A System for Analyzing Black Powder Component and Recycling Grade in Waste Batteries with using LIBS and its Operation Control Method

Abstract

The present invention relates to a system and method of operation for analyzing the type / grade of black powder based on Laser Induced Breakdown Spectroscopy (LIBS) while the components of black powder, which includes lithium and useful metals such as nickel and cobalt, are being transported on a conveyor belt after separating waste batteries down to the cell unit and finely crushing them into powder form, and the system and method of operation thereof. More specifically, the invention relates to a LIBS-based system for analyzing the components and recycling grade of waste battery black powder and a method of operation control thereof, which enables the rapid determination of the type / grade of black powder by securing key information such as the lithium content, nickel content, and cobalt content within the black powder resulting from crushing waste batteries for recycling as quickly as possible, thereby allowing for the prompt determination of settlement amounts or decisions regarding processing for other uses based on the type / grade.

Description

Technology Field

[0001] The present invention relates to a system and method of operation for analyzing the type / grade of black powder based on Laser Induced Breakdown Spectroscopy (LIBS) as illustrated in FIG. 1, while the components of black powder containing lithium, which is produced by separating waste batteries down to the cell unit and finely crushing them into powder form, and useful metals such as nickel and cobalt, are being transported on a conveyor belt. More specifically, the invention relates to a LIBS-based system for analyzing the components and recycling grade of black powder and a method of operation control thereof, which enables the rapid determination of the type / grade of black powder by securing key information such as the lithium content, nickel content, and cobalt content within the black powder produced by crushing waste batteries for recycling as quickly as possible, thereby allowing for the prompt determination of settlement amounts or decisions regarding processing for other uses based on the type / grade. Background Technology

[0002] With the surge in demand for secondary batteries, typified by electric vehicle batteries, there is a rapidly increasing demand for technologies capable of separating, sorting, and recovering key raw materials from waste batteries. LiNi is a cathode active material produced as a flagship product by domestic companies and used in automobiles and other applications. x Co y Mn z The black powder produced by cell-unit grinding of a ternary (NCM) secondary battery of the O2-based lithium-ion battery type consists of lithium metal oxide (Li-Metal Oxide: lithium, nickel, cobalt, and manganese) as the positive electrode material, graphite as the negative electrode material, aluminum and copper as the metal electrode (Foil), a small amount of electrolyte (Electrolyte solution), carbon black, and binder.

[0003] Among the general waste battery recycling industries, there is a method of repurposing degraded waste battery cells for other uses by changing their packaging, but, in contrast, waste battery recycling technology is also developing day by day to extract lithium (Li), an expensive core material that constitutes the cathode, and nickel (Ni), cobalt (Co), and manganese (Mn), which are major metals of the ternary (NCM) system, from black powder (intermediate raw material) produced by crushing waste batteries into cell units.

[0004] Meanwhile, according to Korean Published Patent No. 10-2012-0094619 (published August 27, 2012) disclosed in relation to this, a general waste battery is in the form of a waste battery pack, and the waste battery pack comprises a plurality of electrically connected battery modules and further comprises a plurality of battery cells electrically connected thereto, wherein LiNi is used as the positive electrode active material. x Co y Mn z A method is presented comprising the steps of: obtaining a black powder through cell-unit crushing obtained by disassembling a waste battery pack of a lithium-ion battery type ternary (NCM) secondary battery using O2, separating the powder by particle size to recover valuable metal powder, and obtaining a leaching solution by acid leaching the obtained valuable metal powder in a reducing atmosphere; separating lithium from the leaching solution to obtain a sulfuric acid solution of nickel, cobalt, and manganese; preparing a ternary hydroxide using a co-precipitation method with pH adjustment of the sulfuric acid solution of nickel, cobalt, and manganese; and preparing a positive electrode active material by mixing and sintering the ternary hydroxide and a lithium compound.

[0005] However, this method merely proposes a method of analyzing the concentration of valuable metals using Inductively Combined Plasma Optical Emission Spectroscopy (ICP) after sampling the valuable metal powder following reductive leaching; consequently, it fails to provide a separate method for analyzing the grade of black powder based on the amounts of highly recyclable components such as lithium (Li), nickel (Ni), and cobalt (Co) by analyzing them in advance.

[0006] In the prior art disclosed in Korean Registered Patent No. 10-2253804, a method is presented for extracting a black powder + metal mixture from spent secondary batteries by pulverizing nickel (Ni) and cobalt (Co) while restoring their magnetism through low-temperature pyrolysis; however, this also fails to provide a means to analyze the grade of the black powder based on the amount of lithium (Li), nickel (Ni), and cobalt (Co) components by analyzing them in advance. Furthermore, another prior art disclosed in Korean Published Patent No. 10-2023-0054978 (published April 25, 2023) proposes a method for classifying the recycling grade of spent batteries through inspection of each unit cell contained in the spent battery. This method involves conducting external inspections of the battery cells and charge / discharge tests on the battery in a state prior to crushing to obtain data such as voltage and temperature values ​​during charging, voltage and temperature values ​​during discharging, and furthermore, residual capacity and internal resistance values, and the recycling grade determined based on these data Since it only restricts the method of classifying such waste batteries as material-recycled waste batteries when they fall outside the preset effective range, strictly speaking, it is a technology focused on the reuse of batteries with weakened functionality, and it is unable to propose a method for utilizing waste batteries in the material recycling stage or a technology related to the grading of black powder to distinguish their utilization value.

[0007] Recently, there has been a significant trend toward the increased use of high-nickel NCM batteries, which pursue high energy density by lowering the proportion of cobalt (Co)—a rare metal classified as a conflict mineral that is relatively expensive and relies heavily on the Congo region for production—and instead increasing the nickel (Ni) content. Consequently, in the field of waste battery material recycling technology, distinguishing black powder produced from waste batteries with high cobalt content—which is a conventional product—is becoming an even more critical technical challenge. Prior art literature

[0008] Korean Published Patent No. 10-2012-0094619 (Published Aug. 27, 2012) Korean Registered Patent No. 10-2253804 (Announced May 18, 2021) Korean Published Patent No. 10-2023-0054978 (Published April 25, 2023) The problem to be solved

[0009] The main technical objective of the present invention is to provide a system for analyzing the components and recycling grade of black powder from waste batteries based on LIBS (Laser Induced Breakdown Spectroscopy) and a method for controlling the operation thereof, which is devised to solve the problems of the conventional technology described above and makes it very easy to distinguish the composition and grade of black powder from primary treated waste batteries simply, quickly, and accurately by adding a certain level of data processing using only plasma intensity data.

[0010] The problems of the present invention are not limited to those mentioned above, and other unmentioned problems will be clearly understood by those skilled in the art from the description below. means of solving the problem

[0011] According to one aspect of the present invention for solving the above problems, a LIBS-based black powder classification system is provided, comprising: a sample transport unit that contains black powder of waste batteries subject to component analysis and grade determination and transports it through a conveyor system; a laser irradiation unit that irradiates a pulsed laser to generate plasma from the black powder on the sample transport unit; an optical unit that changes the light path of the pulsed laser or focuses it; a spectroscopic unit that spectrally analyzes the plasma and spectrally analyzes light for the black powder to convert it into a wavelength-specific spectrum; a ratio calculation unit that collects the wavelength-specific spectrum for the black powder from the spectroscopic unit and calculates the ratio of light intensity for two selected wavelengths corresponding to the component composition of the black powder according to the collected wavelength-specific spectrum; and a grade determination unit that determines the grade of the black powder according to the calculated ratio of light intensity.

[0012] In a preferred embodiment of the present invention, the two wavelengths selected by the ratio calculation unit are preferably selected such that when the intensity ratio of the LIBS values ​​of a specific element (e.g., a grade classified according to the component composition of nickel (Ni), cobalt (Co), and manganese (Mn)) which serves as a criterion for classifying a grade having a specific component composition in a black powder material (e.g., a grade classified according to the component composition of nickel (Ni), cobalt (Co), and manganese (Mn)) is calculated for each grade according to the component composition of the black powder and the intensity ratio of the LIBS values ​​of a specific element (e.g., a grade classified according to the component composition of nickel (Ni), cobalt (Co), manganese (Mn)) which serves as a criterion for classifying a grade having a specific component composition in the black powder material, and the intensity ratio of the LIBS values ​​of a specific wavelength selected from the plasma emission spectrum generated for the elements iron (Fe), copper (Cu), zinc (Zn), chromium (Cr), and aluminum (Al) which serve as the impurity base of the black powder) is calculated for each grade according to the component composition of the black powder and the distribution area of ​​the ratio values ​​is accumulated over the entire laser output value range, the two wavelengths are selected such that the distribution area of ​​the accumulated intensity ratio values ​​can be classified with a probability greater than or equal to a set value, to the extent that the quality grade of the black powder can be inferred from the intensity ratio of the LIBS values.

[0013] In another preferred embodiment of the present invention, the two wavelengths selected by the ratio calculation unit are preferably selected to have a resolution sufficient to infer the quality grade of the black powder from the ratio of the LIBS intensity values ​​when calculating the intensity ratio of a first wavelength selected from a plasma emission spectrum generated for one element selected as a group including nickel (Ni), cobalt (Co), and manganese (Mn), which serves as a criterion for classifying grades having a specific component composition in the black powder material (e.g., grades classified according to the component composition of nickel (Ni), cobalt (Co), and manganese (Mn)), and another element selected as a group including nickel (Ni), cobalt (Co), and manganese (Mn) in the black powder material, and when calculating the various distribution states of the ratio values ​​by calculating the intensity ratio according to the component composition of the black powder. Effects of the invention

[0014] According to the present invention for solving the above-mentioned problem, a component composition analysis based on LIBS is performed in real time on black powder corresponding to a primary processed product for the material recycling of battery cells of waste batteries being transported on a conveyor system such as a processing plant equipped with a waste battery recycling system, thereby making it possible to easily, quickly, and accurately determine the component composition of the black powder through the analysis results. Furthermore, by utilizing the analysis results, a grade evaluation of the black powder to be recycled (in particular, a grade evaluation based on the content of expensive rare metals) can be additionally performed, and furthermore, according to the grade determined through this, the settlement amount between recycling companies or the decision to process for other uses can be carried out promptly. Brief explanation of the drawing

[0015] FIG. 1 is a drawing illustrating an example of a LIBS system to which the present invention is applied. FIG. 2 is a configuration diagram of a LIBS-based black powder classification system according to a preferred embodiment of the present invention. The graphs in FIGS. 3a to 3h are graph diagrams showing data on the intensity (Y-axis: Intensity (au)) for various wavelengths obtained when changing the wavelength (X-axis: Wavelength (nm)) of LIBS-based plasma light that detects nickel (Ni), cobalt (Co), and manganese (Mn), which serve as criteria for distinguishing specific elements according to component composition in black powder (e.g., NCM-based batteries). FIG. 4a is a diagram illustrating the state in which the normalized LIBS intensity value of the first wavelength (NiⅠ 359.77 nm) having a wavelength of 359.77 nm selected from the plasma emission spectrum changes according to the change in the composition (concentration (%)) of the nickel (Ni) component included in the black powder, and FIG. 4b is a diagram illustrating the state in which the normalized LIBS intensity value of the second wavelength (NiⅡ 231.6 nm) having a wavelength of 231.6 nm selected from the plasma emission spectrum changes according to the change in the composition (concentration (%)) of the nickel (Ni) component included in the black powder. Figure 5 is a table schematically summarizing various wavelength values ​​of plasma light selected to be suitable for detecting nickel (Ni), cobalt (Co), manganese (Mn), and lithium (Li) contained in black powder as major components constituting the cathode material of a secondary battery from the plasma emission spectrum (e.g., 300.25 nm, 301.2 nm, 308.08 nm, 351.51 nm, 361.05 nm, 361.94 nm, 385.83 nm in the case of nickel (Ni)). FIG. 6 is a flowchart illustrating the state in which a method for classifying black powder grades is implemented through the operation control method of the LIBS-based black powder classification system exemplified in FIG. 2. Figure 7 is a diagram illustrating the specific sequence in which the most critical grade classification step proceeds in the overall flowchart of Figure 6. FIG. 8 is a graph showing the distribution of various ratio values ​​calculated by determining the LIBS intensity ratio of the first wavelength of a first element and the second wavelength of a second element selected from the plasma emission spectrum according to the composition of the black powder, so as to verify the practical utility of black powder grade classification according to the flowcharts of FIG. 6 and 7, and FIG. 9 is an enlarged view of a specific part of FIG. 8. Figure 10 is a graph showing the ratio of light intensity values ​​for LIBS-based plasma light (wavelength λ1: nickel (Ni) plasma light with a wavelength of 361.94 nm) for nickel (Ni), the first element that is a constituent material of the secondary battery, and plasma light (wavelength λ2: manganese (Mn) plasma light with a wavelength of 403.31 nm) for manganese (Mn), the second element that is another constituent material, for four grades (Grade A (NCM811) High Nickel, B (NCM622), C (NCM523), D (NCM111)) while changing the type of cathode material. Figure 11 is a graph showing light intensity ratio value data for four grades (Grade A (NCM811) High Nickel, B (NCM622), C (NCM523), D (NCM111)) while changing the types of cathode materials with different nickel, cobalt, and manganese contents, by changing the wavelength of the plasma light for cobalt (Co) (λ1; 238.89 nm) instead of the LIBS-based plasma light for nickel (Ni), the first element in the figure above (wavelength λ1: nickel (Ni) plasma light with 361.94 nm), and changing the plasma light for manganese (Mn), the second element (Manganese (Mn) plasma light with 403.31 nm), to the plasma light for manganese (Mn) (wavelength λ2: manganese (Mn) plasma light with 259.37 nm). Specific details for implementing the invention

[0016] Preferred embodiments of the present invention, in which the objectives of the present invention can be specifically realized, will be described below with reference to the attached drawings. In describing preferred embodiments of the present invention, the same names and reference numerals are used for identical components, and additional descriptions thereof will be omitted.

[0017] FIGS. 1 and 2 are configuration diagrams of a LIBS-based black powder classification system according to a preferred embodiment of the present invention, FIG. 6 is a flowchart illustrating the state in which a method for classifying the grade of black powder is implemented through the operation control method of the LIBS-based black powder classification system exemplified in FIGS. 1 and 2, and FIG. 7 is a diagram exemplifying the specific sequence in which the most critical grade classification step proceeds in the overall flowchart of FIG. 6. The arrangement forms and number of components of the present invention shown in the embodiments presented in the drawings are not limited to the specific embodiments exemplified in the drawings and various modifications are possible, and the arrangement state, location, and number are not limited to this embodiment alone.

[0018] A LIBS-based black powder classification system (100) according to a preferred embodiment of the present invention, as illustrated in the attached drawings FIG. 1 and FIG. 2,

[0019] A sample transport unit (110) that holds black powder from waste batteries and transports it through a conveyor system;

[0020] A laser irradiation unit (120) that irradiates a pulsed laser to generate plasma from black powder on a sample transport unit;

[0021] An optical unit (130) that changes the light path of the above-mentioned pulse laser or focuses the light;

[0022] A spectroscopic unit (140) that spectrally analyzes the above plasma and spectrally analyzes light for the above black powder to convert it into a wavelength-specific spectrum;

[0023] A ratio calculation unit (151) that collects wavelength-specific spectra for the black powder from the spectroscopic unit (140) and calculates the ratio of light intensity for two selected wavelengths corresponding to the component composition of the black powder according to the collected wavelength-specific spectra; and

[0024] It is preferable that the system includes a grade determination unit (152) that determines the grade of the black powder according to the ratio of the light intensity calculated above.

[0025] Here, the two wavelengths selected by the ratio calculation unit (151) are preferably selected to have a resolution sufficient to infer the quality grade of the black powder from the ratio of the LIBS intensity values ​​when calculating the intensity ratio of a first wavelength selected from a plasma emission spectrum for one element selected as a group including nickel (Ni), cobalt (Co), and manganese (Mn), which serves as a criterion for classifying the black powder material into grades having a specific component composition (e.g., grades classified according to the component composition of nickel (Ni), cobalt (Co), and manganese (Mn)), and another element selected as a group including nickel (Ni), cobalt (Co), and manganese (Mn), and calculating the various distribution states of the ratio values ​​according to the component composition of the black powder.

[0026] Here, graphs showing data on the intensity (Y-axis: Intensity (au)) for various wavelengths obtained when changing the wavelength (X-axis: Wavelength (nm)) of LIBS-based plasma light that detects nickel (Ni), cobalt (Co), and manganese (Mn), which serve as criteria for distinguishing specific elements according to component composition in black powder (e.g., NCM-based batteries), can be presented in FIGS. 3a to 3h.

[0027] And, Fig. 4a may be referenced as a diagram illustrating the state in which the normalized LIBS intensity value of the first wavelength (Ni I 359.77 nm) having a wavelength of 359.77 nm selected from the plasma emission spectrum changes according to the change in the composition (concentration (%)) of the nickel (Ni) component included in the black powder, and Fig. 4b may be referenced as a diagram illustrating the state in which the normalized LIBS intensity value of the second wavelength (Ni II 231.6 nm) having a wavelength of 231.6 nm selected from the plasma emission spectrum changes according to the change in the composition (concentration (%)) of the nickel (Ni) component included in the black powder.

[0028] Thus, the various wavelength values ​​of plasma light selected to be suitable for detecting nickel (Ni), cobalt (Co), manganese (Mn), and lithium (Li) contained in black powder as major components constituting the cathode material of a secondary battery from the plasma emission spectrum (e.g., 300.25 nm, 301.2 nm, 308.08 nm, 351.51 nm, 361.05 nm, 361.94 nm, 385.83 nm in the case of nickel (Ni)) can be schematically summarized as shown in the attached drawing Fig. 5.

[0029] In this way, when calculating the ratio (Intensity Ratio) of the LIBS intensity value of the first wavelength (λ1) selected from the plasma emission spectrum generated for one specific element (Ni, Co, Mn) (first element) constituting the black powder and the LIBS intensity value of the second wavelength (λ2) selected from the plasma emission spectrum generated for another specific element (Ni, Co, Mn) (second element) constituting the black powder according to grades based on the composition of the black powder, various cases exemplified in the attached drawing Fig. 8 may be used.

[0030] Among the cases of FIG. 8, as illustrated in the enlarged view of FIG. 9 of the attached drawing, the grade determination unit (152) can clearly distinguish and determine the type and grade of the black powder to be measured as "NCM811" and "Grade A" or "NCM622" and "Grade B" by the measured intensity ratio value, if the first area (S1) where the ratio value for the first grade (Grade A: NCM811) and the second area (S2) where the ratio value for the second grade (Grade B: NCM523) that is distinguished therefrom have high distinction resolution without any overlapping area (see FIG. 10 of the attached drawing), then the first element and the first wavelength and the second element and the second wavelength are selected (areas ① and ② of FIG. 9).

[0031] Meanwhile, in these cases (regions ① and ② of FIG. 9), the first region (S3) in which the ratio value for the third grade (Grade C: NCM523) is accumulated and the second region (S4) in which the ratio value for the fourth grade (Grade D: NCM111) is accumulated are mutually overlapping and do not have a resolution sufficient to distinguish them (see attached drawing FIG. 10). Therefore, the grade determination unit (152) changes the first element and the first wavelength and the second element and the second wavelength to the wavelength of cobalt (Co) plasma light (λ1; 238.89 nm) as shown in attached drawing FIG. 9 ③ and FIG. 11, and changes the second element and the second wavelength to plasma light for manganese (Mn) (plasma light of manganese (Mn) with wavelength λ2: 259.37 nm) (region ③ of FIG. 9), and the ratio By calculating the ratio of light intensity for two newly selected wavelengths through the output unit (151), the type and grade of the black powder to be measured can be additionally clearly distinguished as “NCM523” and “Grade C” or “NCM111” and “Grade D” based on the additionally measured intensity ratio value.

[0032] Here, it would be preferable to integrate the ratio calculation unit (151) and the grade determination unit (152) into a single controller (150), and it would be even more preferable to additionally include a display unit (160) for outputting and displaying the determination result of the grade determination unit (152).

[0033] According to one embodiment of the most preferred method of the present invention, which specifically summarizes such processes, a method for controlling operation to analyze the type and recycling grade based on black powder component analysis in a LIBS-based waste battery black powder component analysis and recycling grade analysis system is provided, as illustrated in the attached drawing Fig. 7. According to this, as illustrated in the attached drawing Fig. 6,

[0034] A pulse laser irradiation step (S100) in which a pulse laser is irradiated through a laser irradiation unit (120) onto the waste battery black powder of a sample transfer unit (110);

[0035] A path change and plasma concentration step (S200) in which the optical path of a pulsed laser is changed by an optical unit (130) and the plasma reflected by black powder is concentrated;

[0036] A plasma spectroscopy step (S300) in which the concentrated plasma is spectrally separated by a spectroscopic unit (140) and converted into a wavelength-specific spectrum;

[0037] A plasma light intensity ratio calculation step (S400) that calculates the ratio of plasma light intensities of black powder subject to judgment inspection for two wavelengths (λ1, λ2) selected to correspond to the component composition of the black powder according to the collected wavelength spectrum through a ratio calculation unit (151); and

[0038] A method for controlling the operation of a LIBS-based waste battery black powder component analysis and recycling grade analysis system is provided, comprising a grade determination step (S500) in which the type and grade of black powder are determined by a grade determination unit (152) according to the ratio of light intensity calculated in the plasma light intensity ratio calculation step (S4000).

[0039] Here, the two wavelengths (λ1, λ2) selected in the plasma light intensity ratio calculation step (S400) are, when calculating the intensity ratio for each grade according to the component composition of the black powder and calculating the various distribution states of the ratio values ​​by calculating the ratio of the LIBS intensity values, the two wavelengths having a resolution sufficient to infer the quality grade of the black powder from the ratio of the LIBS intensity values, wherein the LIBS intensity value of the first wavelength is selected from the plasma emission spectrum generated for one element selected as a group including nickel (Ni), cobalt (Co), and manganese (Mn), which serves as a criterion for classifying grades having a specific component composition in the black powder material (e.g., grades classified according to the component composition of nickel (Ni), cobalt (Co), and manganese (Mn)), and the LIBS intensity value of the second wavelength is selected from the plasma emission spectrum generated for another element selected as a group including nickel (Ni), cobalt (Co), and manganese (Mn), which is a specific element in the black powder material, and the LIBS intensity value of the second wavelength is calculated. It is desirable to be selected.

[0040] Of course, as explained above, if the area of ​​the overlapping region (S34) is 5% or more of the area of ​​the third region (S3) or the fourth region (S4) (as in the case illustrated in the attached drawing Fig. 10), it is considered that the distribution area of ​​the accumulated ratio values, which can infer the type / grade of black powder from the ratio value of the LIBS intensity value, cannot be distinguished with a probability greater than the set value (high resolution requirement not met), and thus control must be exercised to select and verify a combination of wavelengths other than the two wavelengths (λ1, λ2).

[0041] On the other hand, if the area of ​​the overlapping region (S34) is less than 5% of the area of ​​the third region (S3) or the fourth region (S4), it may be configured to determine the type / grade of the region by comparing the area between the third region boundary value (K3_min) and the area between the fourth region boundary value (K4_max) based on the ratio value of the measured plasma light intensity, and considering it to be included in the region corresponding to the larger value.

[0042] As illustrated in the flowchart of the attached drawing Fig. 7, in a more preferred embodiment of the present invention, more specifically, the grade determination step (S500) is capable of selecting the type / grade of black powder corresponding to the ratio value of the plasma light intensity for two wavelengths (λ1, λ2) selected in the plasma light intensity ratio calculation step (S400).

[0043] If the above ratio value is included only in the first region (S510), it is determined as NCM811 (Grade A) (S511), and [including the output step (S600), "Grade A" is output to the display unit (S610)].

[0044] If the above ratio value is included only in the second region (S520), it is determined as NCM622 (Grade B) (S521), and [output "Grade B" to the display unit including the output step (S600) (S620)].

[0045] If the above ratio value is included only in the third region (S530), it is determined as NCM532 (Grade C) (S531), [including the output step (S600) to output "Grade C" to the display unit (S630)] and

[0046] It would be more preferable to configure it so that when the above ratio value is included only in the fourth region (S530), it is determined as NCM111 (Grade D) (S541) [including the output step (S600) to output "Grade D" to the display unit (S640)].

[0047] Here, the grade determination step (S500) additionally performs a step (S550) of executing an overlapping region problem solving algorithm if the ratio value is not included in only one region but is included in mutually overlapping regions, so that the type / grade of black powder can be selected in response to the ratio value of the plasma light intensity for the two wavelengths (λ1, λ2) selected in the plasma light intensity ratio calculation step (S400).

[0048] As previously examined in more detail, the grade determination unit (152) selects the first element and the first wavelength and the second element and the second wavelength by changing them, and calculates the ratio of light intensity for the two newly selected wavelengths through the ratio calculation unit (151), thereby allowing the type and grade of the black powder to be measured to be further subdivided (e.g., "NCM523" and "Grade C" or "NCM111" and "Grade D") by the additionally measured intensity ratio value, so that they can be clearly distinguished.

[0049] On the other hand, as illustrated in the enlarged view at the bottom of FIG. 10, for example, if the area of ​​the overlapping region (S34) is less than 5% of the area of ​​the third region (S3) or the fourth region (S4), it may be possible to control the area to be determined as the type / grade of the region by comparing the area between the third region boundary value (K3_min) and the area between the fourth region boundary value (K4_max) based on the ratio value of the measured plasma light intensity, and considering it to be included in the region corresponding to the larger value.

[0050] However, if the above ratio value is not specifically included in a certain area, an "ERROR" message may be displayed on the display unit (160).

[0051] In addition, the various embodiments of the method invention according to the present invention described above may be provided as another aspect (category) in the form of a recording medium having program instructions recorded thereon for implementing the operation control method described above.

[0052] As described above, preferred embodiments according to the present invention have been examined, and it is obvious to those skilled in the art that, in addition to the embodiments described above, the present invention may be embodied in other specific forms without departing from the spirit or scope thereof.

[0053] Therefore, the embodiments described above should be regarded as exemplary rather than limiting, and accordingly, the present invention is not limited to the description above but may be modified within the scope of the appended claims and their equivalents. Explanation of the symbols

[0054] 100: LIBS-based black powder sorting system 110: Sample transfer unit 120: Laser Irradiation Unit 130: Optical section 140: Spectroscopic section 150: Control unit 151: Ratio Calculation Unit 152: Grade Decision Department 160: Display section S100: Pulse laser irradiation step S200: Optical path change and plasma concentration step S300: Plasma Spectroscopic Step S400: Plasma light intensity ratio calculation step S500: Grade determination stage S600: Output stage S3: Third Zone S4: The Fourth Area λ1, λ2: 2 wavelengths K3_min: Third region boundary value K4_max: 4th region boundary value

Claims

Claim 1 A LIBS-based black powder classification system (100) comprising: a sample transport unit (110) that contains black powder from waste batteries and transports it via a conveyor system; a laser irradiation unit (120) that irradiates a pulsed laser to generate plasma from the black powder on the sample transport unit; an optical unit (130) that changes the light path of the pulsed laser or focuses it; a spectroscopic unit (140) that spectrally analyzes the plasma and spectrally analyzes light for the black powder to convert it into a wavelength-specific spectrum; and a ratio calculation unit (151) that collects the wavelength-specific spectrum for the black powder from the spectroscopic unit (140) and calculates the ratio of light intensity for two selected wavelengths corresponding to the component composition of the black powder according to the collected wavelength-specific spectrum.The system comprises a grade determination unit (152) that determines the grade of the black powder according to the ratio of light intensity calculated above, wherein the two wavelengths selected by the ratio calculation unit (151) are calculated by each grade according to the component composition of the black powder and the quality grade of the black powder is determined from the ratio of the LIBS intensity value of the first wavelength selected from the plasma emission spectrum generated for one element selected as a group including nickel (Ni), cobalt (Co), and manganese (Mn), which serves as a criterion for classifying grades having a specific component composition in the black powder material (e.g., grades classified according to the component composition of nickel (Ni), cobalt (Co), and manganese (Mn)), and the LIBS intensity value of the second wavelength selected from the plasma emission spectrum generated for another element selected as a group including nickel (Ni), cobalt (Co), and manganese (Mn), which serves as a criterion for classifying grades having a specific component composition in the black powder material, and the ratio of the LIBS intensity value of the second wavelength selected from the plasma emission spectrum generated for another element selected as a group including nickel (Ni), cobalt (Co), and manganese (Mn), which is a specific element in the black powder material, when calculating the various distribution states of the ratio values, the quality grade of the black powder is determined from the ratio value of the LIBS intensity value. A LIBS-based waste battery black powder component analysis and recycling grade analysis system, wherein two wavelengths having resolution sufficient for inference are selected, and the grade determination unit (152) is configured to select the type / grade of black powder corresponding to the ratio value of light intensity for the two wavelengths (λ1, λ2) selected by the ratio calculation unit (151), wherein the ratio value is determined as NCM811 (Grade A) (S511) when the ratio value is included only in a first region (S510), determined as NCM622 (Grade B) (S521) when the ratio value is included only in a second region (S520), determined as NCM532 (Grade C) (S531) when the ratio value is included only in a third region (S530), and determined as NCM111 (Grade D) (S541) when the ratio value is included only in a fourth region (S530). Claim 2 delete Claim 3 delete Claim 4 A LIBS-based waste battery black powder component analysis and recycling grade analysis system according to claim 1, wherein in the case where a first region (S3) in which the ratio value for a specific grade is accumulated by a selected wavelength and a second region (S4) in which the ratio value is accumulated for a grade distinct therefrom overlap each other and does not have a resolution sufficient to distinguish them, and the area of ​​the overlapping region (S34) is 5% or more of the area of ​​the third region (S3) or the fourth region (S4), it is considered that the distribution area of ​​the ratio values ​​accumulated enough to infer the type / grade of black powder from the ratio value of the LIBS intensity value cannot be distinguished with a probability greater than a set value, and is controlled to select and verify a combination of wavelengths other than the two wavelengths (λ1, λ2). Claim 5 A LIBS-based waste battery black powder component analysis and recycling grade analysis system according to claim 1, wherein the grade determination unit (152) is configured to determine the type / grade of black powder corresponding to the ratio value of light intensity for two wavelengths (λ1, λ2) selected by the ratio calculation unit (151), such that when the ratio value is included in both the third region and the adjacent fourth region, the area portion between the third region boundary value (K3_min) and the area portion between the fourth region boundary value (K4_max) are compared based on the measured ratio value of plasma light intensity, and the area portion corresponding to the larger value is considered to be included in the region, thereby determining the type / grade of the corresponding region. Claim 6 A LIBS-based waste battery black powder component analysis and recycling grade analysis system, characterized in that, in claim 4 or 5, when the LIBS-based steel classification system is implemented as a computer-based system, the ratio calculation unit (151) and the grade determination unit (152) are integrated into a single controller (150). Claim 7 In claim 6, the LIBS-based steel classification system is further characterized by including a display unit (160) for outputting and displaying the judgment result of the grade judgment unit (152), in a LIBS-based waste battery black powder component analysis and recycling grade analysis system. Claim 8 A method for controlling operation to classify the type and grade of black powder in a LIBS-based waste battery black powder component analysis and recycling grade analysis system, comprising: a pulse laser irradiation step (S100) of irradiating a pulse laser through a laser irradiation unit (120) onto waste battery black powder of a sample transport unit (110); a path change and plasma concentration step (S200) of changing the optical path of the pulse laser by an optical unit (130) and concentrating the plasma reflected by the black powder; a plasma spectroscopy step (S300) of spectrally analyzing the concentrated plasma by a spectrometer (140) and converting it into a wavelength-specific spectrum; and a plasma light intensity ratio calculation step (S400) of collecting the wavelength-specific spectrum of the black powder through a ratio calculation unit (151) and calculating the ratio of the plasma light intensities of the black powder to be judged for two selected wavelengths (λ1, λ2) corresponding to the component composition of the black powder according to the collected wavelength-specific spectrum. The method comprises a grade determination step (S500) in which the type and grade of the black powder are determined by a grade determination unit (152) according to the ratio of light intensity calculated in the plasma light intensity ratio calculation step (S4000), and the two wavelengths (λ1, λ2) selected in the plasma light intensity ratio calculation step (S400) are a LIBS intensity value of a first wavelength selected from a plasma emission spectrum generated for one element selected as a group including nickel (Ni), cobalt (Co), and manganese (Mn), which serves as a criterion for classifying grades having a specific component composition in the black powder material (e.g., grades classified according to the component composition of nickel (Ni), cobalt (Co), and manganese (Mn), and a specific element in the black powder material, namely nickel (Ni), cobalt (Co),When calculating the intensity ratio of LIBS values ​​of a second wavelength selected from a plasma emission spectrum generated for another element selected from a group including manganese (Mn), and calculating the various distribution states of the ratio values ​​according to grades based on the component composition of the black powder, two wavelengths having a resolution sufficient to infer the quality grade of the black powder from the ratio of LIBS intensity values ​​are selected, and the grade determination step (S500) is such that the type / grade of the black powder corresponding to the ratio value of light intensity for the two wavelengths (λ1, λ2) selected by the ratio calculation unit (151) is determined as NCM811 (Grade A) (S511) when the ratio value is included only in the first region (S510), determined as NCM622 (Grade B) (S521) when the ratio value is included only in the second region (S520), and determined as NCM532 (Grade A) when the ratio value is included only in the third region (S530). A method for controlling the operation of a LIBS-based waste battery black powder component analysis and recycling grade analysis system configured to determine as C) (S531), and to determine as NCM111 (Grade D) (S541) when the ratio value is included only in the fourth region (S530). Claim 9 delete Claim 10 delete Claim 11 A method for controlling the operation of a LIBS-based waste battery black powder component analysis and recycling grade analysis system, characterized in that, in the case of claim 8, where a first region (S3) in which the ratio value for a specific grade is accumulated by a selected wavelength and a second region (S4) in which the ratio value is accumulated for a grade distinguished therefrom overlap each other and does not have a resolution sufficient to distinguish them, and where the area of ​​the overlapping region (S34) is 5% or more of the area of ​​the third region (S3) or the fourth region (S4), the distribution area of ​​the ratio values ​​accumulated enough to infer the type / grade of black powder from the ratio value of the LIBS intensity value is considered not to be distinguishable with a probability greater than a set value, and a step (S550) of executing an overlapping region problem solving algorithm is additionally performed to select and verify a combination of wavelengths other than the two wavelengths (λ1, λ2). Claim 12 A method for controlling the operation of a LIBS-based waste battery black powder component analysis and recycling grade analysis system, characterized in that, in the case of claim 8, a first region (S3) in which the ratio value for a specific grade is accumulated by a selected wavelength and a second region (S4) in which the ratio value for a grade distinct therefrom is accumulated overlapped with each other and does not have a resolution sufficient to distinguish them, and the area of ​​the overlapping region (S34) is less than 5% of the area of ​​the third region (S3) or the fourth region (S4), the area between the third region boundary value (K3_min) and the area between the fourth region boundary value (K4_max) are compared based on the ratio value of the measured plasma light intensity, and the region is considered to be included in the region corresponding to the larger value, thereby determining the type / grade of the region. Claim 13 A method for controlling the operation of a LIBS-based waste battery black powder component analysis and recycling grade analysis system, wherein, in claim 12, the method further comprises a step (S600) of outputting the type / grade of black powder determined in the grade determination step (S500) to an output device (display unit). Claim 14 A recording medium having program instructions recorded thereon for implementing a method of operation control according to any one of paragraphs 8 and 11 through 13.

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