WO2023033522A1 - Tdr을 이용한 전지셀의 내부 결함 검출장치 및 방법 - Google Patents
Tdr을 이용한 전지셀의 내부 결함 검출장치 및 방법 Download PDFInfo
- Publication number
- WO2023033522A1 WO2023033522A1 PCT/KR2022/012971 KR2022012971W WO2023033522A1 WO 2023033522 A1 WO2023033522 A1 WO 2023033522A1 KR 2022012971 W KR2022012971 W KR 2022012971W WO 2023033522 A1 WO2023033522 A1 WO 2023033522A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- battery cell
- electric pulse
- electrode
- tdr
- waveform
- Prior art date
Links
- 230000007547 defect Effects 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000002310 reflectometry Methods 0.000 claims abstract description 6
- 238000005259 measurement Methods 0.000 claims description 58
- 238000001514 detection method Methods 0.000 claims description 23
- 238000003466 welding Methods 0.000 claims description 21
- 239000007772 electrode material Substances 0.000 claims description 6
- 230000000644 propagated effect Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 169
- 230000000052 comparative effect Effects 0.000 description 13
- 238000007689 inspection Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/20—Investigating the presence of flaws
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/382—Arrangements for monitoring battery or accumulator variables, e.g. SoC
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/389—Measuring internal impedance, internal conductance or related variables
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/392—Determining battery ageing or deterioration, e.g. state of health
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/50—Testing of electric apparatus, lines, cables or components for short-circuits, continuity, leakage current or incorrect line connections
- G01R31/52—Testing for short-circuits, leakage current or ground faults
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4285—Testing apparatus
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/569—Constructional details of current conducting connections for detecting conditions inside cells or batteries, e.g. details of voltage sensing terminals
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/08—Locating faults in cables, transmission lines, or networks
- G01R31/11—Locating faults in cables, transmission lines, or networks using pulse reflection methods
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/172—Arrangements of electric connectors penetrating the casing
- H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
- H01M50/178—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for pouch or flexible bag cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to an apparatus and method for detecting internal defects of a battery cell using a TDR.
- secondary batteries capable of charging and discharging have been widely used as energy sources for wireless mobile devices.
- secondary batteries are attracting attention as an energy source for electric vehicles, hybrid electric vehicles, etc., which are proposed as a solution to air pollution such as existing gasoline vehicles and diesel vehicles using fossil fuels. Therefore, the types of applications using secondary batteries are diversifying due to the advantages of secondary batteries, and it is expected that secondary batteries will be applied to more fields and products than now.
- These secondary batteries are sometimes classified into lithium ion batteries, lithium ion polymer batteries, lithium polymer batteries, etc., depending on the composition of electrodes and electrolytes. It is increasing.
- secondary batteries include a cylindrical battery and a prismatic battery in which the electrode assembly is embedded in a cylindrical or prismatic metal can, and a pouch type in which the electrode assembly is embedded in a pouch-type case of an aluminum laminate sheet, depending on the shape of the battery case.
- the electrode assembly which is classified as a battery and is embedded in a battery case, is a power generating device capable of charging and discharging, consisting of a positive electrode, a negative electrode, and a separator structure interposed between the positive electrode and the negative electrode.
- a jelly-roll type in which a separator is wound on the surface
- a stack type in which a plurality of positive and negative electrodes of a predetermined size are sequentially stacked in a state in which a separator is interposed.
- the positive electrode and the negative electrode are formed by applying a positive electrode slurry containing a positive electrode active material and a negative electrode slurry including a negative electrode active material to a positive electrode current collector and a negative electrode current collector, respectively, and then drying and rolling the same.
- an electrode tab is formed on one side of the electrode assembly to connect the battery cell to the outside, and an electrode lead is welded to the electrode tab.
- the electrode lead is drawn out of the battery case.
- disconnection due to cracks in the electrode tab may occur due to a difference in elongation between the holding part and the uncoated part, and a physical external force due to welding.
- various defects such as poor welding between electrode tabs and electrode leads, cracks at the boundary between the uncoated portion and the holding portion that occur during the electrode tab formation process, dendrite growth that causes internal short circuits, and damage to the separator that may occur during the assembly process are various. can occur on location.
- assembling a battery module or a battery pack including the defects causes a problem in that performance is greatly deteriorated, so it is important to detect them in advance and distinguish them from normal battery cells.
- a CT inspection method, an X-ray inspection method, or an eddy current inspection method has been used as a non-destructive inspection method.
- the conventional method described above is capable of detecting internal defects, but takes some inspection time, is very inefficient in terms of the process, and has a problem in that inspection accuracy is not high.
- the present invention has been made to solve the above problems, and an object of the present invention is to provide a battery cell internal defect detection device and method capable of quickly and accurately detecting various internal defects of a battery cell in an actual mass production process.
- An apparatus for detecting internal defects of a battery cell has a structure in which an electrode assembly having at least one or more electrode tabs formed on one or both sides thereof is accommodated in a battery case, and the electrode tab is connected to an electrode lead drawn out of the battery case
- a battery cell having a TDR (Time Domain Reflectometry) module for applying an electric pulse to the inside of the battery cell and detecting a reflected wave of the electric pulse and comparing a measurement waveform generated by detecting a defect with a reference waveform ; and a signal line electrically connecting the TDR module and the electrode lead of the battery cell, wherein the electric pulse is applied along the longitudinal direction of the battery cell.
- TDR Time Domain Reflectometry
- the TDR module the electric pulse generator for generating an electric pulse applied to the inside of the battery cell; a reflected wave detector detecting a reflected wave of the electric pulse; and a determination unit that generates a measurement waveform through the reflected wave of the electric pulse sensed by the reflected wave detector, compares the measured waveform with a reference waveform, and determines that a defect has occurred when an offset occurs.
- the change rate of the impedance represented by the measurement waveform compared to the reference waveform is 10% or more, it can be determined as an offset of defect occurrence.
- the region of the battery cell is a welding part in which the electrode tab of the battery cell and the electrode lead are joined by welding, an electrode tab part in which the electrode tab is located, a holding part in which an electrode active material is applied, and a boundary portion that is a boundary area between the electrode tab portion and the holding portion.
- the reference waveform may be a measurement waveform generated by detecting a reflected wave reflected by applying an electric pulse into the normal battery cell.
- the TDR module may include a first TDR module for applying an electric pulse signal through a first electrode lead; and a second TDR module for sequentially applying an electric pulse signal through a second electrode lead, wherein the signal line comprises: a first signal line electrically connecting the first electrode lead and the first TDR module; and a second signal line electrically connecting the second electrode lead and the second TDR module.
- a ground line electrically connecting the TDR module and the ground surface on which the battery cell is disposed.
- the battery cell may be disposed parallel to the ground plane in the longitudinal direction.
- a fixing member for fixing the electrode lead of the battery cell may be further included.
- the present invention provides a method for detecting internal defects of a battery cell.
- a method for detecting internal defects of a battery cell includes applying an electric pulse to the inside of a battery cell by a TDR module through a signal line electrically connected to an electrode lead of the battery cell; Generating a measurement waveform by detecting, by a TDR module, a reflected wave generated as the electric pulse propagates along the length direction of the battery cell through a signal line; and comparing the measurement waveform generated by the TDR module with a reference waveform to detect whether or not a defect has occurred.
- the TDR module compares the measured waveform with a reference waveform and an offset occurs, it may be determined that a defect has occurred.
- the TDR module may compare a measurement waveform and a reference waveform generated for each region of a battery cell divided along the length direction of the battery cell to determine whether a defect occurs for each region.
- the area of the battery cell includes a welding portion in which the electrode tab of the battery cell and the electrode lead are joined by welding, an electrode tab portion in which the electrode tab is located, a holding portion in which an electrode active material is applied, and the electrode tab and holding portion.
- a boundary portion that is a negative boundary area may be included.
- the TDR module applying an electric pulse to the inside of the battery cell through the signal line connected to the electrode lead of the normal battery cell; Generating a measurement waveform by receiving, by a TDR module, a reflected wave generated as the electric pulse propagates along the length direction of the normal battery cell through a signal line; and setting the measurement waveform as a reference waveform.
- TDR Time Domain Reflectometry
- FIG. 1 is a cross-sectional view showing the structure of a general battery cell.
- FIG. 2 is a schematic diagram showing an internal defect detection device and measurement waveforms of a battery cell according to one embodiment of the present invention.
- FIG. 3 is a block diagram showing the configuration of a TDR module according to one embodiment of the present invention.
- 4A and 4B are schematic diagrams showing an internal defect detection device and measurement waveforms of a battery cell according to another embodiment of the present invention.
- FIG. 5 is a flowchart illustrating a sequence of a method for detecting internal defects of a battery cell according to one embodiment of the present invention.
- 6A to 6D are graphs showing measurement waveforms generated by the device for detecting internal defects of a battery cell according to the embodiment of FIG. 2 .
- being disposed "on” may include the case of being disposed at the bottom as well as at the top.
- the "length direction” of the battery cell means the direction in which the electrode tab is withdrawn
- the "width direction” means a direction perpendicular to the length direction
- An apparatus for detecting internal defects of a battery cell has a structure in which an electrode assembly having at least one or more electrode tabs formed on one or both sides thereof is accommodated in a battery case, and the electrode tab is connected to an electrode lead drawn out of the battery case
- a battery cell having a TDR (Time Domain Reflectometry) module for applying an electric pulse into the battery cell and comparing a measurement waveform generated by detecting a reflected wave of the electric pulse with a reference waveform to detect whether a defect occurs; and a signal line electrically connecting the TDR module and the electrode lead of the battery cell, wherein the electric pulse is applied along the longitudinal direction of the battery cell.
- TDR Time Domain Reflectometry
- the conventional method for detecting internal defects of a battery cell has a problem in that it takes some inspection time, is very inefficient in the process, and is difficult to apply to the actual process because the inspection accuracy is not high.
- the present invention is characterized by using a TDR module capable of detecting internal defects of a battery cell through a measurement waveform generated by applying an electric pulse through an electrode lead of the battery cell and detecting a reflected wave of the electric pulse.
- a TDR module capable of detecting internal defects of a battery cell through a measurement waveform generated by applying an electric pulse through an electrode lead of the battery cell and detecting a reflected wave of the electric pulse.
- the electric pulse propagates along the length direction of the battery cell, it provides an advantage of detecting internal defects in various regions of the battery cell divided along the length direction of the battery cell.
- the principle of detecting whether or not a defect has occurred by the TDR module is to use the fact that a reflection phenomenon occurs when an electric pulse traveling along the length of a battery cell reaches a place where an impedance change occurs inside the battery cell. That is, when there is an internal defect in the battery cell, since the change in impedance appears differently, the generation time and arrival time of the reflected wave by the electric pulse are different. Using this point, it is possible to determine whether a battery cell has a defect and a location where a defect occurs by deriving and comparing measurement waveforms for impedance over time from the reflected wave.
- FIG. 1 is a cross-sectional view showing the structure of a general battery cell.
- an electrode assembly 20 having at least one electrode tab 30 or 40 formed on one or both sides thereof is accommodated in a battery case 10, and the electrode tab 30, 40) is a structure connected to the electrode leads 31 and 41 drawn out of the battery case 10.
- the electrode leads 31 and 41 include a positive lead 31 and a negative lead 41, and the positive lead 31 and the negative lead 41 are opposite to each other in the battery case 10. It may be withdrawn, but the structure is not limited thereto. Since the electrode assembly and elements constituting the electrode assembly are known to those skilled in the art, a detailed description thereof will be omitted.
- Figure 2 is a schematic diagram showing the internal defect detection device 100 of the battery cell according to the first embodiment of the present invention and the measured waveform.
- 3 is a block diagram showing the configuration of the TDR module 110 according to the first embodiment of the present invention.
- an electrode assembly 20 having at least one or more electrode tabs 30 and 40 formed on both sides is accommodated in a battery case 10 And, with respect to a battery cell having a structure in which the electrode tabs 30 and 40 are connected to the electrode leads 31 and 41 drawn out of the battery case 10, an electric pulse is applied to the inside of the battery cell, TDR module 110 for detecting whether a defect has occurred by comparing a measurement waveform generated by detecting a reflected wave of an electric pulse with a reference waveform; and a signal line 120 electrically connecting the TDR module 110 and the electrode lead 31 of the battery cell. At this time, as the electric pulse propagates along the longitudinal direction of the battery cell, a reflected wave is generated.
- FIG. 2 shows a case in which the TDR module 110 applies an electric pulse signal through the anode lead 31 .
- the TDR module applies an electric pulse signal through the cathode lead 41, and in this case, the TDR module is electrically connected to the cathode lead 41 through a signal line.
- the TDR module 110 serves to detect whether a defect has occurred by generating an electric pulse and generating a measurement waveform through a reflected wave.
- the TDR module 110 includes an electric pulse generator 111 for generating an electric pulse applied to the inside of the battery cell; a reflected wave detector 112 for detecting a reflected wave of the electric pulse; and a determination unit 113 that generates a measurement waveform through the reflected wave of the electrical pulse detected by the reflected wave detector 112, compares the measured waveform with a reference waveform, and determines that a defect has occurred when an offset occurs; includes
- the electric pulse generator 111 may generate an electric pulse and apply it to the inside of the battery cell at predetermined time intervals.
- the time during which the electric pulse travels back and forth to the location of the defect may be determined as the predetermined time interval.
- the predetermined time interval is a negative lead to which the TDR module 110 is not connected from the TDR module 110 applying the electric pulse ( 41).
- the reflected wave detector 112 may detect a reflected wave reflected by various internal components of the battery cell while the electric pulse signal applied by the electric pulse generator 111 propagates along the length direction of the battery cell and returns. That is, by measuring the reflected wave of the electric pulse, it is possible to check the change in impedance value generated while the electric pulse applied to the inside of the battery cell by the TDR module 110 reciprocates inside the battery cell.
- the determination unit 113 generates a measurement waveform through the reflected wave of the electric pulse detected by the reflected wave detector 112 .
- the measured waveform expresses the impedance of the reflected signal of the electric pulse as a value over time.
- a measurement waveform with time as the horizontal axis and impedance as the vertical axis can be generated.
- the measured waveform shown in FIG. 2 is also expressed as an impedance (Z) value over time.
- the determining unit 113 may compare the generated measurement waveform with the reference waveform and determine that a defect occurs when an offset occurs.
- the case where the offset occurs is a case where the measurement waveform and the reference waveform do not match, and refers to a case where the impedance change ratio of the reference waveform to the measurement waveform is 10% or more.
- the reference waveform may be a measurement waveform generated by applying an electric pulse to the inside of a normal battery cell and detecting a reflected wave of the electric pulse.
- an offset occurs by generating a measurement waveform for a battery cell to be detected in the same manner as a normal battery cell and comparing it with the reference waveform, it is determined that a defect has occurred.
- the TDR module 110 for applying the electric pulse reciprocates from the negative electrode lead 41 to which the TDR module 110 is not connected.
- the electric pulse was applied at predetermined time intervals.
- FIG. 2 it was possible to generate measurement waveforms for each area of the battery cell divided along the length direction of the battery cell.
- the region of the battery cell includes a welding portion (a) in which the electrode tab 30 of the battery cell and the electrode lead 31 are joined by welding, an electrode tab portion (b) where the electrode tab 30 is located, and an electrode active material. It includes a holding part (d) which is an applied area, and a boundary part (c) which is a boundary area between the electrode tab part and the holding part.
- the signal line 120 serves to electrically connect the TDR module 110 and the battery cell through the electrode lead 31.
- the electric pulse generated by the electric pulse generator 111 of the TDR module 110 passes through the signal line 120 and is applied to the inside of the electric cell through the electrode lead 31 of the electric cell.
- the reflected wave generated inside the battery cell from the applied electric pulse is also transmitted to the reflected wave detector 112 of the TDR module 110 by sequentially passing through the electrode lead 31 and the signal line 120 of the battery cell.
- the battery cell is disposed on the ground plane 131, and the ground plane 131 and the TDR module 110 are electrically connected by the ground line 130.
- the ground plane 131 and the ground line 130 it is possible to prevent a safety problem that may occur when an electric pulse propagates to the outside instead of inside the battery cell due to an unexpected cause. That is, the TDR module 110 can safely apply an electric pulse into the battery cell.
- the battery cell may be disposed parallel to the ground surface 131 in the longitudinal direction. If the battery cell is not disposed parallel to the ground plane 131, it is difficult to accurately apply the electric pulse from the TDR module 110 in the longitudinal direction of the battery cell, and it may be difficult to generate an accurate measurement waveform. That is, when the battery cells are disposed parallel to the ground plane 131 in the longitudinal direction, the accuracy of detecting internal defects of the battery cells can be increased.
- the battery cell may be stably fixed by further including a fixing member 140 to fix the electrode leads 31 and 41 of the battery cell.
- a fixing member 140 for fixing the electrode leads 31 and 41 to the space between the ground plane 131 and the electrode leads 31 and 41 is further included so that the connection between the battery cell and the TDR module 110 is disconnected.
- a fixing member 140 is provided in a space between the ground surface 131 and the electrode leads 31 and 41 to support the lower surfaces of the electrode leads 31 and 41 .
- the fixing member 140 is not particularly limited as long as it has a shape capable of fixing the electrode leads 31 and 41 .
- it may be provided in a shape protruding from the ground surface 131 to support both sides of the electrode leads 31 and 41 .
- FIGS. 4A and 4B are schematic diagrams showing an internal defect detection device 100 'of a battery cell according to a second embodiment of the present invention and measurement waveforms.
- FIG. 4A shows that an electric pulse is applied from the first TDR module 110a connected to the anode lead 31 through the first signal line 120a and a measurement waveform is generated through a reflected wave of the electric pulse.
- FIG. 4B shows that an electric pulse is applied from the second TDR module 110b connected to the cathode lead 41 through the second signal line 120b, and a measurement waveform is generated through a reflected wave of the electric pulse.
- the measured waveforms shown in FIGS. 4A and 4B are expressed as impedance (Z) values over time.
- the TDR module 110 of the internal defect detection device 100' of the battery cell of the present embodiment is configured through the first TDR module 110a applying an electric pulse through the positive electrode lead 31 and the negative electrode lead 41. and a second TDR module 110b for sequentially applying electric pulse signals, and the signal line 120 is a first signal line 120a electrically connecting the anode lead 31 and the first TDR module 110a. ; and a second signal line 120b electrically connecting the cathode lead 41 and the second TDR module 110b. That is, the first TDR module 110a and the second TDR module 110b electrically connected to the positive lead 31 and the negative lead 41 through the first signal line 120a and the second signal line 120b, respectively. It differs in that electric pulses are applied in this sequence.
- components common to those in the first embodiment are given common reference numerals, and detailed descriptions thereof will be omitted.
- the first TDR module 110a to which the positive lead 31 is electrically connected through the first signal line 120a but also the negative lead 41 is electrically connected through the second signal line 120b.
- 2 TDR module (110b) is further included.
- the second TDR module 110b sequentially applies the electric pulse through the negative lead 41.
- the electric pulse applied by the first TDR module 110a and the electric pulse applied by the second TDR module 110b cause interference, making it difficult to form an accurate measurement waveform.
- electrical pulses may be applied to the positive lead 31 to detect defects in all regions of the positive electrode along the length direction of the battery cell.
- the positive electrode welding portion a1 which is an area where the positive electrode tab 30 of the battery cell and the positive electrode lead 31 are joined by welding
- the positive electrode tab portion where the positive electrode tab 30 is located ( b1)
- defects occurring in the positive electrode holding portion d1 which is the area coated with the positive electrode active material
- the positive electrode boundary portion c1 which is the boundary between the positive electrode tab portion b1 and the positive electrode holding portion d1
- the negative electrode welding portion a2 which is an area where the negative electrode tab 40 of the battery cell and the negative electrode lead 41 are joined by welding, and the negative electrode tab portion where the negative electrode tab 40 is located ( b2), the negative electrode holding part d2, which is the area coated with the negative electrode active material, and the negative electrode boundary part c1, which is the boundary between the negative electrode tab part b2 and the negative electrode holding part d2, can be detected.
- the first TDR module 110a first applies the electric pulse to the anode and then the second TDR module 110b applies the electric pulse to the cathode has been described.
- the order of applying the electric pulse is not particularly limited, and it is also possible to first apply the electric pulse to the cathode and then apply the electric pulse to the anode.
- the present invention provides a method for detecting internal defects of a battery cell.
- FIG. 5 is a flowchart illustrating a sequence of a method for detecting internal defects of a battery cell according to one embodiment of the present invention.
- a reference waveform serving as a criterion for determining whether a defect is detected is generated.
- the TDR module applies an electric pulse to the inside of the battery cell through a signal line electrically connected to the electrode lead of the normal battery cell (S10); generating a measurement waveform by detecting, by a TDR module, a reflected wave generated as the electric pulse propagates along the longitudinal direction of the battery cell through a signal line (S20); and setting the measurement waveform as a reference waveform (S30).
- the measurement waveform of the battery cell to be detected is generated in the same way as generating the reference waveform for the normal battery cell.
- the TDR module applies an electric pulse to the inside of the battery cell through a signal line electrically connected to the electrode lead of the battery cell to be detected (S40); generating a measurement waveform by detecting, by a TDR module, a reflected wave generated as the electric pulse propagates along the length direction of the battery cell through a signal line (S50); and comparing the measurement waveform generated by the TDR module with a reference waveform to detect whether or not a defect has occurred (S60).
- the TDR module compares the measured waveform with the reference waveform and determines that a defect has occurred if an offset has occurred.
- the TDR module compares a measured waveform and a reference waveform generated for each region of the battery cell divided along the length direction of the battery cell to determine whether a defect occurs for each region of the battery cell.
- the area of the battery cell includes a welding portion where the electrode tab of the battery cell and an electrode lead are joined by welding, an electrode tab portion where the electrode tab is located, a holding portion where an electrode active material is applied, and a boundary between the electrode tab and the holding portion. It may include a boundary that is an area.
- An electrode assembly having a plurality of positive electrode tabs formed on one side and a plurality of negative electrode tabs formed on the other side is accommodated in a battery case, and the positive and negative electrode tabs are respectively connected to positive and negative electrode leads drawn out of the battery case.
- a normal battery cell was prepared.
- a battery cell was manufactured in the same manner as in the reference example, except that only some of the plurality of positive electrode tabs were welded to the positive electrode lead and a defect was added to the welding portion, which is a region where the electrode tab and the electrode lead were joined by welding.
- a battery cell was manufactured in the same manner as in Reference Example, except that a crack was generated in at least one of the plurality of positive electrode tabs by applying an external impact to the positive electrode tab portion where the plurality of positive electrode tabs were located.
- a battery cell was manufactured in the same manner as in the reference example, except that a portion of the positive electrode active material located at the boundary between the positive electrode tab and the positive electrode holding portion, which is an area coated with the positive electrode active material, was removed.
- a battery cell was manufactured in the same manner as in the reference example, except that an internal short circuit between the positive electrode and the negative electrode was caused by penetrating the holding portion, which is the region where the positive electrode active material was applied, with a nail.
- the measurement waveform of the normal battery cell of the example was generated by the defect detection device of the battery cell of the first embodiment shown in FIG. 2 and set as a reference waveform. Measurement waveforms of the battery cells of Comparative Examples 1 to 4 were generated in the same manner and compared with the reference waveform. At this time, the reference waveform and measurement waveform are represented as impedance values over time.
- FIG. 6A shows a comparison between the measured waveform of the battery cell of Comparative Example 1 and the reference waveform using the battery cell defect detection device 100 of the first embodiment. As shown in FIG. 6A, it was confirmed that a measurement waveform having a difference of 10% or more in impedance value compared to the reference waveform appeared at the welded part (a) of the battery cell. Through this, it was possible to detect that the battery cell of Comparative Example 1 had a defect in the welding portion (a).
- FIG. 6B shows a comparison between the measured waveform of the battery cell of Comparative Example 2 and the reference waveform using the battery cell defect detection device 100 of the first embodiment. As shown in FIG. 6B, it was confirmed that a measurement waveform having a difference of 10% or more in impedance value compared to the reference waveform appeared in the electrode tab part (b) of the battery cell. Through this, it was possible to detect that the battery cell of Comparative Example 2 had a defect in the electrode tab part (b).
- FIG. 6C shows a comparison between the measured waveform of the battery cell of Comparative Example 3 and the reference waveform using the battery cell defect detection device 100 of the first embodiment. As shown in FIG. 6C, it was confirmed that a measurement waveform having a difference of 10% or more in impedance value compared to the reference waveform appeared at the boundary portion (c) of the battery cell. Through this, it was possible to detect that the battery cell of Comparative Example 3 had a defect at the boundary portion (c).
- FIG. 6D shows a comparison between the measured waveform of the battery cell of Comparative Example 4 and the reference waveform using the battery cell defect detection device of the first embodiment. As shown in FIG. 6D, it was confirmed that a measurement waveform having a difference of 10% or more in impedance value compared to the reference waveform appeared in the holding part (d) of the battery cell. Through this, it was possible to detect that the battery cell of Comparative Example 4 had a defect in the holding part (d).
- TDR Time Domain Reflectometry
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Health & Medical Sciences (AREA)
- Connection Of Batteries Or Terminals (AREA)
- Tests Of Electric Status Of Batteries (AREA)
Abstract
Description
Claims (15)
- 일측 또는 양측에 각각 적어도 하나 이상의 전극 탭들이 형성된 전극 조립체가 전지 케이스 내에 수납되고, 상기 전극 탭이 전지 케이스의 외부로 인출된 전극리드에 연결된 구조를 갖는 전지셀에 대하여,상기 전지셀 내부로 전기 펄스를 인가하고, 상기 전기 펄스의 반사파를 감지하여 생성되는 측정파형을 기준파형과 비교하여 결함 발생 여부를 검출하는 TDR(Time Domain Reflectometry) 모듈; 및상기 TDR 모듈과 전지셀의 전극리드를 전기적으로 연결하는 신호선;을 포함하되,상기 전기 펄스는 전지셀의 길이 방향을 따라 인가되는 전지셀의 내부 결함 검출 장치.
- 제1항에 있어서,상기 TDR 모듈은,상기 전지셀 내부로 인가되는 전기 펄스를 생성하는 전기 펄스 생성기;상기 전기 펄스의 반사파를 감지하는 반사파 감지기; 및상기 반사파 감지기가 감지한 전기 펄스의 반사파를 통해 측정파형을 생성하고, 상기 측정파형을 기준파형과 비교하여 오프셋(offset)이 발생한 경우 결함이 발생한 것으로 판정하는 판정부;를 포함하는 전지셀의 내부 결함 검출 장치.
- 제2항에 있어서,상기 기준파형 대비 측정파형이 나타내는 임피던스의 변화율이 10% 이상일 때, 결함 발생의 오프셋으로 판정하는 전지셀의 내부 결함 검출 장치.
- 제1항에 있어서,상기 TDR 모듈은, 전지셀의 길이 방향을 따라 구분되는 전지셀의 영역별로 생성된 측정파형을 기준파형과 비교하여, 상기 전지셀의 영역별로 결함 발생 여부를 검출하는 전지셀의 내부 결함 검출 장치.
- 제4항에 있어서,상기 전지셀의 영역은 전지셀의 전극탭과 전극리드가 용접에 의해 접합된 영역인 용접부, 전극탭이 위치하는 전극탭부, 전극 활물질이 도포된 영역인 유지부, 및 상기 전극탭부와 유지부의 경계 영역인 경계부를 포함하는 전지셀의 내부 결함 검출 장치.
- 제1항에 있어서,상기 기준파형은 정상 전지셀 내부로 전기 펄스를 인가하여 반사된 반사파를 감지하여 생성되는 측정파형인 전지셀의 내부 결함 검출 장치.
- 제1항에 있어서,상기 TDR 모듈은,제1 전극리드를 통해 전기 펄스 신호를 인가하는 제1 TDR 모듈; 및제2 전극리드를 통해 전기 펄스 신호를 순차로 인가하는 제2 TDR 모듈;을 포함하고,상기 신호선은,제1 전극리드와 제1 TDR 모듈을 전기적으로 연결하는 제1 신호선; 및제2 전극리드와 제2 TDR 모듈을 전기적으로 연결하는 제2 신호선;을 포함하는 전지셀의 내부 결함 검출 장치.
- 제1항에 있어서,상기 전지셀이 상부에 배치되는 접지면을 TDR 모듈과 전기적으로 연결하는 접지선을 더 포함하는 전지셀의 내부 결함 검출 장치.
- 제8항에 있어서,상기 전지셀은 길이방향으로 접지면과 평행하게 배치된 전지셀의 내부 결함 검출 장치.
- 제1항에 있어서,상기 전지셀의 전극리드를 고정시키기 위한 고정부재를 더 포함하는 전지셀의 내부 결함 검출 장치.
- 전지셀의 전극리드와 전기적으로 연결된 신호선을 통해 TDR 모듈이 전지셀의 내부로 전기 펄스를 인가하는 단계;상기 전기 펄스가 전지셀의 길이 방향을 따라 전파되면서 발생한 반사파를 TDR 모듈이 신호선을 통해 감지하여 측정파형을 생성하는 단계; 및상기 TDR 모듈이 생성한 측정파형을 기준파형과 비교하여 결함 발생 여부를 검출하는 단계;를 포함하는 전지셀의 내부 결함 검출 방법.
- 제11항에 있어서,상기 결함 발생 여부를 검출하는 단계에서, TDR 모듈이 측정파형을 기준파형과 비교하여 오프셋이 발생한 경우, 결함이 발생한 것으로 판정하는 전지셀의 내부 결함 검출 방법.
- 제11항에 있어서,상기 TDR 모듈이 전지셀의 길이 방향을 따라 구분되는 전지셀의 영역별로 생성된 측정파형과 기준파형을 비교하여 상기 전지셀의 영역별로 결함 발생 여부를 판정하는 전지셀의 내부 결함 검출 방법.
- 제13항에 있어서,상기 전지셀의 영역은 전지셀의 전극탭과 전극리드가 용접에 의해 접합된 영역인 용접부, 전극탭이 위치하는 전극탭부, 전극 활물질이 도포된 영역인 유지부, 및 상기 전극탭과 유지부의 경계 영역인 경계부를 포함하는 전지셀의 내부 결함 검출 방법.
- 제11항에 있어서,정상 전지셀의 전극리드와 연결된 신호선을 통하여 TDR 모듈이 전지셀의 내부로 전기 펄스를 인가하는 단계;상기 전기 펄스가 정상 전지셀의 길이 방향을 따라 전파되며 발생한 반사파를 신호선을 통해 TDR 모듈이 수신하여 측정파형을 생성하는 단계; 및상기 측정파형을 기준파형으로 설정하는 단계를 더 포함하는 전지셀의 내부 결함 검출 방법.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18/269,219 US20240061047A1 (en) | 2021-08-31 | 2022-08-30 | Device and method for detecting internal defect of battery cell by using tdr |
EP22865024.8A EP4249904A4 (en) | 2021-08-31 | 2022-08-30 | APPARATUS AND METHOD FOR DETECTING INTERNAL DEFECTS OF A BATTERY CELL USING TDR |
CN202280008406.7A CN116636064A (zh) | 2021-08-31 | 2022-08-30 | 使用tdr检测电池单体内部缺陷的设备和方法 |
JP2023537371A JP2024500140A (ja) | 2021-08-31 | 2022-08-30 | Tdrを用いた電池セルの内部欠陥検出装置および方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020210115841A KR20230032724A (ko) | 2021-08-31 | 2021-08-31 | Tdr을 이용한 전지셀의 내부 결함 검출장치 및 방법 |
KR10-2021-0115841 | 2021-08-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023033522A1 true WO2023033522A1 (ko) | 2023-03-09 |
Family
ID=85412957
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2022/012971 WO2023033522A1 (ko) | 2021-08-31 | 2022-08-30 | Tdr을 이용한 전지셀의 내부 결함 검출장치 및 방법 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20240061047A1 (ko) |
EP (1) | EP4249904A4 (ko) |
JP (1) | JP2024500140A (ko) |
KR (1) | KR20230032724A (ko) |
CN (1) | CN116636064A (ko) |
WO (1) | WO2023033522A1 (ko) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140111220A1 (en) * | 2011-05-11 | 2014-04-24 | Emazys Technologies Aps | Method for fault diagnosis on solar modules |
KR20180063927A (ko) * | 2016-12-02 | 2018-06-14 | 주식회사 나루이엠에스 | 초음파 송수신을 이용한 전기차용 배터리 불량 자동 판별 장치 및 방법 |
KR102094539B1 (ko) * | 2018-12-11 | 2020-03-27 | (주)제이디 | 배터리 비파괴 검사 장치 |
KR20200035594A (ko) * | 2018-09-27 | 2020-04-06 | 주식회사 엘지화학 | 가압력을 이용한 전지셀의 비파괴적 단선 여부 평가 방법 |
JP2020165859A (ja) | 2019-03-29 | 2020-10-08 | 日産自動車株式会社 | 二次電池用インピーダンス測定装置および二次電池の状態推定装置、並びに二次電池システムおよび二次電池用充電装置 |
KR102265423B1 (ko) * | 2019-09-19 | 2021-06-15 | 주식회사 그릿에이트 | 초음파센서를 이용한 배터리 안전상태 진단 모니터링 시스템 |
KR20210115841A (ko) | 2020-03-16 | 2021-09-27 | 삼성전자주식회사 | 전자 장치 및 전자 장치의 테마를 부분적으로 운용하는 방법 |
-
2021
- 2021-08-31 KR KR1020210115841A patent/KR20230032724A/ko active Search and Examination
-
2022
- 2022-08-30 CN CN202280008406.7A patent/CN116636064A/zh active Pending
- 2022-08-30 JP JP2023537371A patent/JP2024500140A/ja active Pending
- 2022-08-30 WO PCT/KR2022/012971 patent/WO2023033522A1/ko active Application Filing
- 2022-08-30 US US18/269,219 patent/US20240061047A1/en active Pending
- 2022-08-30 EP EP22865024.8A patent/EP4249904A4/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140111220A1 (en) * | 2011-05-11 | 2014-04-24 | Emazys Technologies Aps | Method for fault diagnosis on solar modules |
KR20180063927A (ko) * | 2016-12-02 | 2018-06-14 | 주식회사 나루이엠에스 | 초음파 송수신을 이용한 전기차용 배터리 불량 자동 판별 장치 및 방법 |
KR20200035594A (ko) * | 2018-09-27 | 2020-04-06 | 주식회사 엘지화학 | 가압력을 이용한 전지셀의 비파괴적 단선 여부 평가 방법 |
KR102094539B1 (ko) * | 2018-12-11 | 2020-03-27 | (주)제이디 | 배터리 비파괴 검사 장치 |
JP2020165859A (ja) | 2019-03-29 | 2020-10-08 | 日産自動車株式会社 | 二次電池用インピーダンス測定装置および二次電池の状態推定装置、並びに二次電池システムおよび二次電池用充電装置 |
KR102265423B1 (ko) * | 2019-09-19 | 2021-06-15 | 주식회사 그릿에이트 | 초음파센서를 이용한 배터리 안전상태 진단 모니터링 시스템 |
KR20210115841A (ko) | 2020-03-16 | 2021-09-27 | 삼성전자주식회사 | 전자 장치 및 전자 장치의 테마를 부분적으로 운용하는 방법 |
Also Published As
Publication number | Publication date |
---|---|
EP4249904A1 (en) | 2023-09-27 |
JP2024500140A (ja) | 2024-01-04 |
EP4249904A4 (en) | 2024-06-05 |
CN116636064A (zh) | 2023-08-22 |
KR20230032724A (ko) | 2023-03-07 |
US20240061047A1 (en) | 2024-02-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2020213846A1 (ko) | 와전류를 이용한 전지셀 내부의 균열 검사 방법 및 검사 장치 | |
WO2020009337A1 (ko) | 파우치형 2차전지의 전극 손상 검사방법 및 파우치형 2차전지의 전극 손상 검사장치 | |
WO2018128395A1 (ko) | 이차 전지의 저전압 불량 검사 방법 및 장치 | |
WO2020171426A1 (ko) | 배터리 셀 연결용 버스 바, 배터리 팩 및 이의 제조 방법 | |
WO2020105976A1 (ko) | 지그 가압 방식의 가압 단락 검사 방법 | |
WO2019164300A1 (ko) | 이차전지셀의 절연저항측정방법 | |
WO2020231054A1 (ko) | 전극 조립체 및 이의 검사 방법 | |
WO2020106030A1 (ko) | 이차전지셀 파우치성형모듈 | |
WO2022145905A1 (ko) | 전극시트의 불량 검출 시스템 | |
WO2020106031A1 (ko) | 이차전지셀의 절연저항측정장치 | |
WO2023033522A1 (ko) | Tdr을 이용한 전지셀의 내부 결함 검출장치 및 방법 | |
WO2018147586A2 (ko) | 초음파를 이용한 알루미늄 파우치 실링을 위한 비파괴검사 판정시스템 | |
WO2021261980A1 (ko) | 금속 호일 피로 시험 장치 및 이를 사용한 방법 | |
WO2021112481A1 (ko) | 전극조립체 제조방법 및 제조장치, 그를 포함한 이차전지 제조방법 | |
WO2022260452A1 (ko) | 원통형 이차전지용 용접 상태 검사장치 및 검사방법 | |
WO2023287078A1 (ko) | 전지의 용접 상태 검사 방법 | |
WO2022203265A1 (ko) | 습윤 상태의 전극 시편에 대한 접착력 측정 시스템 및 이를 이용한 습윤 상태의 전극 시편에 대한 접착력 측정 방법 | |
WO2021153922A1 (ko) | 이차전지 및 이차전지의 제조 방법 | |
WO2022097991A1 (ko) | 전지 셀의 균열 검사를 위한 와전류 센서 및 이를 포함하는 전지 셀의 균열 검출 시스템 | |
WO2022234956A1 (ko) | 전지셀 제조 방법 및 제조 시스템 | |
WO2022270866A1 (ko) | 내부 트레이의 오조립 또는 작동 중 틀어짐 감지방법 및 전지셀 활성화 트레이 | |
WO2022260268A1 (ko) | 용접 상태 검사 장치 및 검사 방법 | |
WO2023075273A1 (ko) | 전지셀의 전극 탭 단선 검사장치 | |
WO2022215879A1 (ko) | 전극셀 검사장치 및 검사방법 | |
WO2023182784A1 (ko) | 이차전지용 실링 갭 측정설비 및 측정방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22865024 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023537371 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280008406.7 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 18269219 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2022865024 Country of ref document: EP Effective date: 20230621 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |