unit configured to adjust the size of the laser beam according to the identified size of the abnormal growth body; And
It includes a beam forming unit for shaping a laser beam having a Gaussian-shaped energy distribution into a rectangular laser beam, thereby flattening the energy distribution of the laser beam,
The laser beam is an electrode repair device for an all-solid thin film battery in which energy over time has discontinuity and is irradiated to the abnormal growth body.
delete According to claim 1,
The laser irradiation unit,
And a focus change optical unit provided on an optical path of the laser beam and focusing the laser beam out of the surface of the electrode active material layer.
delete delete According to claim 1,
The image inspection unit,
An imaging unit acquiring an image of the surface of the electrode active material layer;
A reference image storage unit that stores an image of an electrode active material layer made of uniform grain as a reference image;
By comparing the picked-up image with the reference image, it is determined whether the growth body included in the picked-up image is larger than the average grain size of the reference image or different from the average shape of the grain pattern appearing on the reference image to determine an abnormal growth body. Electrode repair apparatus for an all-solid thin film battery comprising a determination unit.
The method of claim 6,
The image inspection unit,
Electrode repair apparatus for an all-solid thin film battery further comprising an information acquisition unit for acquiring at least one of the position and size information of the abnormal growth body.
delete According to claim 1,
Electrode repair apparatus for an all-solid thin film battery having a wavelength of the laser beam is 300nm to 1500nm.
Providing an electrode active material layer formed on the current collector;
Identifying an abnormal growth body formed on the electrode active material layer; And
The process of planarizing the electrode active material layer by selectively removing the identified abnormal growth body using a laser beam; includes,
The electrode active material layer is a positive electrode active material layer of lithium-based metal oxide,
The abnormal growth body is a grain having a different growth direction from other grains among the grains forming the electrode active material layer,
The planarization process,
Adjusting the size of the laser beam according to the identified size of the abnormal growth body;
Forming a laser beam having a Gaussian energy distribution into a rectangular laser beam so that the energy distribution of the laser beam is flattened; And
It includes the step of irradiating the laser beam is the size is adjusted and shaped to the abnormal growth body,
In the process of irradiating the laser beam to the abnormal growth body, the electrode repair method for an all-solid thin film battery that irradiates the laser beam so that energy with time becomes discontinuous.
delete The method of claim 10,
The planarization process,
And focusing and irradiating the focus of the laser beam out of the electrode active material layer through a focus changing optical unit provided on the optical path of the laser beam.
delete The method of claim 10,
The process of identifying the abnormal growth body,
Obtaining an image of the surface of the electrode active material layer;
Setting an image of an electrode active material layer made of uniform grain as a reference image;
Comparing the reference image and the captured image; And
And determining whether the growth body included in the captured image is larger than the average grain size of the reference image or different from the average shape of the grain pattern appearing on the reference image, thereby determining the abnormal growth body. Way.
The method of claim 10,
A method of repairing an electrode for an all-solid thin film battery, further comprising obtaining at least one of the identified location and size information of the abnormal growth body.
delete Providing a positive electrode active material layer repaired by at least any one of claims 10, 12, and 14 to 15;
Forming a positive electrode by heat-treating the positive electrode active material layer;
Forming a solid electrolyte on the anode through a vapor deposition method; And
The process of forming a negative electrode on the solid electrolyte; All solid film manufacturing method comprising a.

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