Method and device for creating multi-single-beam in multi-single-mode from single-beam in single-mode, multi-single-beam generated thereby, method for measuring multi-single-beam, and rechargeable battery welded using said multi-single-beam

Abstract

Provided is a device for creating a multi-single-beam in multi-single-mode from a single-beam in single-mode. The device includes: an incident fiber on which a single-beam in single-mode is incident; a collimating lens which is embedded in a housing connected to the incident fiber and through which the single-beam incident on the entrance of the housing passes, and which converts the single-beam in single-mode into a multi-single-beam in multi-single-mode and allows same to proceed in parallel; a focus lens which is embedded in the housing to collect the single-beams in multi-single-mode, which have passed through the collimating lens, and directs same to an outlet; and an emission fiber connected to the outlet of the housing to emit the multi-single-beam in multi-single-mode.

Description

A method and device for making a multi-single beam of a multi-single mode using a single beam of a single mode, a multi-single beam made by the method, a method for measuring the multi-single beam, and a secondary battery welded with the multi-single beam

[0001] The present disclosure relates to a method and device for converting a multi single beam of multi single mode from a single beam of single mode used for welding, a multi single beam made by that method, a method of measuring that multi single beam, and a rechargeable battery welded with that multi single beam.

[0002] Recent industrial demands have led to the active development of batteries with high energy density and safety. For example, lithium-ion batteries are being used not only in information and communication devices, but also in the automotive sector. Safety is particularly important in the automotive sector, as it is directly related to life.

[0003] Lithium-ion batteries currently on the market use electrolytes containing flammable organic solvents, which poses a risk of overheating and fire in the event of a short circuit. To address this issue, all-solid-state secondary batteries using solid electrolytes are being proposed.

[0004] All-solid-state secondary batteries do not use flammable organic solvents, significantly reducing the risk of fire or explosion even if a short circuit occurs. Therefore, these all-solid-state batteries significantly improve safety compared to lithium-ion batteries that use electrolytes.

[0005] The above-described information disclosed in the background technology of this invention is only intended to improve understanding of the background of the present disclosure and may therefore include information that does not constitute prior art.

[0006] In order to secure weldability in the process of manufacturing all-solid-state secondary batteries, square secondary batteries, cylindrical secondary batteries, and modules and packs, welding is performed with high-power energy to secure the strength of thin, medium, and thick plate components and to secure sealing technology.

[0007] However, the unstable melt pool increases the discontinuous indication area of ​​the weld, and the instability of the molten metal flow increases the side effect of spatter metal foreign matter generated during welding. Therefore, an increase in welding speed is required to improve productivity.

[0008] Furthermore, the keyhole mechanism of aluminum metal welding aims to overcome the decrease in surface tension flow within the molten pool as welding speed increases, through the stable heat input of laser welding. Therefore, by minimizing thermal conductivity and latent heat loss of the aluminum base material during welding, stable weld quality and control of spatter-like metal foreign matter are enabled.

[0009] One embodiment provides a method and device for creating a multi-single beam of a multi-single mode from a single beam of a single mode.

[0010] One embodiment provides a multi-single beam made by a method of making a single beam of a single mode into a multi-single beam of a multi-single mode.

[0011] One embodiment provides a method for measuring a multi-single beam created by making a single beam of a single mode into a multi-single beam of a multi-single mode.

[0012] One embodiment provides a secondary battery welded with a multi-single beam formed by a method of making a single beam of a single mode into a multi-single beam of a multi-single mode.

[0013] A device for creating a multi-single beam of a multi-single mode from a single beam of a single mode according to one embodiment includes an incident fiber for incidenting a single beam of a single mode, a collimating lens built into a housing connected to the incident fiber and converting the single beam of the single mode into a multi-single beam of a multi-single mode and propagating the single beam incident to an entrance of the housing while passing the single beam therethrough, the collimating lens built into the housing for collecting the single beam of the multi-single mode passing through the collimating lens and propagating the single beam to an exit, and an exit fiber connected to the exit of the housing for emitting the multi-single beam of the multi-single mode.

[0014] The magnification factor of the focusing lens magnification (ffoc) for the aiming lens magnification (fcoll) is expressed by the equation M = ffoc / fcoll), and the magnification constant (M) may be 1.2 to 1.8.

[0015] The above aiming lens may be provided in a single unit, and the above focusing lens may be provided in a plurality of units in a sequential manner.

[0016] A device for creating a multi-single beam from a single beam according to one embodiment further includes a propagation fiber provided between the exit of the housing and the emitting fiber, so as to be able to select a beam guided at a set angle and an unguided beam from the incident multi-single beam of the multi-single mode.

[0017] The above-mentioned incident fiber can transmit a single beam of the single mode through a material having a first refractive index, and the housing can transmit a multi-single beam of the converted multi-single mode through a material having a second refractive index higher than the first refractive index.

[0018] A method for generating a multi-single beam of a multi-single mode from a single beam of a single mode according to one embodiment includes a first step of injecting a single beam of a single mode into an entrance of a housing through an incident fiber, a second step of converting the incident single beam of the single mode into a multi-single beam of a multi-single mode through a collimating lens built into the housing and propagating the beam in parallel, a third step of collecting the multi-single beam of the multi-single mode that has passed through the collimating lens through a focusing lens built into the housing and emitting the multi-single beam of the multi-single mode through an exit, and a fourth step of emitting the multi-single beam of the multi-single mode by being connected to the exit of the housing through an exit fiber.

[0019] In the third step, the magnification constant (M) of the focusing lens magnification (ffoc) with respect to the aiming lens magnification (fcoll) is expressed by the formula M = ffoc / fcoll), and the magnification constant (M) can be set to 1.2 to 1.8.

[0020] The first step can transmit a single beam of the single mode through a material having a first refractive index, and the second step can transmit a multi-single beam of the converted multi-single mode through a material having a second refractive index higher than the first refractive index.

[0021] A multi-single beam of a multi-single mode according to one embodiment includes a single beam of a single mode transmitted through a material having a first refractive index, a single portion having a reduced phase difference and a homogeneous density while transmitting through a material having a second refractive index higher than the first refractive index, and a multi-section formed in multiple portions in the single portion.

[0022] When viewed from the side, the multi-section can form multiple peaks and valleys.

[0023] When viewed from a plane, the multi-part can form a speckle shape by a plurality of peaks and valleys.

[0024] A method for measuring a multi-single beam of a multi-single mode according to one embodiment includes a first step of scanning a multi-single beam of a multi-single mode made of a single beam of a single mode through a measuring tip in a 3D measuring cylinder; a second step of measuring a spatial power density distribution and a shape of the multi-single beam of the multi-single mode in a focal range of an optical device by transmitting the multi-single beam to a deflection mirror; and a third step of transmitting the multi-single beam of the multi-single mode to a detector configured according to the output and wavelength of the multi-single beam.

[0025] The above first step may be via a rotating measuring tip having an opening point.

[0026] A secondary battery welded with a multi-single beam of a multi-single mode made of a single beam of a single mode according to one embodiment comprises a case containing an electrode assembly, and a cap plate welded to seal an opening of the case, wherein the case and the cap plate are welded with a multi-single beam made of a single beam to form a welded portion, and the welded portion further includes a reinforcing portion protruding from an outer surface of the cap plate.

[0027] A first distance (L1) from the welding depth of the above welding part to the outer surface of the case and a second distance (L2) from the welding depth to the outer surface of the cap plate are set, and the first distance is shorter than the second distance (L1 <L2) 형성될 수 있다.

[0028] The welded portion including the above reinforcement portion sets a width (W) set in a direction parallel to the cap plate and a height (H) set in a direction parallel to the case, and the ratio (W / H) of the width (W) to the height (H) may be 0.5 to 2.0.

[0029] The above weld may include an equiaxed tear-shaped bead.

[0030] The above beads may be formed in multiple pieces having a width smaller than the width in the width direction with respect to the entire width of the welded portion.

[0031] The above reinforcement portion may protrude 5 to 200 μm further than the outer surface of the cap plate.

[0032] One embodiment is a multi-single beam welded with a multi-single beam of a single mode, so that weldability can be secured even for thin plate, medium plate, and thick plate parts in secondary battery, module, and pack processes.

[0033] In one embodiment, the multi-single beam can smoothly discharge gas and impurities from the keyhole, reduce the occurrence of pores, and improve the quality of the weld bead during high-speed welding due to the stabilization of the melting pool.

[0034] In one embodiment, a multi-single beam provides a stable heat input for laser welding by reducing the surface tension flow force moving into the molten pool when the mechanical welding speed increases in the keyhole of aluminum metal welding, thereby minimizing the thermal conductivity and latent heat of the aluminum base material that may be lost during welding.

[0035] Through this, one embodiment can control stable welding quality and spatter metal foreign matter.

[0036] Figure 1 is a cross-sectional view showing an all-solid-state secondary battery according to one embodiment of the present invention.

[0037] FIG. 2 is a cross-sectional view showing the formation of a lithium metal layer of an all-solid-state secondary battery according to one embodiment.

[0038] FIG. 3 is a stereoscopic image of a single beam of a single mode used in a method and device for creating a multi-single beam of a multi-single mode with a single beam of a single mode according to one embodiment of the present invention.

[0039] FIG. 4 is a stereoscopic image of a multi-single beam of a multi-single mode created by a method and device for creating a multi-single beam of a multi-single mode with a single beam of a single mode according to one embodiment of the present invention.

[0040] FIG. 5 is a planar image of a multi-single beam of a multi-single mode produced by a method and device for producing a multi-single beam of a multi-single mode with a single beam of a single mode according to one embodiment of the present invention.

[0041] FIG. 6 is a configuration diagram of a device that creates a multi-single beam of a multi-single mode with a single beam of a single mode according to one embodiment of the present invention.

[0042] FIG. 7 illustrates beam dispersion during the process of converting a single beam of a single mode into a multi-single beam of a multi-single mode between a collimating lens and a focusing lens in the device of FIG. 6.

[0043] FIG. 8 illustrates the process of gathering beams during which a multi-single beam of a multi-single mode is converted into a multi-single beam of a multi-single mode through the focusing lens of FIG. 7.

[0044] Fig. 9 is a perspective view of a radio fiber showing a state in which a multi-single beam of a multi-single mode created through the focusing lens of Fig. 8 is propagated.

[0045] Fig. 10 is a cross-sectional view of Fig. 9.

[0046] FIG. 11 is a flowchart of a method for creating a multi-single beam of a multi-single mode with a single beam of a single mode according to one embodiment of the present invention.

[0047] FIGS. 12 to 15 are a perspective view (a) and a plan view (b) of a multi-single beam of a multi-single mode made by a device and method for making a multi-single beam of a multi-single mode with a single beam of a single mode according to one embodiment of the present invention.

[0048] FIG. 16 is a configuration diagram of a device for measuring a multi-single beam of a multi-single mode created by a device and method for creating a multi-single beam of a multi-single mode with a single beam of a single mode according to one embodiment of the present invention.

[0049] Fig. 17 is a flowchart of a method for measuring a multi-single beam in a multi-single mode using the device of Fig. 16.

[0050] FIG. 18 is a state diagram of a multi-single beam welded with a multi-single beam of a multi-single mode, made by a device and method for making a multi-single beam of a multi-single mode with a single beam of a single mode according to one embodiment of the present invention.

[0051] Fig. 19 is a perspective view of a secondary battery in which the cap plate and case are welded with the multi-single beam of the multi-single mode of Fig. 18.

[0052] Figure 20 is a side image of the weld in Figure 19.

[0053] Fig. 21 is a planar image of the weld in Fig. 19.

[0054] Fig. 22 is a cross-sectional image of a weld along line AA of Fig. 21.

[0055] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings so that those skilled in the art can easily implement the present invention. The present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0056] Additionally, throughout the specification, whenever a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

[0057] To clearly illustrate various layers and regions in the drawings, their thicknesses are enlarged, and similar parts are designated by the same drawing reference numerals throughout the specification. When an element such as a layer, film, region, or plate is said to be "over" or "on" another element, this includes not only the case where it is "directly over" the other element, but also the case where there is another element in between. Conversely, when an element is said to be "directly over" another element, it means that there is no other element in between.

[0058] Furthermore, the term "layer" here includes not only shapes formed on the entire surface when observed in a plan view, but also shapes formed on a portion of the surface. Here, "or" is not interpreted in an exclusive sense; for example, "A or B" is interpreted to include A, B, A+B, etc.

[0059] Cathode for all-solid-state secondary batteries

[0060] In one embodiment, a positive electrode for an all-solid-state secondary battery is provided, comprising a current collector and a positive electrode active material layer positioned on the current collector, wherein the positive electrode active material layer comprises at least one of a positive electrode active material, a sulfide-based solid electrolyte, a binder, and a conductive material. However, without limitation thereto, the positive electrode for an all-solid-state secondary battery may comprise more or less components than the components described above.

[0061] In one embodiment, the positive electrode for the all-solid-state secondary battery is manufactured by applying a positive electrode composition including at least one of a positive electrode active material, a sulfide-based solid electrolyte, a binder, and a conductive agent to a current collector, followed by drying and rolling.

[0062] positive electrode active material

[0063] The above-mentioned positive electrode active material can be applied without limitation as long as it is generally used in all-solid-state secondary batteries. For example, the above-mentioned positive electrode active material may be a compound capable of reversible intercalation and deintercalation of lithium, and may include a compound represented by any one of the following chemical formulas.

[0064] Li a A 1-b X b D2(0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5);

[0065] Li a A 1-b X b O 2-c D c (0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05);

[0066] Li a E 1-b X b O 2-c D c (0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05);

[0067] Li a E 2-b Xb O 4-c D c (0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05);

[0068] Li a Ni 1-b-c Co b X c D α (0.90 ≤ a ≤1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.5, 0 <α ≤ 2);

[0069] Li a Ni 1-b-c Co b X c O 2-α T α (0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, 0 < α < 2);

[0070] Li a Ni 1-b-c Co b X c O 2-α T2(0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, 0 < α < 2);

[0071] Li a Ni 1-b-c Mr b X c D α (0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, 0 < α ≤ 2);

[0072] Li a Ni 1-b-c Mr b X c O 2-α T α (0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, 0 < α < 2);

[0073] Li a Ni 1-b-c Mr b X c O 2-αT2(0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.05, 0 <α < 2);

[0074] The a Nor b E c G d O2(0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.5, 0.001 ≤ d ≤ 0.1);

[0075] The a Nor b Co c Mn d G e O2(0.90 ≤ a ≤ 1.8, 0 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.5, 0 ≤ d ≤0.5, 0.001 ≤ e ≤ 0.1);

[0076] The a NiG b O2(0.90 ≤ a ≤ 1.8, 0.001 ≤ b ≤ 0.1);

[0077] The a CoG b O2(0.90 ≤ a ≤ 1.8, 0.001 ≤ b ≤ 0.1);

[0078] The a Mn 1-b G b O2(0.90 ≤ a ≤ 1.8, 0.001 ≤ b ≤ 0.1);

[0079] The a Mn2G b O4(0.90 ≤ a ≤ 1.8, 0.001 ≤ b ≤ 0.1);

[0080] The a Mn 1-g G g PO4(0.90 ≤ a ≤ 1.8, 0 ≤ g ≤ 0.5);

[0081] QO2; QS2; LiQS2;

[0082] V2O5; LiV2O5;

[0083] LiZO2;

[0084] LiNiVO4;

[0085] Li (3-f) J2(PO4)3(0 ≤ f ≤ 2);

[0086] Li (3-f) Fe2(PO4)3(0 ≤ f ≤ 2);

[0087] Li a FePO4(0.90 ≤ a ≤ 1.8).

[0088] In the above chemical formulas, A is selected from the group consisting of Ni, Co, Mn, and combinations thereof; X is selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements, and combinations thereof; D is selected from the group consisting of O, F, S, P, and combinations thereof; E is selected from the group consisting of Co, Mn, and combinations thereof; T is selected from the group consisting of F, S, P, and combinations thereof; G is selected from the group consisting of Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, and combinations thereof; Q is selected from the group consisting of Ti, Mo, Mn, and combinations thereof; Z is selected from the group consisting of Cr, V, Fe, Sc, Y, and combinations thereof; J is selected from the group consisting of V, Cr, Mn, Co, Ni, Cu, and combinations thereof.

[0089] The above-mentioned positive electrode active material may be, for example, lithium cobalt oxide (LCO), lithium nickel oxide (LNO), lithium nickel cobalt oxide (NC), lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese oxide (NCM), lithium nickel manganese oxide (NM), lithium manganese oxide (LMO), or lithium iron phosphate (LFP).

[0090] The above positive electrode active material may include a lithium nickel-based oxide represented by the following chemical formula 1, a lithium cobalt-based oxide represented by the following chemical formula 2, a lithium iron phosphate-based compound represented by the following chemical formula 3, or a combination thereof.

[0091] [Chemical Formula 1]

[0092] Li a1 Ni x1 M 1 y1 M 2 1-x1-y1 O2

[0093] In the above chemical formula 1, 0.9≤a1≤1.8, 0.3≤x1≤1, 0≤y1≤0.7, and M1 and M2 are each independently one or more elements selected from the group consisting of Al, B, Ba, Ca, Ce, Co, Cr, Cu, F, Fe, Mg, Mn, Mo, Nb, P, S, Si, Sr, Ti, V, W, and Zr.

[0094] [Chemical Formula 2]

[0095] Li a2 Co x2 M 3 1-x2 O2

[0096] In the above chemical formula 2, 0.9≤a2≤1.8, 0.6≤x2≤1, and M3 is one or more elements selected from the group consisting of Al, B, Ba, Ca, Ce, Cr, Cu, F, Fe, Mg, Mn, Mo, Nb, P, S, Si, Sr, Ti, V, W, and Zr.

[0097] [Chemical Formula 3]

[0098] Li a3 Fe x3 M 4 (1-x3) PO4

[0099] In the above chemical formula 3, 0.9≤a3≤1.8, 0.6≤x3≤1, and M4 is one or more elements selected from the group consisting of Al, B, Ba, Ca, Ce, Co, Cr, Cu, F, Fe, Mg, Mn, Mo, Nb, P, S, Si, Sr, Ti, V, W, and Zr.

[0100] The average particle diameter (D50) of the positive electrode active material may be 1 μm to 25 μm, for example, 3 μm to 25 μm, 5 μm to 25 μm, 5 μm to 20 μm, 8 μm to 20 μm, or 10 μm to 18 μm. A positive electrode active material having such a particle diameter range can be harmoniously mixed with other components within the positive electrode active material layer and can realize high capacity and high energy density.

[0101] The above-mentioned positive electrode active material may be in the form of a secondary particle formed by agglomeration of a plurality of primary particles, or may be in the form of a single particle. In addition, the above-mentioned positive electrode active material may be spherical or nearly spherical in shape, or may be polyhedral or irregular in shape.

[0102] Sulfide-based solid electrolyte

[0103] Sulfide-based solid electrolytes include, for example, Li2S-P2S5, Li2S-P2S5-LiX (where X is a halogen element, for example, I or Cl), Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-P2S5-LiI, Li2S-B2S3, Li2S-P2S5-Z. m S n (m, n are integers, Z is Ge, Zn or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (p, q are integers, and M is P, Si, Ge, B, Al, Ga or In), or a combination thereof.

[0104] Such sulfide-based solid electrolytes can be obtained, for example, by mixing Li2S and P2S5 in a molar ratio of 50:50 to 90:10, or 50:50 to 80:20, and optionally heat-treating them. Within the above mixing ratio range, a sulfide-based solid electrolyte having excellent ionic conductivity can be produced. Here, the ionic conductivity can be further improved by further including other components such as SiS2, GeS2, and B2S3.

[0105] Methods for mixing sulfur-containing raw materials for producing sulfide-based solid electrolytes include mechanical milling or the solution method. Mechanical milling involves placing the starting raw materials in a reactor and vigorously stirring them with a ball mill or similar device to finely atomize and mix them. Using the solution method, the starting raw materials are mixed in a solvent to obtain a solid electrolyte as a precipitate. Furthermore, heat treatment after mixing can solidify the crystals of the solid electrolyte and improve ionic conductivity. For example, a sulfide-based solid electrolyte can be produced by mixing sulfur-containing raw materials and heat-treating them twice or more, resulting in a sulfide-based solid electrolyte with high ionic conductivity and robustness.

[0106] For example, the sulfide-based solid electrolyte particles may include argyrodite-type sulfides. The argyrodite-type sulfides may include, for example, Li a M b P c S d A e (wherein a, b, c, d and e are all 0 or more and 12 or less, M is a metal other than Li or a combination of multiple metals other than Li, and A is F, Cl, Br, or I) and a specific example is Li 7-x PS 6-x A x(x is 0.2 or more and 1.8 or less, and A is F, Cl, Br, or I) can be expressed by the chemical formula. The above argyrodite-type sulfide is specifically Li3PS4, Li7P3S 11 , Li7PS6, Li6PS5Cl, Li6PS5Br, Li 5.8 PS 4.8 Cl 1.2 , Li 6.2 PS 5.2 Br 0.8 It could be the back.

[0107] Sulfide-based solid electrolyte particles containing these argyrodite-type sulfides have an ionic conductivity of 10, which is the ionic conductivity of a typical liquid electrolyte at room temperature. -4 10 inland -2 It has a high ionic conductivity approaching the S / cm range, can form a close bond between a positive electrode active material and a solid electrolyte without causing a decrease in ionic conductivity, and can further form a close interface between the electrode layer and the solid electrolyte layer. An all-solid-state battery including this can have improved battery performance, such as rate characteristics, Coulombic efficiency, and cycle life characteristics.

[0108] An argyrodite-type sulfide-based solid electrolyte can be prepared, for example, by mixing lithium sulfide, phosphorus sulfide, and optionally, a lithium halide. After mixing, a heat treatment may be performed. The heat treatment may include, for example, two or more heat treatment steps.

[0109] According to one embodiment, the average particle diameter (D50) of the sulfide-based solid electrolyte particles may be 5.0 ㎛ or less, for example, 0.1 ㎛ to 5.0 ㎛, 0.1 ㎛ to 4.0 ㎛, 0.1 ㎛ to 3.0 ㎛, 0.5 ㎛ to 2.0 ㎛, or 0.1 ㎛ to 1.5 ㎛. Alternatively, the sulfide-based solid electrolyte particles may be small particles having an average particle diameter (D50) of 0.1 ㎛ to 1.0 ㎛, or may be large particles having an average particle diameter (D50) of 1.5 ㎛ to 5.0 ㎛, depending on the location or purpose of use. The sulfide-based solid electrolyte particles having such a particle diameter range can effectively penetrate between solid particles in a battery, and have excellent contact with an electrode active material and connectivity between solid electrolyte particles. The average particle size of the sulfide-based solid electrolyte particles may be measured from a microscope image, for example, by measuring the sizes of about 20 particles in a scanning electron microscope image to obtain a particle size distribution and calculating D50 from this.

[0110] The content of the solid electrolyte in the positive electrode for the all-solid-state battery may be 0.5 wt% to 35 wt%, for example, 1 wt% to 35 wt%, 5 wt% to 30 wt%, 8 wt% to 25 wt%, or 10 wt% to 20 wt%. This is the content relative to the total weight of components in the positive electrode, and specifically, it can be said to be the content relative to the total weight of the positive electrode active material layer.

[0111] In one embodiment, the positive electrode active material layer may include 50 wt% to 99.35 wt% of the positive electrode active material, 0.5 wt% to 35 wt% of the sulfide-based solid electrolyte, 0.1 wt% to 10 wt% of the fluorine-based resin binder, and 0.05 wt% to 5 wt% of the vanadium oxide, based on 100 wt% of the positive electrode active material layer. When this content range is satisfied, the positive electrode for an all-solid-state secondary battery can implement high capacity and high ionic conductivity while maintaining high adhesiveness, and the viscosity of the positive electrode composition can be maintained at an appropriate level, thereby improving processability.

[0112] bookbinder

[0113] The binder serves to adhere the positive electrode active material particles well to each other and also to adhere the positive electrode active material well to the current collector, and representative examples thereof include, but are not limited to, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, etc.

[0114] Challenge

[0115] The above-described positive electrode active material layer may further include a conductive material. The conductive material is used to impart conductivity to the electrode, and may include, for example, carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fibers, and carbon nanotubes; metal-based materials containing copper, nickel, aluminum, silver, and the like in the form of metal powder or metal fibers; conductive polymers such as polyphenylene derivatives; or combinations thereof.

[0116] The conductive material may be included in an amount of 0.1 wt% to 5 wt%, or 0.1 wt% to 3 wt%, based on the total weight of each component of the positive electrode for the all-solid-state battery, or based on the total weight of the positive electrode active material layer. Within the above content range, the conductive material can improve electrical conductivity without degrading battery performance.

[0117] When the positive electrode active material layer further includes a conductive material, the positive electrode active material layer may include 45 wt% to 99.25 wt% of the positive electrode active material, 0.5 wt% to 35 wt% of the sulfide-based solid electrolyte, 0.1 wt% to 10 wt% of the fluorine-based resin binder, 0.05 wt% to 5 wt% of the vanadium oxide, and 0.1 wt% to 5 wt% of the conductive material, based on 100 wt% of the positive electrode active material layer.

[0118] Meanwhile, the positive electrode for the lithium secondary battery may further include an oxide-based inorganic solid electrolyte in addition to the above-described solid electrolyte. The oxide-based inorganic solid electrolyte may be, for example, Li 1+x Ti 2-x Al(PO4)3(LTAP)(0≤x≤4), Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 (0 <x<2, 0≤y<3), BaTiO3, Pb(Zr,Ti)O3(PZT), Pb 1-x La x Zr 1-y Ti y O3(PLZT)(0≤x<1, 0≤y<1), PB(Mg3Nb 2 / 3 )O3-PbTiO3(PMN-PT), HfO2, SrTiO3, SnO2, CeO2, Na2O, MgO, NiO, CaO, BaO, ZnO, ZrO2, Y2O3, Al2O3, TiO2, SiO2, lithium phosphate (Li3PO4), lithium titanium phosphate (Li x Ti y(PO4)3, 0 <x<2, 0<y<3), Li 1+x+y (Al, Ga) x (Ti, Ge) 2-x Si y P 3-y O 12 (0≤x≤1, 0≤y≤1), lithium lanthanum titanate (Li x La y TiO3, 0 <x<2, 0<y<3), Li2O, LiAlO2, Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2계 세라믹스, 가넷(Garnet)계 세라믹스 Li 3+x La3M2O 12 (M= Te, Nb, or Zr; x is an integer from 1 to 10), or a combination thereof.

[0119] All-solid-state secondary battery

[0120] In one embodiment, an all-solid-state secondary battery is provided, which includes the aforementioned positive electrode and negative electrode and a solid electrolyte layer positioned between the positive electrode and negative electrode. The all-solid-state secondary battery may also be referred to as an all-solid-state battery or an all-solid-state lithium secondary battery.

[0121] Fig. 1 is a cross-sectional view of an all-solid-state secondary battery according to one embodiment. Referring to Fig. 1, the all-solid-state secondary battery (100) may have a structure in which an electrode assembly in which a negative electrode (400) including a negative electrode current collector (401) and a negative electrode active material layer (403), a solid electrolyte layer (300), and a positive electrode (200) including a positive electrode active material layer (203) and a positive electrode current collector (201) are laminated is housed in a case such as a pouch. The all-solid-state secondary battery (100) may further include an elastic layer (500) on the outer side of at least one of the positive electrode (200) and the negative electrode (400). Although Fig. 1 illustrates one electrode assembly including a negative electrode (400), a solid electrolyte layer (300), and a positive electrode (200), an all-solid-state battery may be manufactured by laminating two or more electrode assemblies.

[0122] cathode

[0123] An anode for an all-solid-state battery may include, for example, a current collector and a layer of anode active material positioned on the current collector. The layer of anode active material includes a cathode active material and may further include a binder, a conductive material, and / or a solid electrolyte.

[0124] The above negative active material may include a material capable of reversibly intercalating / deintercalating lithium ions, lithium metal, an alloy of lithium metal, a material capable of doping and dedoping lithium, or a transition metal oxide.

[0125] The material capable of reversibly intercalating / deintercalating the lithium ions may include a carbon-based negative electrode active material, for example, crystalline carbon, amorphous carbon, or a combination thereof. Examples of the crystalline carbon include graphite such as natural graphite or artificial graphite in an amorphous, plate-like, flake-like, spherical, or fibrous form, and examples of the amorphous carbon include soft carbon or hard carbon, mesophase pitch carbide, calcined coke, and the like.

[0126] As the above lithium metal alloy, an alloy of lithium and one or more metals selected from Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn can be used.

[0127] As the material capable of doping and dedoping the lithium, a Si-based negative electrode active material or a Sn-based negative electrode active material can be used, and the Si-based negative electrode active material may be silicon, a silicon-carbon composite, or SiO. x(0<x<2), Si-Q 합금(상기 Q는 알칼리 금속, 알칼리 토금속, 13족 원소, 14족 원소, 15족 원소, 16족 원소, 전이금속, 희토류 원소 및 이들의 조합으로 이루어진 군에서 선택되는 원소이며, Si은 아님), 상기 Sn계 음극 활물질로는 Sn, SnO2, Sn-R 합금(상기 R은 알칼리 금속, 알칼리 토금속, 13족 원소, 14족 원소, 15족 원소, 16족 원소, 전이금속, 희토류 원소 및 이들의 조합으로 이루어진 군에서 선택되는 원소이며, Sn은 아님) 등을 들 수 있고, 또한 이들 중 적어도 하나와 SiO2를 혼합하여 사용할 수도 있다. 상기 원소 Q 및 R로는 Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Tl, Ge, P, As, Sb, Bi, S, Se, Te, Po, 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다.

[0128] The silicon-carbon composite may be, for example, a silicon-carbon composite including a core comprising crystalline carbon and silicon particles and an amorphous carbon coating layer positioned on the surface of the core. The crystalline carbon may be artificial graphite, natural graphite, or a combination thereof. As the amorphous carbon precursor, coal pitch, mesophase pitch, petroleum pitch, coal oil, petroleum heavy oil, or a polymer resin such as a phenol resin, a furan resin, or a polyimide resin may be used. At this time, the content of silicon may be 10 wt% to 50 wt% with respect to the total weight of the silicon-carbon composite. In addition, the content of the crystalline carbon may be 10 wt% to 70 wt% with respect to the total weight of the silicon-carbon composite, and the content of the amorphous carbon may be 20 wt% to 40 wt% with respect to the total weight of the silicon-carbon composite. In addition, the thickness of the amorphous carbon coating layer may be 5 nm to 100 nm.

[0129] The average particle diameter (D50) of the above silicon particles may be 10 nm to 20 μm, for example, 10 nm to 500 nm. The silicon particles may exist in an oxidized form, and at this time, the atomic content ratio of Si:O in the silicon particles, which indicates the degree of oxidation, may be 99:1 to 33:67. The silicon particles may be SiO x It can be a particle, in which case SiO x In the range of x, it can be greater than 0 and less than 2. Here, the average particle diameter (D50) is measured by a particle size analyzer using laser diffraction and means the diameter of particles having a cumulative volume of 50% by volume in the particle size distribution.

[0130] The above Si-based negative electrode active material or Sn-based negative electrode active material can be used in combination with a carbon-based negative electrode active material. The mixing ratio of the Si-based negative electrode active material or Sn-based negative electrode active material and the carbon-based negative electrode active material can be 1:99 to 90:10 by weight.

[0131] The content of the negative active material in the above negative active material layer may be 95 wt% to 99 wt% with respect to the total weight of the negative active material layer.

[0132] In one embodiment, the negative electrode active material layer further includes a binder and may optionally further include a conductive material. The content of the binder in the negative electrode active material layer may be 1 wt% to 5 wt% based on the total weight of the negative electrode active material layer. In addition, when the negative electrode active material layer further includes a conductive material, the negative electrode active material layer may include 90 wt% to 98 wt% of the negative electrode active material, 1 wt% to 5 wt% of the binder, and 1 wt% to 5 wt% of the conductive material.

[0133] The above binder serves to adhere the negative active material particles well to each other and also to adhere the negative active material well to the current collector. The binder may include an insoluble binder, a water-soluble binder, or a combination thereof.

[0134] The above-described non-aqueous binder may include, for example, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, a polymer comprising ethylene oxide, an ethylene propylene copolymer, polystyrene, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyamideimide, polyimide, or a combination thereof.

[0135] The water-soluble binder may be a rubber-based binder or a polymer resin binder. The rubber-based binder may be selected from styrene-butadiene rubber, acrylated styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylic rubber, butyl rubber, fluororubber, and combinations thereof. The polymer resin binder may be selected from polyethylene oxide, polyvinylpyrrolidone, polyepichlorohydrin, polyphosphazene, polyacrylonitrile, ethylene propylene diene copolymer, polyvinylpyridine, chlorosulfonated polyethylene, latex, polyester resin, acrylic resin, phenol resin, epoxy resin, polyvinyl alcohol, and combinations thereof.

[0136] When a water-soluble binder is used as the negative electrode binder, a thickener capable of imparting viscosity may be used together, and the thickener may include, for example, a cellulose-based compound. The cellulose-based compound may include carboxymethyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, an alkali metal salt thereof, or a combination thereof. Na, K, or Li may be used as the alkali metal. The amount of the thickener used may be 0.1 to 3 parts by weight based on 100 parts by weight of the negative electrode active material.

[0137] The conductive material is used to provide conductivity to the electrode, and may include, for example, carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fibers, and carbon nanotubes; metal-based materials in the form of metal powder or metal fibers, including copper, nickel, aluminum, and silver; conductive polymers such as polyphenylene derivatives; or mixtures thereof.

[0138] The negative electrode current collector may be selected from copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, and a combination thereof.

[0139] As another example, the negative electrode for the all-solid-state battery may be a precipitation-type negative electrode. The precipitation-type negative electrode refers to a negative electrode that does not include a negative electrode active material when the battery is assembled, but in which lithium metal or the like is precipitated when the battery is charged, and this acts as a negative electrode active material.

[0140] FIG. 2 is a schematic cross-sectional view of an all-solid-state secondary battery including a precipitation-type negative electrode according to one embodiment. Referring to FIG. 2, the precipitation-type negative electrode (400') may include a current collector (401) and a negative electrode coating layer (405) positioned on the current collector. An all-solid-state battery including such a precipitation-type negative electrode (400') starts initial charging in a state in which no negative electrode active material is present, and upon charging, high-density lithium metal or the like is precipitated between the current collector (401) and the negative electrode coating layer (405) to form a lithium metal layer (404), which may function as a negative electrode active material. Accordingly, in an all-solid-state battery that has been charged at least once, the precipitation-type negative electrode (400') may include a current collector (401), a lithium metal layer (404) positioned on the current collector, and a negative electrode coating layer (405) positioned on the metal layer. The above lithium metal layer (404) refers to a layer in which lithium metal, etc. is precipitated during the charging process of the battery, and may be referred to as a metal layer or a negative electrode active material layer.

[0141] The above cathode coating layer (405) may include a metal, a carbon material, or a combination thereof that acts as a catalyst.

[0142] The metal may include, for example, gold, platinum, palladium, silicon, silver, aluminum, bismuth, tin, zinc, or a combination thereof, and may be composed of one type of these or may be composed of an alloy of several types. When the metal is present in the form of particles, the average particle diameter (D50) thereof may be about 4 μm or less, for example, 10 nm to 4 μm.

[0143] The carbon material may be, for example, crystalline carbon, amorphous carbon, or a combination thereof. The crystalline carbon may be, for example, natural graphite, artificial graphite, mesophase carbon microbeads, or a combination thereof. The amorphous carbon may be, for example, carbon black, activated carbon, acetylene black, Denka black, Ketjen black, or a combination thereof.

[0144] When the above-described negative electrode coating layer (405) includes both the metal and the carbon material, the mixing ratio of the metal and the carbon material may be, for example, a weight ratio of 1:10 to 2:1. In this case, the precipitation of lithium metal can be effectively promoted and the characteristics of the all-solid-state battery can be improved. The above-described negative electrode coating layer (405) may include, for example, a carbon material supported with a catalytic metal, or may include a mixture of metal particles and carbon material particles.

[0145] The above cathode coating layer (405) may include, for example, the metal and amorphous carbon, in which case it can effectively promote the precipitation of lithium metal.

[0146] The above cathode coating layer (405) may further include a binder, and the binder may be a conductive binder. In addition, the above cathode coating layer (405) may further include general additives such as fillers, dispersants, and ionic conductive agents.

[0147] The thickness of the cathode coating layer (405) may be, for example, 100 nm to 20 ㎛, or 500 nm to 10 ㎛, or 1 ㎛ to 5 ㎛.

[0148] The above-described precipitated negative electrode (400') may further include, for example, a thin film on the surface of the current collector, i.e., between the current collector and the negative electrode coating layer. The thin film may include an element capable of forming an alloy with lithium. The element capable of forming an alloy with lithium may be, for example, gold, silver, zinc, tin, indium, silicon, aluminum, bismuth, etc., and may be composed of one type thereof or may be composed of multiple types of alloys. The thin film may further flatten the precipitated form of the lithium metal layer (404) and further improve the characteristics of the all-solid-state battery. The thin film may be formed by, for example, a vacuum deposition method, a sputtering method, a plating method, etc. The thickness of the thin film may be, for example, 1 nm to 500 nm.

[0149] solid electrolyte layer

[0150] The solid electrolyte layer (300) may include a sulfide-based solid electrolyte, an oxide-based solid electrolyte, etc. The specific details of the sulfide-based solid electrolyte and the oxide-based solid electrolyte are as described above.

[0151] In one example, the solid electrolyte included in the positive electrode (200) and the solid electrolyte included in the solid electrolyte layer (300) may include the same compound or different compounds. For example, when both the positive electrode (200) and the solid electrolyte layer (300) include an argyrodite-type sulfide-based solid electrolyte, the overall performance of the all-solid-state secondary battery may be improved. In addition, for example, when both the positive electrode (200) and the solid electrolyte layer (300) include the above-described coated solid electrolyte, the all-solid-state secondary battery may implement high capacity and high energy density while implementing excellent initial efficiency and lifespan characteristics.

[0152] Meanwhile, the average particle diameter (D50) of the solid electrolyte included in the positive electrode (200) may be smaller than the average particle diameter (D50) of the solid electrolyte included in the solid electrolyte layer (300). In this case, the energy density of the all-solid-state battery can be maximized while increasing the mobility of lithium ions, thereby improving the overall performance. For example, the average particle diameter (D50) of the solid electrolyte included in the positive electrode (200) may be 0.1 ㎛ to 1.0 ㎛, or 0.1 ㎛ to 0.8 ㎛, and the average particle diameter (D50) of the solid electrolyte included in the solid electrolyte layer (300) may be 1.5 ㎛ to 5.0 ㎛, or 2.0 ㎛ to 4.0 ㎛, or 2.5 ㎛ to 3.5 ㎛. When this particle size range is satisfied, the energy density of the all-solid-state secondary battery can be maximized while lithium ion transport is facilitated, resistance is suppressed, and the overall performance of the all-solid-state secondary battery can be improved. Here, the average particle diameter (D50) of the solid electrolyte can be measured using a particle size analyzer using laser diffraction. Alternatively, the particle size can be measured by selecting 20 or so random particles from a microscope image such as a scanning electron microscope, obtaining a particle size distribution, and calculating the D50 value from this.

[0153] The above solid electrolyte layer may further include a binder in addition to the solid electrolyte. At this time, the binder may be styrene butadiene rubber, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, an acrylate polymer, or a combination thereof, but is not limited thereto, and any binder used in the relevant technical field may be used. The acrylate polymer may be, for example, butyl acrylate, polyacrylate, polymethacrylate, or a combination thereof.

[0154] The above solid electrolyte layer can be formed by adding a solid electrolyte to a binder solution, coating the same on a base film, and drying the same. The solvent of the binder solution may be isobutyryl isobutyrate, xylene, toluene, benzene, hexane, or a combination thereof. Since the solid electrolyte layer formation process is widely known in the art, a detailed description thereof will be omitted.

[0155] The thickness of the solid electrolyte layer may be, for example, 10 ㎛ to 150 ㎛.

[0156] The above solid electrolyte layer may further include an alkali metal salt, and / or an ionic liquid, and / or a conductive polymer.

[0157] The above alkali metal salt may be, for example, a lithium salt. The content of the lithium salt in the solid electrolyte layer may be 1 M or more, for example, 1 M to 4 M. In this case, the lithium salt may improve ion conductivity by enhancing the lithium ion mobility of the solid electrolyte layer.

[0158] The above lithium salts include, for example, LiSCN, LiN(CN)2, Li(CF3SO2)3C, LiC4F9SO3, LiN(SO2CF2CF3)2, LiCl, LiF, LiBr, LiI, LiB(C2O4)2, LiBF4, LiBF3(C2F5), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LIODFB), lithium difluoro(oxalato)borate (LiDFOB), lithium bis(trifluoro methanesulfonyl)imide (LiTFSI, LiN(SO2CF3)2), lithium bis(fluorosulfonyl)imide (LiFSI, It may include LiN(SO2F)2), LiCF3SO3, LiAsF6, LiSbF6, LiClO4 or mixtures thereof.

[0159] In addition, the lithium salt may be an imide-based one, and for example, the imide-based lithium salt may include lithium bis(trifluoro methanesulfonyl)imide (LiTFSI, LiN(SO2CF3)2), lithium bis(fluorosulfonyl)imide (LiFSI, LiN(SO2F)2). The lithium salt may maintain or improve ionic conductivity by appropriately maintaining chemical reactivity with an ionic liquid.

[0160] The above ionic liquid has a melting point below room temperature and is a salt or room-temperature molten salt that is liquid at room temperature and consists only of ions.

[0161] The above ionic liquid may be a compound including a) one or more cations selected from ammonium-based, pyrrolidinium-based, pyridinium-based, pyrimidinium-based, imidazolium-based, piperidinium-based, pyrazolium-based, oxazolium-based, pyridazinium-based, phosphonium-based, sulfonium-based, triazolium-based, and mixtures thereof, and b) one or more anions selected from BF4-, PF6-, AsF6-, SbF6-, AlCl4-, HSO4-, ClO4-, CH3SO3-, CF3CO2-, Cl-, Br-, I-, BF4-, SO4-, CF3SO3-, (FSO2)2N-, (C2F5SO2)2N-, (C2F5SO2)(CF3SO2)N-, and (CF3SO2)2N-.

[0162] The ionic liquid may be at least one selected from the group consisting of, for example, N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, N-butyl-N-methylpyrrolidinium bis(3-trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide.

[0163] In the above solid electrolyte layer, the weight ratio of the solid electrolyte and the ionic liquid may be 0.1:99.9 to 90:10, for example, 10:90 to 90:10, 20:80 to 90:10, 30:70 to 90:10, 40:60 to 90:10, or 50:50 to 90:10. A solid electrolyte layer satisfying the above range can maintain or improve ionic conductivity by improving the electrochemical contact area with the electrode. Accordingly, the energy density, discharge capacity, rate characteristics, etc. of the all-solid-state battery can be improved.

[0164] The above-mentioned all-solid-state battery may be a unit battery having a structure of positive electrode / solid electrolyte layer / negative electrode, a bi-cell having a structure of positive electrode / solid electrolyte layer / negative electrode / solid electrolyte layer / positive electrode, or a laminated battery in which the structure of the unit battery is repeated.

[0165] The shape of the above-mentioned all-solid-state battery is not particularly limited, and may be, for example, coin-shaped, button-shaped, sheet-shaped, stacked, cylindrical, flat, etc. In addition, the above-mentioned all-solid-state battery can be applied to large-scale batteries used in electric vehicles, etc. For example, the above-mentioned all-solid-state battery can be used in hybrid vehicles such as plug-in hybrid electric vehicles (PHEVs). In addition, it can be used in fields requiring large amounts of power storage, and for example, it can be used in electric bicycles or power tools.

[0166] FIG. 3 is a stereoscopic image of a single beam of a single mode used in a method and device for creating a multi-single beam of a multi-single mode with a single beam of a single mode according to an embodiment of the present invention, FIG. 4 is a stereoscopic image of a multi-single beam of a multi-single mode created in a method and device for creating a multi-single beam of a multi-single mode with a single beam of a single mode according to an embodiment of the present invention, and FIG. 5 is a planar image of a multi-single beam of a multi-single mode created in a method and device for creating a multi-single beam of a multi-single mode with a single beam of a single mode according to an embodiment of the present invention.

[0167] Referring to FIGS. 3 and 4, a multi-single beam (2) of a multi-single mode made of a single beam (1) of a single mode includes a single section (21) and a multi section (22).

[0168] FIG. 6 is a block diagram of a device for creating a multi-single beam of a multi-single mode from a single beam of a single mode according to one embodiment of the present invention, FIG. 7 illustrates beam dispersion during a process in which a single beam of a single mode is converted into a multi-single beam of a multi-single mode between a collimating lens and a focusing lens in the device of FIG. 6, and FIG. 8 illustrates beam gathering during a process in which a multi-single beam of a multi-single mode is converted into a multi-single beam of a multi-single mode while passing through the focusing lens of FIG. 7.

[0169] Referring to FIGS. 6 to 8, a device for creating a multi-single beam from a single beam includes an incident fiber (31), a housing (41), a collimating lens (42), a focusing lens (43), and an exit fiber (51).

[0170] The input fiber (31) is configured to input a single beam (1) of a single mode and is connected to the inlet (411) of the housing (41). The output fiber (51) is connected to the outlet (412) of the housing (41) and is configured to output a multi-single beam (2) of a multi-single mode.

[0171] The device of one embodiment includes as its main parts a collimating lens (42) and a focusing lens (43) provided within a housing (41). The collimating lens (42) is formed as a concave lens, and the focusing lens (43) is formed as a convex lens.

[0172] The aiming lens (42) passes a single beam (1) incident on the entrance (411) of the housing (41), and converts the single beam (1) of a single mode into a multi-single beam (2) of a multi-single mode and propagates it in parallel. As an example, the aiming lens (42) is provided in a single unit.

[0173] The focus lens (43) collects the multi-single beam (2) of the multi-single mode that has passed through the aiming lens (42) and directs it to the exit (412). That is, the focus lens (43) increases the density of the multi-single beam (2) of the multi-single mode and directs it to the exit (412). As an example, a plurality of focus lenses (43) are provided in sequence and in parallel.

[0174] The magnification factor of the focusing lens (43) magnification (ffoc) relative to the aiming lens (42) magnification (fcoll) is expressed by the formula M = ffoc / fcoll. The magnification constant (M) is 1.2 to 1.8. For example, if the magnification constant (M) is less than 1.2, the focusing lens (43) magnification (ffoc) is too small, so that the density of the multi-single beam (2) of the multi-single mode becomes too low, and as a result, the number of peaks and valleys in the multi-section (22) may be too small.

[0175] If the magnification constant (M) exceeds 1.8, the magnification (ffoc) of the focus lens (43) is too large, so that the density of the multi-single beam (2) of the multi-single mode becomes too high, and as a result, the number of peaks and valleys in the multi-section (22) may be too large.

[0176] When the magnification constant (M) is 1.2 to 1.8, the magnification (ffoc) of the focus lens (43) is appropriate, so that the density of the multi-single beam (2) of the multi-single mode becomes appropriate, and thus the number of peaks and valleys in the multi-section (22) can be appropriate. For example, the number of peaks is appropriately 5 to 6.

[0177] That is, the multi-single beam (2) having 5 to 6 peaks stabilizes the melting pool, thereby facilitating the discharge of gas and impurities from the keyhole (KH, see Fig. 18) during high-speed welding. As a result, the occurrence of pores in the weld area is reduced, and the quality of the weld bead can be improved.

[0178] Fig. 9 is a perspective view of a radio fiber showing a state in which a multi-single beam of a multi-single mode created through the focusing lens of Fig. 8 is propagated, and Fig. 10 is a cross-sectional view of Fig. 9.

[0179] Referring to FIGS. 9 and 10, the device of one embodiment may further include a propagation fiber (52) provided between the outlet (412) of the housing (41) and the output fiber (51). The propagation fiber (52) selects a guided beam (b1) and an unguided beam (b2) from the incident multi-single beam (2) of the multi-single mode at a first angle (θ1) set in an acceptance cone (511). Only the selected guided beam (b1) is propagated to the output fiber (51) and used for welding.

[0180] The multi-single beam (2) of the multi-single mode is emitted at a first angle (θ1) set in the acceptance cone (511), converted to a second angle (θ2) with respect to the central axis of the radio fiber (52), and finally selected while being converted to a third angle (θ3) with respect to a line perpendicular to the inner surface of the radio fiber (52).

[0181] The incident fiber (31) transmits a single beam (1) of a single mode through a material having a first refractive index. The housing (41) transmits a multi-single beam (2) of a converted multi-single mode through a material having a second refractive index higher than the first refractive index. The multi-single beam (2) can be used for welding by being emitted as a guided beam (b1) selected from a propagation fiber (52), as illustrated in FIGS. 9 and 10.

[0182] Fig. 11 is a flowchart of a method for creating a multi-single beam of a multi-single mode using a single beam of a single mode according to one embodiment of the present invention. Referring to Fig. 11, the method for creating a multi-single beam of a single beam of one embodiment includes a first step (ST1), a second step (ST2), a third step (ST3), and a fourth step (ST4).

[0183] In the first stage (ST1), a single beam (1) of a single mode is incident through an incident fiber (31) into the entrance (411) of a housing (41). In the second stage (ST2), the incident single beam (1) of a single mode is dispersed through a collimating lens (42) built into the housing (41) to be converted into a multi-single beam (2) of a multi-single mode and propagated in parallel.

[0184] That is, the first stage (ST1) transmits a single beam (1) of a single mode through a material having a first refractive index. The second stage (ST2) transmits a multi-single beam (2) of a converted multi-single mode through a material having a second refractive index higher than the first refractive index.

[0185] In the third step (ST3), the multi-single beam (2) of the multi-single mode that passes through the collimating lens (42) is collected through the focusing lens (43) built into the housing (41) and outputted to the exit (412). In the third step (ST3), the magnification constant (M) of the focusing lens (43) magnification (ffoc) relative to the collimating lens (42) magnification (fcoll) is expressed by the formula M = ffoc / fcoll, and the magnification constant (M) is set to 1.2 to 1.8.

[0186] The fourth step (ST4) is connected to the exit (412) of the housing (41) via the emission fiber (51) and emits a multi-single beam (2) in a multi-single mode. In addition, when a radio fiber (52) is provided, the fourth step (ST4) further emits the multi-single beam (2) via the radio fiber (52).

[0187] The incident single mode single beam (1) is converted into a multi-single mode multi-single beam (2) while passing through the collimating lens (42) and the focusing lens (43) in the housing (41). The multi-single mode multi-single beam (2) is transmitted through a material having a high refractive index of the propagation fiber (52) and the emission fiber (51). At this time, among the many multi-modes of the multi-single beam (2), several multi-modes are reduced, thereby generating a homogeneous, high-density multi-single beam (2) with a reduced phase difference. The multi-single mode multi-single beam (2) is finally emitted through the emission fiber (51).

[0188] FIGS. 12 to 15 are a perspective view (a) and a plan view (b) of a multi-single beam of a multi-single mode made by a device and method for making a multi-single beam of a multi-single mode with a single beam of a single mode according to one embodiment of the present invention.

[0189] Referring to FIGS. 12 to 15, the multi-single beam (2) of the multi-single mode emitted by the emission fiber (51) has a speckle and horn shape with multiple peaks and valleys in the top-hat form factor.

[0190] Referring to FIGS. 12 and 13, a multi-single beam (201, 202) of a multi-single mode transmits a single beam (1) of a single mode through a material having a first refractive index, and transmits through a material having a second refractive index higher than the first refractive index, and includes a single portion (21) having a reduced phase difference and a homogeneous density while reducing the multi-mode, and a multi-portion (23, 24) formed in multiple portions in the single portion (21).

[0191] When viewing the multi-single beam (201, 202) of the multi-single mode from the side (a), the multi-section (23, 24) forms multiple peaks and valleys and has five horns. When viewing from the plane (b), the multi-section (23) forms a speckle shape by multiple peaks and valleys and has five horns.

[0192] Referring to FIGS. 14 and 15, a multi-single beam (203, 204) of a multi-single mode transmits a single beam (1) of a single mode through a material having a first refractive index, and transmits through a material having a second refractive index higher than the first refractive index, and includes a single portion (21) having a homogeneous density, in which the phase difference is reduced while the multi-mode is reduced, and a multi-portion (25, 26) formed in multiple portions in the single portion (21).

[0193] When the multi-single beam (203, 204) of the multi-single mode is viewed from the side (a), the multi-section (25, 26) forms multiple peaks and valleys and has five horns. When viewed from the plane (b), the multi-section (25, 26) forms a speckle shape by multiple peaks and valleys and has five to six horns.

[0194] FIG. 16 is a configuration diagram of a device for measuring a multi-single beam of a multi-single mode created by a device and method for creating a multi-single beam of a multi-single mode with a single beam of a single mode according to one embodiment of the present invention, and FIG. 17 is a flowchart of a method for measuring a multi-single beam of a multi-single mode using the device of FIG. 16.

[0195] Referring to FIGS. 16 and 17, a method for measuring a multi-single beam of a multi-single mode includes a first step (ST10), a second step (ST20), and a third step (ST30). This measurement method measures the shape of a multi-single beam (2) of a multi-single mode having a speckle and horn shape with multiple peaks and valleys in a top-hat form factor.

[0196] Step 1 (ST10) scans a multi-mode multi-single beam (2) created from a single-mode single beam (1) through a rotating measurement tip (161) within a 3D measurement cylinder. The rotating measurement tip (161) has an aperture point, and as an example, the aperture may be 20 μm. Step 1 (ST10) scans the multi-single beam (2) through the rotating measurement tip (161) having an aperture point.

[0197] The second step (ST20) transmits to a deflection mirror (162) to measure the spatial power density distribution and the shape of a multi-mode multi-single beam (2) in the focal range of the optical device. The third step (ST30) transmits to a detector (163) configured according to the output and wavelength of the multi-mode multi-single beam (2).

[0198] FIG. 18 is a state diagram of a multi-single beam welded with a multi-single beam of a multi-single mode made by a device and method for making a multi-single beam of a multi-single mode with a single beam of a single mode according to one embodiment of the present invention, and FIG. 19 is a perspective view of a secondary battery in which a cap plate and a case are welded with the multi-single beam of the multi-single mode of FIG. 18.

[0199] Referring to FIGS. 18 to 19, the secondary battery (18) includes a case (181), a cap plate (182), and a welded portion (183), and the welded portion (183) is welded with a multi-single beam (2). The case (181) houses an electrode assembly (not shown), and the cap plate (182) seals and welds an opening of the case (181).

[0200] That is, the multi-single beam (2) having 5 to 6 peaks stabilizes the melting pool, thereby facilitating the discharge of gas and impurities from the keyhole (KH) during high-speed welding. As a result, the welded portion (183) includes a reinforcing portion (184) that protrudes further than the outer surface of the cap plate (182), reduces the occurrence of pores, and improves the quality of the weld bead.

[0201] Fig. 20 is a side image of the weld in Fig. 19, Fig. 21 is a planar image of the weld in Fig. 19, and Fig. 22 is a cross-sectional image of the weld along line AA in Fig. 21.

[0202] Referring to FIGS. 18 to 23, a first distance (L1) from the welding depth (WD) of the welded portion (184) to the outer surface of the case (181) and a second distance (L2) from the welding depth (WD) to the outer surface of the cap plate (182) are set, and the first distance (L1) is set to be shorter (L1) than the second distance (L2). <L2) 형성된다. 이 길이 관계(L1<L2)는 캡 플레이트(182) 측에 보강부(184)의 용이한 형성을 가능하게 한다.

[0203] The welded portion (183) including the reinforcing portion (184) sets a width (W) that is set in a direction parallel to the cap plate (182) and a height (H) that is set in a direction parallel to the case (181). The ratio (W / H) of the width (W) to the height (H) may be 0.5 to 2.0. If it is less than 0.5, the role of the reinforcing portion (184) is minimal, and if it is more than 2.0, the welding speed can be increased, but the speed is lowered, so the productivity is not fully utilized.

[0204] The weld (183) includes an equiaxed tear-shaped bead. The bead forms a plurality of beads (B3) having a width (W1) smaller than the width (W) in the width direction with respect to the entire width (W) of the weld (183). The multi-single beam (2) of the multi-single mode forms a plurality of beads (B3) having a small width (W1).

[0205] The reinforcing portion (184) may protrude 5 to 200 μm further than the outer surface of the cap plate (182). If it is 5 μm, the role of the reinforcing portion (184) is minimal, and if it exceeds 200 μm, the welding speed can be increased, but since the speed is lowered, productivity cannot be fully utilized.

[0206] The above description is only one embodiment for implementing the all-solid-state secondary battery according to the present disclosure, and the present disclosure is not limited to the above-described embodiment, and as claimed in the following claims, it will be understood that the technical spirit of the present disclosure encompasses a range in which various modifications can be implemented without departing from the gist of the present disclosure by anyone having ordinary skill in the art to which the invention pertains.

[0207] - Explanation of symbols -

[0208] 1: Single beam in single mode 2: Multi single beam in multi single mode

[0209] 18: Secondary battery 21: Single battery

[0210] 22, 23, 24, 25, 26: Multi-part 31: Fiber inlet

[0211] 41: Housing 42: Sighting lens

[0212] 43: Focusing lens 51: Output fiber

[0213] 52: Radio fiber 161: Rotation measurement tip

[0214] 162: Deflection mirror 163: Detector

[0215] 181: Case 182: Cap plate

[0216] 183: Welded section 184: Reinforced section

[0217] 201, 202: Multi-single beam in multi-single mode

[0218] 203, 204: Multi-single beam in multi-single mode

[0219] 411: Entrance 412: Exit

[0220] 511: Acceptance cone b1: Guided beam

[0221] b2: Unguided beam B3: Bead

[0222] H: Height L1: First distance

[0223] L2: 2nd street W: width

[0224] W1: Small width WD: Weld depth

[0225] θ1: first angle θ2: second angle

[0226] θ3: third angle

Claims

1. An incident fiber that incidents a single beam of single mode; A collimating lens built into a housing connected to the above-mentioned incident fiber, which passes the single beam incident through the entrance of the housing, converts the single beam of the single mode into a multi-single beam of the multi-single mode, and propagates it in parallel; A focusing lens built into the housing to collect the single beam of the multi-single mode through the aiming lens and direct it to an exit; and An output fiber that is connected to the outlet of the above housing and emits a multi-single beam of the above multi-single mode. A device for creating a multi-single beam of a multi-single mode with a single beam of a single mode including .

2. In paragraph 1, The magnification factor of the focusing lens magnification (ffoc) for the collimating lens magnification (fcoll) is M is expressed as ffoc / fcoll, A device for creating a multi-single beam of a multi-single mode with a single beam of a single mode, wherein the magnification constant (M) is 1.2 to 1.

8.

3. In paragraph 1, A device that creates a multi-single beam of a multi-single mode with a single beam of a single mode, wherein the above-mentioned aiming lens is provided in a single number and the above-mentioned focusing lens is provided in a plurality of numbers in a sequential manner.

4. In paragraph 1, Further including a propagation fiber provided between the exit of the housing and the output fiber, A device for creating a multi-single beam of a multi-single mode by using a single beam of a single mode to select a beam guided at a set angle and a beam not guided from the multi-single beam of the multi-single mode that is incident.

5. In paragraph 1, The above-mentioned fiber is Transmitting a single beam of the single mode through a material having a first refractive index, The above housing A device for creating a multi-single beam of a multi-single mode by transmitting a multi-single beam of a multi-single mode converted through a material having a second refractive index higher than the first refractive index.

6. The first step is to introduce a single beam of single mode into the entrance of the housing through the input fiber; A second step of converting the incident single beam of the single mode into a multi-single beam of the multi-single mode and propagating it in parallel through a collimating lens built into the housing; A third step of collecting the multi-single beam of the multi-single mode through the aiming lens through the focusing lens built into the housing and emitting it to the exit; and A fourth step of emitting a multi-single beam of the multi-single mode by connecting to the exit of the housing through the output fiber. A method for creating a multi-single beam of a multi-single mode with a single beam of a single mode including .

7. In paragraph 6, In the third step above, The magnification constant (M) of the focusing lens magnification (ffoc) for the collimating lens magnification (fcoll) is It is expressed as M = ffoc / fcoll, A method for creating a multi-single beam of a multi-single mode using a single beam of a single mode, wherein the above magnification constant (M) is set to 1.2 to 1.

8.

8. In paragraph 6, The above first step is Transmitting a single beam of the single mode through a material having a first refractive index, The second step above is Transmitting a multi-single beam of a converted multi-single mode through a material having a second refractive index higher than the first refractive index, How to create a multi-single beam of multi-single mode with a single beam of single mode.

9. A single beam of a single mode is transmitted through a material having a first refractive index, and a single beam is transmitted through a material having a second refractive index higher than the first refractive index, and the multi-single mode is reduced while the phase difference is reduced and the single part has a homogeneous density; and Multi-part formed in multiple parts in the above single part Multi-single beam with multi-single mode including .

10. In paragraph 9, When viewed from the side, the above multi-part A multi-single beam with multiple single modes forming multiple peaks and valleys.

11. In paragraph 10, When viewed from a flat surface, the multi-part A multi-single beam with multiple single modes forming a speckle shape by multiple peaks and valleys.

12. ... A second step of measuring the spatial power density distribution and the multi-single beam shape of the multi-single mode in the focal range of the optical device by transmitting it to a deflection mirror; and The third stage transmits the output and wavelength of the multi-single beam in the multi-single mode to a detector configured according to the configuration. A method for measuring a multi-single beam of a multi-single mode including .

13. In paragraph 12, The above first step is A method for measuring a multi-single beam in a multi-single mode through a rotating measuring tip having an aperture point.

14. A case containing an electrode assembly; and A cap plate is included that seals the opening of the case and is welded, The above case and the above cap plate It is made of a single beam and welded into a multi-single beam to form a welded joint. The above welding part A reinforcing portion protruding from the outer surface of the cap plate, A secondary battery welded with a multi-single beam of a single mode including a single beam of a single mode.

15. In paragraph 14, A first distance (L1) from the welding depth of the above welding part to the outer surface of the case, A second distance (L2) is set from the above welding depth to the outer surface of the cap plate, The first distance above is shorter than the second distance (L1 <L2) 형성되는, 싱글 모드의 싱글 빔으로 만든 멀티 싱글 모드의 멀티 싱글 빔으로 용접한 이차 전지.

16. In paragraph 15, The welded portion including the above reinforcement portion A width (W) set in a direction parallel to the above cap plate, Set the height (H) to be set in the direction parallel to the above case, The ratio of width (W) to height (H) (W / H) is A secondary battery welded with a multi-single mode multi-single beam made of a single beam of a single mode, 0.5 to 2.

0.

17. In paragraph 14, The above welding part A secondary battery welded with a multi-single-mode multi-single beam made of a single-mode single beam including an equiaxed tear-shaped bead.

18. In paragraph 17, The above beads A secondary battery welded with a multi-single-mode multi-single beam formed with a single-mode single beam, which forms a plurality of beads having a width smaller than the width in the width direction with respect to the entire width of the welded portion.

19. In paragraph 14, The above reinforcement part A secondary battery welded with a multi-single-mode multi-single beam made of a single-mode single beam that protrudes 5㎛ to 200㎛ further than the outer surface of the cap plate.

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