WO2023101283A1 - 셀 불량 비파괴 검출 방법 - Google Patents
셀 불량 비파괴 검출 방법 Download PDFInfo
- Publication number
- WO2023101283A1 WO2023101283A1 PCT/KR2022/018344 KR2022018344W WO2023101283A1 WO 2023101283 A1 WO2023101283 A1 WO 2023101283A1 KR 2022018344 W KR2022018344 W KR 2022018344W WO 2023101283 A1 WO2023101283 A1 WO 2023101283A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cell
- lic
- peak intensity
- anode
- lic6
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229910013458 LiC6 Inorganic materials 0.000 claims abstract description 28
- 230000001066 destructive effect Effects 0.000 claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 6
- 239000006183 anode active material Substances 0.000 claims abstract description 5
- 230000007547 defect Effects 0.000 claims description 28
- 230000002950 deficient Effects 0.000 claims description 20
- 229910013465 LiC12 Inorganic materials 0.000 claims description 13
- 238000001514 detection method Methods 0.000 claims description 12
- 230000007423 decrease Effects 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 25
- 229910052744 lithium Inorganic materials 0.000 description 25
- 239000010410 layer Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910002804 graphite Inorganic materials 0.000 description 11
- 239000010439 graphite Substances 0.000 description 11
- 239000011149 active material Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910012578 LiNi0.4Mn0.3Co0.3O2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000002441 X-ray diffraction 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
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
- G01N23/2055—Analysing diffraction patterns
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/02—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material
- G01N23/06—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and measuring the absorption
- G01N23/18—Investigating the presence of flaws defects or foreign matter
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/05—Investigating materials by wave or particle radiation by diffraction, scatter or reflection
- G01N2223/056—Investigating materials by wave or particle radiation by diffraction, scatter or reflection diffraction
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/30—Accessories, mechanical or electrical features
- G01N2223/304—Accessories, mechanical or electrical features electric circuits, signal processing
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/30—Accessories, mechanical or electrical features
- G01N2223/33—Accessories, mechanical or electrical features scanning, i.e. relative motion for measurement of successive object-parts
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/60—Specific applications or type of materials
- G01N2223/646—Specific applications or type of materials flaws, defects
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
Definitions
- the present invention relates to a non-destructive detection method for cell defects.
- Such a lithium secondary battery is manufactured by manufacturing a positive electrode and a negative electrode, stacking them together with a separator to form an electrode assembly, and embedding the electrode assembly together with an electrolyte in a secondary battery case.
- the electrode of the secondary battery is a sliding phenomenon caused by the coating of the electrode active material slurry during the manufacturing process, and as the loading for each position is different, a sliding defect in which the ratio of the positive electrode and the negative electrode is reversed may occur at the sliding site. .
- the positive electrode when assembling the positive electrode and the negative electrode, the positive electrode has a larger area than the negative electrode, resulting in an overhang defect in which the ratio of the positive electrode and the negative electrode is reversed.
- lithium precipitation is accelerated in the corresponding area as the cycle progresses, and if lithium precipitation is severe, it may lead to ignition. A process of selecting and removing cells is necessary.
- An object of the present invention is to provide a cell defect non-destructive detection method capable of quickly detecting an overhang or sliding defect without disassembling the cell.
- the XRD scan it is characterized in that whether or not the LiC 6 peak of the anode is observed in the region after the signal of the anode current collector is output.
- the cell charging in step (b) may be performed at 4V or more.
- step (c) may be performed once inward from one end of the cathode, or may be performed twice inward from one end and inward from the other end.
- the observation of the LiC 6 peak may be measured as LiC 6 peak intensity (I LiC6 /(I LiC6 +I LiC12 )) compared to the sum of LiC 6 peak intensity and LiC 12 peak intensity.
- the LiC 6 peak when the LiC 6 peak is observed immediately after the signal of the anode current collector in the XRD scan, it may be determined as defective. Specifically, the area where the LiC 6 peak intensity (I LiC6 /(I LiC6 +I LiC12 )) relative to the sum of the LiC 6 peak intensity and the LiC 12 peak intensity immediately after the signal of the anode current collector appears in the XRD scan is 0.3 or more If observed, it may be judged as defective.
- the cell charging in step (b) is performed with SOC of 80% or more, and the LiC 6 peak intensity (I When a region in which LiC6 /(I LiC6 +I LiC12 )) is 0.8 or more is observed, it may be judged as defective.
- the defective cell may mean an overhanging cell or a sliding cell.
- FIG. 1 is a perspective view schematically showing an overhang cell according to Comparative Example 1;
- FIG. 2 is a perspective view schematically showing a sliding cell.
- Example 3 is a perspective view schematically showing a normal cell according to Example 1;
- a cell defect non-destructive detection method According to an embodiment of the present invention, a cell defect non-destructive detection method
- a non-destructive detection method for cell defects is provided, in which it is confirmed whether or not the LiC 6 peak of the anode is observed in the region after the signal of the anode current collector is output.
- the cell defect may mean an overhanging cell or a sliding cell.
- the anode 102 facing the separator 103 at the end is formed with a larger area than the cathode 101, so that the ratio between the anode and the cathode is reversed.
- the overhang cell 100 as shown in FIG. 2, the end of the cathode 202 slides due to the characteristics of the electrode according to the slurry coating, and the cathode 201 facing the anode 201 with the separator 203 therebetween in the corresponding area ( In order to determine the defect of a cell such as the sliding cell 200 in which the loading of 202 is lowered, the cell has to be disassembled to determine the assembly defect.
- the inventors of the present application studied a method of detecting defects in such a cell without disassembling the cell, and using in situ XRD analysis while charging the cell to a certain extent without disassembling the cell, and defective cell assembly such as overhang or sliding. It was confirmed that it could be screened out and came to complete the present invention.
- a defective cell when using an anode containing a carbon-based material, particularly graphite, a defective cell may be detected through observation of LiC 6 peak.
- stage III in which lithium is inserted at intervals of two graphite layers, and stage in which lithium is inserted at intervals of one graphite layer II, and, when further charging is performed, it changes to stage I in which lithium is intercalated in all of the graphite layers.
- the ratio of the cathode to the anode is reversed in the region of the cathode end, so that the cathode loading is lower than the cathode loading, and the cathode end is significantly overcharged during charging. , and accordingly, when the cathode end is measured by XRD, the LiC 6 peak is observed quite clearly.
- the LiC 6 peak intensity which is the behavior in which lithium is charged into the negative electrode at the end of the negative electrode, increases faster than the LiC 6 peak intensity in the middle of the negative electrode, which is the behavior in which lithium is charged into the negative electrode.
- the present application can detect defects in the cell nondestructively, and can detect defects within 3 to 5 minutes, which is the in situ XRD measurement time, which is very efficient in terms of process and cost.
- the anode should include a carbon-based material, particularly graphite, as an anode active material.
- the cell charging in step (b) may be performed at 4V or higher, and may be performed at SOC 50 or higher based on SOC.
- the in situ XRD measurement is performed without a separate disassembly process for the cell charged in this way.
- This XRD scan was performed at a room temperature of 25° C., the X-ray output conditions were 60 kv and 35 mA, and the measurement method was performed in static mode (2Theta: 7-14 degrees). The scan time was performed by fixing it at 4-minute intervals simultaneously with the charging process.
- This XRD scan is performed from the end of the cathode to the inside, because defects such as overhang or sliding occur at the end of the cathode. More specifically, the step (c) may be performed once inward from one end of the cathode, or may be performed twice inward from one end and inward from the other end.
- an XRD scan is performed from the end of the cathode to the inside to check whether the LiC 6 peak of the cathode is observed.
- the signal of the anode current collector can be easily recognized because the peak of the metal used as the anode current collector is observed in XRD.
- the observation of the LiC 6 peak may be measured as the LiC 6 peak intensity (I LiC6 /(I LiC6 +I LiC12 )) compared to the sum of the LiC 6 peak intensity and the LiC 12 peak intensity.
- the method of detecting defects based on this is, as an example, the LiC 6 peak intensity of the anode in the region after the signal of the anode current collector appears in the XRD scan decreases from the end of the cathode to the inside. If so, it may be judged as defective.
- the LiC 6 peak intensity appears strong due to overcharging at the end of the cathode, and rather the intensity tends to decrease toward the inside.
- the LiC 6 peak intensity increases as lithium is easily inserted toward the inner side. From this, it is possible to detect defects.
- the LiC 6 peak when the LiC 6 peak is observed immediately after the signal of the anode current collector in the XRD scan, it may be judged to be defective. More specifically, immediately after the signal of the anode current collector in the XRD scan, the LiC 6 peak If a region in which the LiC 6 peak intensity (I LiC6 /(I LiC6 +I LiC12 )) is greater than 0.3, specifically greater than 0.3, and more specifically 0.3 to 0.9, compared to the sum of the intensity and the LiC 12 peak intensity, is defective . may be judged by On the other hand, a value close to 0, for example, a value less than 0.3 is determined as a normal cell.
- the LiC 6 peak intensity appears strongly at the end of the negative electrode due to overcharging, whereas in a normal cell, lithium absorption and release does not occur at the end of the negative electrode, so the LiC 6 peak does not appear. It is possible to detect a defective cell sufficiently just by observing the LiC 6 peak of .
- the cell charging in step (b) is performed with SOC of 80% or more, and the LiC 6 peak intensity compared to the sum of the LiC 6 peak intensity and the LiC 12 peak intensity in the region after the signal of the anode current collector is output. If a region in which the peak intensity (I LiC6 /(I LiC6 +I LiC12 )) is 0.8 or more is observed, it may be determined as defective.
- a cell defect can be determined in a very simple manner without disassembling the cell.
- a mixture of artificial graphite, a binder (SBR and CMC mixed at a weight ratio of 2:1), and carbon black at a weight ratio of 95:3.5:1.5 as a conductive material and water as a dispersion medium were used to obtain a weight ratio between the mixture and the dispersion medium.
- a slurry for an active material layer mixed at a ratio of 1:2 was prepared.
- the slurry for the active material layer was coated on one surface of a copper (Cu) thin film having a thickness of 10 ⁇ m, which is an anode current collector, and dried under vacuum at 130° C. for 1 hour to form an active material layer.
- the active material layer thus formed was rolled by a roll pressing method to prepare a negative electrode having an active material layer having a thickness of 80 ⁇ m.
- a slurry for a positive electrode active material layer was prepared by mixing LiNi 0.4 Mn 0.3 Co 0.3 O 2 as a positive electrode active material, carbon black as a conductive material, and PVDF as a binder in a weight ratio of 92.5: 3.5: 4 in an N-methylpyrrolidone solvent, Using a slot die, the slurry for the positive electrode active material layer was coated on one surface of an aluminum (Al) thin film having a thickness of 10 ⁇ m, which is a positive electrode current collector, and dried under vacuum at 130° C. for 1 hour to form an active material layer. The thus formed active material layer was rolled by a roll pressing method to prepare a positive electrode having an active material layer having a thickness of 80 ⁇ m.
- An electrode assembly was prepared by interposing a porous polyethylene separator between the positive electrode and the negative electrode prepared as described above, the electrode assembly was placed inside a case, and an electrolyte was injected into the case to prepare a lithium secondary battery.
- both ends of the positive electrode were stacked so as to deviate from the end of the negative electrode, and as shown in FIG. 1, an overhang cell was manufactured in which the area of the positive electrode at one end was larger than the area of the negative electrode.
- both ends of the positive electrode were stacked so that they were positioned inside both ends of the negative electrode, and a normal cell was manufactured as shown in FIG. 3 .
- XRD scan was performed while charging the lithium secondary battery prepared in Comparative Example 1 at 1C up to 4.35V/38mA under constant current/constant voltage (CC/CV) conditions at 25°C.
- CC/CV constant current/constant voltage
- the XRD scan was performed at a room temperature of 25° C., the X-ray output conditions were 60 kv and 35 mA, and the measurement method was performed in static mode (2Theta: 7-14 degrees). The scan time was performed by fixing it at 4-minute intervals simultaneously with the charging process.
- LiC 6 peak intensity compared to the sum of LiC 6 peak intensity and LiC 12 peak intensity in regions (1), (2), and (3) of FIG. 1 below (I LiC6 / (I LiC6 +I LiC12 ) ) was obtained and shown in FIG. 4 below.
- the LiC 6 peak intensity (I LiC6 /(I LiC6 +I LiC12 )) compared to the sum of the LiC 6 peak intensity and the LiC 12 peak intensity calculates the area of the peak defined by LiC 6 and the area of the peak defined by LiC 12 , can be obtained by calculating their ratio.
- the LiC 6 peak intensity in (1) of FIG. 1 is indicated in red
- the LiC 6 peak intensity in (2) is indicated in yellow
- the LiC 6 peak intensity in (3) is indicated in blue.
- XRD scan was performed while charging the lithium secondary battery prepared in Example 1 at 1C up to 4.35V/38mA under constant current/constant voltage (CC/CV) conditions at 25°C.
- CC/CV constant current/constant voltage
- the XRD scan was performed at a room temperature of 25° C., the X-ray output conditions were 60 kv and 35 mA, and the measurement method was performed in static mode (2Theta: 7-14 degrees). The scan time was performed by fixing it at 4-minute intervals simultaneously with the charging process.
- the LiC 6 peak intensity (I LiC6 /(I LiC6 +I LiC12 )) and graphite (001) compared to the sum of the LiC 6 peak intensity and the LiC 12 peak intensity in the region (4) of FIG. 3 below
- the interlayer spacing of that is, the crystal lattice value was obtained and shown in FIG. 5 below.
- the cell defect non-destructive detection method according to the present invention is a very simple method of measuring a cell that has been charged by XRD and observing the LiC6 peak at the end of the negative electrode where overhang or sliding may occur, without disassembling the cell. It is efficient in terms of fairness and cost because it can quickly detect overhang or sliding cell defects.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
Claims (9)
- 셀 불량 비파괴 검출 방법으로서,(a) 음극 활물질로서 탄소계 물질을 포함하는 셀을 준비하는 단계;(b) 상기 셀을 충전하는 단계; 및(c) 상기 충전된 셀을 음극의 단부에서 내측으로 XRD 스캔하는 단계;를 포함하고,상기 XRD 스캔에서 음극 집전체의 신호가 나온 후의 영역에서의 음극의 LiC6 peak 관찰 여부를 확인하는 것인 셀 불량 비파괴 검출 방법.
- 제1항에 있어서,상기 단계 (b)의 셀 충전은 4V 이상으로 수행되는 셀 불량 비파괴 검출 방법.
- 제1항에 있어서,상기 단계 (c)는 음극의 일단부에서 내측으로 1회 수행되거나, 일단부에서 내측으로 및 타단부에서 내측으로 2회 수행되는 셀 불량 비파괴 검출 방법.
- 제1항에 있어서,상기 LiC6 peak의 관찰은 LiC6 peak 강도와 LiC12 peak 강도의 합 대비 LiC6 peak 강도(ILiC6/(ILiC6+ILiC12))로 측정되는 것인 셀 불량 비파괴 검출 방법.
- 제4항에 있어서,상기 XRD 스캔에서 음극 집전체의 신호가 나온 후의 영역에서의 음극의 LiC6 peak 강도가 음극의 단부에서 내측으로 갈수록 감소하는 경우 불량으로 판단하는 것인 셀 불량 비파괴 검출 방법.
- 제1항에 있어서,상기 XRD 스캔에서 음극 집전체의 신호가 나온 직후 LiC6 peak가 관찰되는 경우 불량으로 판단하는 것인 셀 불량 비파괴 검출 방법.
- 제6항에 있어서,상기 XRD 스캔에서 음극 집전체의 신호가 나온 직후 상기 LiC6 peak 강도와 LiC12 peak 강도의 합 대비 LiC6 peak 강도(ILiC6/(ILiC6+ILiC12))가 0.3 이상인 영역이 관찰되는 경우, 불량으로 판단하는 셀 불량 비파괴 검출 방법.
- 제1항에 있어서,상기 단계 (b)의 셀 충전은 SOC 80% 이상으로 수행되고, 상기 음극 집전체의 신호가 나온 후의 영역에서의 상기 LiC6 peak 강도와 LiC12 peak 강도의 합 대비 LiC6 peak 강도(ILiC6/(ILiC6+ILiC12))가 0.8 이상인 영역이 관찰되는 경우, 불량으로 판단하는 셀 불량 비파괴 검출 방법.
- 제1항에 있어서,상기 셀 불량은 오버행 셀 또는 슬라이딩 셀을 의미하는 셀 불량 비파괴 검출 방법.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202280018499.1A CN117043587A (zh) | 2021-12-02 | 2022-11-18 | 检测单体故障的非破坏性方法 |
JP2023552241A JP2024509128A (ja) | 2021-12-02 | 2022-11-18 | セル不良の非破壊検出方法 |
EP22901641.5A EP4279907A1 (en) | 2021-12-02 | 2022-11-18 | Non-destructive method for detecting cell failure |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2021-0171212 | 2021-12-02 | ||
KR1020210171212A KR20230083109A (ko) | 2021-12-02 | 2021-12-02 | 셀 불량 비파괴 검출 방법 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023101283A1 true WO2023101283A1 (ko) | 2023-06-08 |
Family
ID=86612723
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2022/018344 WO2023101283A1 (ko) | 2021-12-02 | 2022-11-18 | 셀 불량 비파괴 검출 방법 |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP4279907A1 (ko) |
JP (1) | JP2024509128A (ko) |
KR (1) | KR20230083109A (ko) |
CN (1) | CN117043587A (ko) |
WO (1) | WO2023101283A1 (ko) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130271089A1 (en) * | 2005-08-03 | 2013-10-17 | Rachid Yazami | Battery state of health assessment system |
WO2016021614A1 (ja) * | 2014-08-04 | 2016-02-11 | 新神戸電機株式会社 | リチウムイオン電池及びリチウムイオン電池の不良判別方法 |
JP2016051642A (ja) * | 2014-09-01 | 2016-04-11 | 株式会社コベルコ科研 | 電池の評価方法及びこれに用いる評価用セル |
KR20160060036A (ko) * | 2013-08-05 | 2016-05-27 | 넥세온 엘티디 | 구조화된 입자 |
KR20190023817A (ko) * | 2017-08-30 | 2019-03-08 | 서울대학교산학협력단 | 리튬 이온 전지에서 리튬 이온 거동의 분석 방법 |
-
2021
- 2021-12-02 KR KR1020210171212A patent/KR20230083109A/ko active Search and Examination
-
2022
- 2022-11-18 EP EP22901641.5A patent/EP4279907A1/en active Pending
- 2022-11-18 WO PCT/KR2022/018344 patent/WO2023101283A1/ko active Application Filing
- 2022-11-18 CN CN202280018499.1A patent/CN117043587A/zh active Pending
- 2022-11-18 JP JP2023552241A patent/JP2024509128A/ja active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130271089A1 (en) * | 2005-08-03 | 2013-10-17 | Rachid Yazami | Battery state of health assessment system |
KR20160060036A (ko) * | 2013-08-05 | 2016-05-27 | 넥세온 엘티디 | 구조화된 입자 |
WO2016021614A1 (ja) * | 2014-08-04 | 2016-02-11 | 新神戸電機株式会社 | リチウムイオン電池及びリチウムイオン電池の不良判別方法 |
JP2016051642A (ja) * | 2014-09-01 | 2016-04-11 | 株式会社コベルコ科研 | 電池の評価方法及びこれに用いる評価用セル |
KR20190023817A (ko) * | 2017-08-30 | 2019-03-08 | 서울대학교산학협력단 | 리튬 이온 전지에서 리튬 이온 거동의 분석 방법 |
Also Published As
Publication number | Publication date |
---|---|
JP2024509128A (ja) | 2024-02-29 |
KR20230083109A (ko) | 2023-06-09 |
EP4279907A1 (en) | 2023-11-22 |
CN117043587A (zh) | 2023-11-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2015037867A1 (ko) | 리튬 전극 및 그를 포함하는 리튬 이차전지 | |
WO2012165758A1 (ko) | 리튬 이차전지 | |
WO2013154253A1 (ko) | 다공성 코팅층을 포함하는 전극, 상기 전극의 제조방법 및 상기 전극을 포함하는 전기화학소자 | |
WO2011159083A2 (ko) | 전기화학소자용 전해질, 그 제조방법 및 이를 구비한 전기화학소자 | |
WO2015037868A1 (ko) | 리튬 전극 및 그를 포함하는 리튬 이차전지 | |
WO2013095057A1 (ko) | 활물질이 패턴 코팅된 젤리-롤형 전극조립체 및 이를 구비한 이차전지 | |
WO2009099279A2 (ko) | 리튬 이차 전지 및 이의 제조 방법 | |
WO2016053063A1 (ko) | 고무계 바인더를 포함하는 양극 활물질 슬러리 및 이로부터 제조된 양극 | |
WO2011145871A2 (ko) | 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지 | |
EP2258019A2 (en) | Battery having enhanced electrical insulation capability | |
WO2016053059A1 (ko) | 이종의 바인더를 포함하는 양극 활물질 슬러리 및 이로부터 제조된 양극 | |
WO2012161480A2 (ko) | 출력 밀도 특성이 향상된 고출력의 리튬 이차전지 | |
WO2018084675A1 (ko) | 이차 전지의 반응 추정 방법 및 이에 사용되는 전지셀을 포함하는 이차전지 | |
WO2020111649A1 (ko) | 리튬 이차전지용 양극 및 이를 포함하는 리튬 이차전지 | |
WO2015105365A1 (ko) | 고 연신 특성의 분리막을 가진 전극조립체 및 이를 포함하는 이차전지 | |
WO2020251165A1 (ko) | 추가 열처리 공정이 도입된 리튬 이차전지의 제조방법 및 이로부터 제조된 리튬 이차전지 | |
WO2018212446A1 (ko) | 리튬 이차 전지 | |
WO2021241899A1 (ko) | 리튬 이차전지의 퇴화 원인 진단 방법 | |
WO2021101041A1 (ko) | 이차전지의 활성화 방법 | |
WO2023101283A1 (ko) | 셀 불량 비파괴 검출 방법 | |
WO2020149686A1 (ko) | 이차전지용 음극의 제조방법 | |
WO2021125694A1 (ko) | 내부 단락 평가용 전지 셀 및 이를 이용한 전지 셀의 내부 단락 평가 방법 | |
WO2021080212A1 (ko) | 가압식 분리막 저항 측정 장치 및 측정 방법 | |
WO2022086103A1 (ko) | 이차 전지용 전극, 이를 포함하는 이차 전지 및 전극 제조 방법 | |
WO2021261754A1 (ko) | 저항층이 형성된 전극의 제조방법 |
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: 22901641 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2022901641 Country of ref document: EP Effective date: 20230818 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023552241 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280018499.1 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 18281835 Country of ref document: US |