WO2025002597A1 - Verfahren zur wiederherstellung von elektrochemischen eigenschaften einer lithium-folie - Google Patents
Verfahren zur wiederherstellung von elektrochemischen eigenschaften einer lithium-folie Download PDFInfo
- Publication number
- WO2025002597A1 WO2025002597A1 PCT/EP2024/051944 EP2024051944W WO2025002597A1 WO 2025002597 A1 WO2025002597 A1 WO 2025002597A1 EP 2024051944 W EP2024051944 W EP 2024051944W WO 2025002597 A1 WO2025002597 A1 WO 2025002597A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- laser beam
- lithium foil
- beam source
- lithium
- laser
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
- B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
- B23K26/062—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam
- B23K26/0622—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam by shaping pulses
- B23K26/0624—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam by shaping pulses using ultrashort pulses, i.e. pulses of 1 ns or less
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
- B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
- B23K26/064—Shaping the laser beam, e.g. by masks or multi-focusing by means of optical elements, e.g. lenses, mirrors or prisms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/08—Devices involving relative movement between laser beam and workpiece
- B23K26/082—Scanning systems, i.e. devices involving movement of the laser beam relative to the laser head
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
- B23K26/355—Texturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
- B23K26/362—Laser etching
- B23K26/364—Laser etching for making a groove or trench, e.g. for scribing a break initiation groove
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
- B23K26/40—Removing material taking account of the properties of the material involved
-
- 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
-
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/08—Non-ferrous metals or alloys
- B23K2103/12—Copper or alloys thereof
-
- 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 invention relates to a method for surface treatment of a lithium foil and a battery foil for a solid-state battery.
- Lithium foils or lithium metal foils as well as lithium-coated copper foils are promising for use in battery systems, especially solid-state batteries, due to their excellent electrochemical properties.
- the lithium serves as an anode material.
- Lithium is an alkali metal which is highly reactive. Therefore, the storage and use of lithium is particularly challenging. False Treated or stored lithium foils lead to deterioration of battery performance and capacity.
- US 6,951,120 B2 discloses a processing of crystalline lithium niobate with a laser.
- the laser has a laser beam with a wavelength close to the absorption edge of lithium niobate.
- the laser beam is emitted in pulses of short duration and at a repetition rate that is selected such that the surface of the lithium niobate is removed without damaging the base material.
- the laser beam and the substrate can be displaced relative to one another in order to create a trench with the desired geometry in the lithium niobate.
- the invention is based on the object of restoring the electrochemical properties of a lithium foil which has been exposed to an improper atmosphere, in particular water, oxygen and/or nitrogen.
- the problem underlying the invention is solved by a method having the features of claim 1.
- the method provides for surface treatment of a lithium foil by means of a pulsed laser beam source, whereby the ion resistance of the lithium foil is reduced by the surface treatment.
- the laser beam source is designed to remove lithium compounds formed on the lithium foil and to introduce a structure into the surface of the lithium foil.
- the process cleans the surface of the lithium foil by removing the lithium compounds. This leads to a reduction in ion resistance. It is surprising that the lithium compounds can be removed using a pulsed laser beam source. On the other hand, the process structures the surface of the lithium foil. This leads to a further reduction in ion resistance due to the larger surface area, so that surprisingly a lower ion resistance can be achieved in the restored lithium foil than in an untreated and correctly handled lithium foil. Consequently, when the processed lithium foil is used in a battery, the batteries can achieve increased performance and capacity. In addition, the process is particularly efficient because the removal and structuring can be carried out at the same time.
- a “lithium foil” is understood to mean a flat material containing lithium.
- the flat material can also have a carrier material, such as a copper foil. Accordingly, a copper foil coated with lithium is also to be regarded as a lithium foil.
- a pulse energy of the laser beam source is in a range between 4 pj and 6 mJ, in particular less than 50 pj or greater than 250 pj. It is advantageous if the pulse rate of the laser beam source is greater than 10 kHz. It is also advantageous if the beam diameter of the laser beam source on the surface of the lithium foil is in a range between 25 gm and 600 gm. This has the advantage that the ion resistance of the lithium foil is further reduced. Accordingly, the use of the processed lithium foil, for example in a solid-state battery, results in increased battery capacity and performance.
- the surface treatment process involves providing a lithium foil which has previously undergone a reaction which increases the ion resistance, in particular a reaction with water, oxygen and/or nitrogen. This occurs, for example, if the lithium foil is stored improperly or if a leak occurs. As a result, a large number of lithium compounds, in particular lithium oxide, lithium nitrides, lithium hydroxides and lithium carbonates, have formed in the lithium foil.
- the provision of such a lithium foil is particularly well suited to the use of the laser beam source with the parameters mentioned, so that a significant reduction in the ion resistance can be expected.
- the laser beam source introduces a structure into the surface of the lithium foil with a structure depth of at least 10% and/or of at least 2.5 gm and/or of at most 30% and/or of at most 10 gm, in particular at most 5 gm, compared to the non-structured areas of the surface of the lithium foil. This is accompanied by a further reduction in the ion resistance. It is also advantageous if the laser beam source is set up in such a way that it has a pulse shape with a pulse peak power which is at least 10% above an average pulse power of the laser beam source. This is accompanied by a defined structural shaping of the structure introduced into the surfaces.
- the laser beam source is preferably designed as an ultrashort pulse laser, in particular as an ns laser, ps laser or fs laser. This achieves high intensities at moderate average power levels, so that targeted heat input to the surface is ensured.
- the laser beam source can be designed as a NIR laser.
- the laser beam source has a beam quality M 2 in a range between 1 and 5 and/or the laser beam source is designed as a single mode laser or as a multi-mode laser. This ensures targeted melting and/or evaporation of the surface of the lithium foil.
- the surface treatment especially the laser treatment, is carried out in a dry room atmosphere. This ensures that the reaction of the lithium foil with water in the ambient air is reduced.
- drying room atmosphere is set in such a way that the dew point is at most - 15 .
- a beam deflection unit in particular a scanner optics, is used to guide the beam of the laser beam source during surface processing. This ensures high speed during laser processing.
- the position and/or the peripheral geometry of the lithium foil is recorded during surface processing, in particular laser processing.
- An optical sensor system in particular a camera system and/or optical coherence tomography (VisonLine), can be used for this purpose.
- VisonLine optical coherence tomography
- the processing position of the laser beam source in particular the beam deflection unit, is adjusted depending on the position and/or the peripheral geometry of the lithium foil. Consequently, automated path programming can be provided.
- the surface, in particular the surface roughness, and/or the cutting position of the lithium foil is recorded.
- a distance sensor and/or an optical coherence tomography and/or laser triangulation can be used.
- the cutting position can be controlled by means of the surface and/or the cutting position, so that a higher contour accuracy can be ensured.
- a further advantageous development of the invention provides that a lithium foil is processed at least partially continuously by the laser beam source, in particular the beam deflection unit, following the position of the lithium foil.
- the compensation of the relative movement of the lithium foil and the laser beam source can be compensated by means of a control unit. Accordingly, a lithium foil can be unrolled from a roll and the lithium foil can be processed at the same time. This makes it possible to achieve consistent processing results and a high degree of contour accuracy.
- the problem underlying the invention is also solved by a battery foil with the features of claim 15. Accordingly, the battery foil is made from a lithium foil processed in a method according to one of claims 1 to 16. The battery foil therefore represents a foil whose surface has been cleaned of lithium compounds and structured.
- FIG. 1 Flow diagram for a method according to the invention
- Fig. 3 ablated and structured lithium foil.
- a clean lithium foil 10 with a carrier layer 12 made of copper and a lithium layer 14 arranged on the carrier layer 12 is first provided (S10).
- the lithium foil 10 then becomes contaminated, e.g. due to improper storage and contact with ambient air (S20).
- lithium compounds 18, in particular lithium oxide, lithium nitrides, lithium hydroxides, lithium carbonates are formed on a surface 16 of the lithium foil 10, in particular on the lithium layer 14, which increases the ion resistance of the lithium foil 10.
- the excellent electrochemical properties of the lithium foil 10 are lost. Accordingly, such a contaminated lithium foil 10 results in poorer battery capacity and performance.
- the lithium foil 10 is processed using a pulsed laser beam source 20 with a laser beam 21.
- a dry atmosphere with a dew point of at most -15° is provided (S30).
- the ion resistance of the lithium foil 10 is then reduced by setting up the laser beam source 20 to remove lithium compounds 14 formed on the lithium foil 10, in particular on the lithium layer 14, and to introduce a structure 22 into the surface 16 of the lithium foil 10 (S40).
- the structure 22 introduced into the surface 16 of the lithium foil 10 has a structure depth 24 of at least 10% and/or of 2.5 ⁇ m compared to the non-structured areas 26.
- the lithium foil 10 shown in Fig. 3 can be used as a battery foil 100 with excellent electrochemical properties for e.g. a solid-state battery.
- the laser beam source 20 has a pulse energy in a range between 4 gj and 6 mJ, a pulse rate greater than 10 kHz and a beam diameter on the lithium foil 10, in particular on the lithium compounds 14 and/or on the lithium layer 14, in a range between 25 gm and 600 gm.
- the laser beam source 20 is configured such that it has a pulse shape with a pulse peak power which is at least 10% above an average pulse power of the laser beam source 20.
- the laser beam source 20 is designed as an ultrashort pulse laser, in particular as an ns laser, ps laser or as an fs laser.
- the laser beam source 20 has a beam quality M2 in a range between 1 and 5.
- the laser beam source 20 is designed as a single mode laser or as a multi mode laser.
- the laser beam source 20 has a
- Beam deflection unit 28 in particular a scanner optics, on.
- a sensor device 30 is provided which is designed to detect the position and/or the peripheral geometry and/or the surface 16, in particular the surface roughness, and/or the cutting position of the lithium foil 10 during surface processing.
- control device 32 which controls the parameters and/or the position of the laser beam source 20 and/or the position of the lithium foil 10, in particular as a function of the sensor data provided by the sensor device 30.
- the hatch of the laser beam 21 can preferably be reduced.
- the hatch can preferably be in a range between 0.006 mm and 0.2 mm. Pulse rates of 200 kHz and 360 kHz can be selected.
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Laser Beam Processing (AREA)
Abstract
Description
Claims
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020257043699A KR20260017436A (ko) | 2023-06-26 | 2024-01-26 | 리튬 호일의 전기화학적 특성을 재생성하기 위한 방법 |
| CN202480043195.XA CN121419852A (zh) | 2023-06-26 | 2024-01-26 | 用于恢复锂箔的电化学性能的方法 |
| EP24702890.5A EP4731374A1 (de) | 2023-06-26 | 2024-01-26 | Verfahren zur wiederherstellung von elektrochemischen eigenschaften einer lithium-folie |
| US19/426,079 US20260115830A1 (en) | 2023-06-26 | 2025-12-19 | Method for reproducing electrochemical properties of a lithium foil |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102023116767.7 | 2023-06-26 | ||
| DE102023116767 | 2023-06-26 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US19/426,079 Continuation US20260115830A1 (en) | 2023-06-26 | 2025-12-19 | Method for reproducing electrochemical properties of a lithium foil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2025002597A1 true WO2025002597A1 (de) | 2025-01-02 |
Family
ID=89806626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2024/051944 Ceased WO2025002597A1 (de) | 2023-06-26 | 2024-01-26 | Verfahren zur wiederherstellung von elektrochemischen eigenschaften einer lithium-folie |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20260115830A1 (de) |
| EP (1) | EP4731374A1 (de) |
| KR (1) | KR20260017436A (de) |
| CN (1) | CN121419852A (de) |
| WO (1) | WO2025002597A1 (de) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6951120B2 (en) | 2002-03-19 | 2005-10-04 | Wisconsin Alumni Research Foundation | Machining of lithium niobate by laser ablation |
-
2024
- 2024-01-26 KR KR1020257043699A patent/KR20260017436A/ko active Pending
- 2024-01-26 WO PCT/EP2024/051944 patent/WO2025002597A1/de not_active Ceased
- 2024-01-26 EP EP24702890.5A patent/EP4731374A1/de active Pending
- 2024-01-26 CN CN202480043195.XA patent/CN121419852A/zh active Pending
-
2025
- 2025-12-19 US US19/426,079 patent/US20260115830A1/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6951120B2 (en) | 2002-03-19 | 2005-10-04 | Wisconsin Alumni Research Foundation | Machining of lithium niobate by laser ablation |
Non-Patent Citations (2)
| Title |
|---|
| KRIEGLER JOHANNES ET AL: "Enhanced performance and lifetime of lithium-ion batteries by laser structuring of graphite anodes", APPLIED ENERGY., vol. 303, 1 September 2021 (2021-09-01), GB, pages 117693, XP093087411, ISSN: 0306-2619, DOI: 10.1016/j.apenergy.2021.117693 * |
| LUCAS HILLE: "Laser structuring of graphite anodes and NMC cathodes - Proportionate influence on electrode characteristics and cell performance", ELECTROCHIMICA ACTA, vol. 392, 1 October 2021 (2021-10-01), AMSTERDAM, NL, pages 139002, XP093155385, ISSN: 0013-4686, Retrieved from the Internet <URL:https://www.sciencedirect.com/science/article/pii/S0013468621012925/pdfft?md5=9925441cdaeba62738259626c2371c98&pid=1-s2.0-S0013468621012925-main.pdf> DOI: 10.1016/j.electacta.2021.139002 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US20260115830A1 (en) | 2026-04-30 |
| KR20260017436A (ko) | 2026-02-05 |
| CN121419852A (zh) | 2026-01-27 |
| EP4731374A1 (de) | 2026-04-29 |
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