Classifications

• • 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
  • H01M4/04—Processes of manufacture in general
  • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• • 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
  • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
  • H01M10/365—Zinc-halogen accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M12/00—Hybrid cells; Manufacture thereof
  • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
  • H01M12/085—Zinc-halogen cells or batteries
• • 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
  • H01M4/04—Processes of manufacture in general
  • H01M4/049—Manufacturing of an active layer by chemical means
  • H01M4/0495—Chemical alloying
• • 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
  • H01M4/24—Electrodes for alkaline accumulators
  • H01M4/244—Zinc electrodes
• • 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
  • H01M4/24—Electrodes for alkaline accumulators
  • H01M4/26—Processes of manufacture
• • 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
  • H01M4/581—Chalcogenides or intercalation compounds thereof
  • H01M4/5815—Sulfides
• • 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

• Energy storage technologies are playing an increasingly important role in electric power grids. These energy storage assets provide smoothing to better match generation and demand on a grid.
• the services performed by energy storage devices are beneficial to electric power grids across multiple time scales, from milliseconds to years.
• Of benefit are potentially low-cost rechargeable battery chemistries that can enable long duration large scale energy storage.
• an additive for an iron negative electrode of an alkaline electrochemical cell may include a powder of discrete granules including agglomerated particles, the agglomerated particles including at least one metal sulfide.
• the discrete granules may have a mean particle size of greater than about 30 microns and less than about 800 microns on a weight percentage basis.
• the discrete granules of the agglomerated particles of the at least one metal sulfide may have a median pore size of greater than about 75 nanometers and less than about 15 microns as determined by mercury intrusion porosimetry.
• processing the feedstock into the discrete granules may include forming the particulate material into one or more intermediate bodies, and changing the size of the one or more intermediate bodies to form the discrete granules.
• Forming the particulate material into the one or more intermediate bodies may include cold pressing the particulate material. Cold pressing the particulate material may include forming briquettes of the particulate material.
• changing the size of the one or more intermediate bodies to form the discrete granules may include sintering the one or more intermediate bodies together to form the discrete granules.
• exposing the formed structure to the sulfide source gas while maintaining the selected concentration of the sulfide source gas may include exposing the formed structure to the sulfide source gas while maintaining the selected concentration of the sulfide source gas and a second processing temperature that is below the first processing temperature such that a sulfidation reaction of the zinc oxide occurs to form zinc sulfide.
• the first processing temperature may be at or above 800 degrees Celsius and the second processing temperature may be at or below 600 degrees Celsius.
• the second processing temperature may be at or below 400 degrees Celsius.
• the sulfide source gas is H2S and the selected concentration of the sulfide source gas is between 0.25% and 1%.
• FIG. 1 A is a schematic representation of an electrochemical cell.
• FIG. IB is a schematic representation of a rechargeable battery.
• FIG. 2A is a schematic representation of an iron-negative electrode including a bed of a powder blend, the powder blend including a first powder of an iron-containing active material and a second powder of an additive material.
• FIG. 4 is a flowchart of an exemplary method 400 of making an additive for an iron negative electrode of an alkaline electrochemical cell.
• a plurality of electrochemical cells 100 in FIG. 1A may be connected electrically in series to form a stack. In certain other embodiments, a plurality of electrochemical cells 100 may be connected electrically in parallel. In certain other embodiments, the electrochemical cells 100 are connected in a mixed series-parallel electrical configuration to achieve a favorable combination of delivered current and voltage.
• a rechargeable battery 10 may include a positive electrode 12, a negative electrode 14, and a separator 16 within a container 18 filled with electrolyte 20 to a level 22 at least as high as the respective tops 32, 34 of the electrodes 12, 14. The space above the level 22 of the electrolyte 20 may be referred to as the headspace 24.
• the positive electrode 12 may be electrically connected to a positive terminal 42 of the rechargeable battery 10 and may contain active material that may undergo reduction reactions during discharging and oxidation reactions during charging.
• the negative electrode 14 may be electrically connected to a negative terminal 44 of the rechargeable battery 10 and may contain active material that may undergo oxidation reactions during discharging and reduction reactions during charging of the rechargeable battery 10.
• the rechargeable battery 10 in FIG. IB is merely an example of one electrochemical cell according to various embodiments and is not intended to be limiting.
• the electrolyte 20 may be an aqueous or nonaqueous alkaline, neutral, or acidic solution.
• the electrolyte solution may contain potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH) or combinations of these.
• a battery 10 may include a separator 16 that allows transfer of ions between the electrodes 12, 14 via the electrolyte.
• a separator may be chosen based on an ability to allow selective transfer of desired molecules or materials while substantially limiting or preventing transfer of undesired molecules or materials.
• some separator membranes are ion-selective and allow the transfer of negative (or positive) ions while substantially preventing transfer of positive (or negative) ions.
• separator materials may be chosen based on an ability to allow or prevent the cross-over of gas bubbles from one side (associated with one electrode) to the opposite side (associated with the counter-electrode).
• the container 18 may be made of any suitable materials and construction capable of containing the electrolyte, electrodes, and at least a minimum amount of gas pressure.
• the container 18 may be made of metals, plastics, composite materials, or others.
• the battery container 18 may be sealed so as to prevent the escape of any gases generated during operation of the battery.
• the battery container 18 may include a pressure relief valve to allow release of gases when a gas pressure within the battery container 18 exceeds a pre-determined threshold.
• the electrodes 12, 14 are shown substantially spaced apart in the figures, in some embodiments the electrodes may be very close to one another or even compressed against one another with a separator 16 in between.
• the figures may illustrate a single positive electrode 12 and a single negative electrode 14, battery systems within the scope of the present disclosure may also include two or more positive electrodes 12 and/or two or more negative electrodes 14.
• the negative electrode 102 of the electrochemical cell 100 and/or the negative electrode 14 of the rechargeable battery 10 may include metal or metal oxides such as iron, zinc, cadmium, or other metals and/or oxides or hydroxides of these or other metals, unless otherwise specified or made clear from the context. Further, it shall be generally understood that the negative electrode 102 of the electrochemical cell 100 and the negative electrode 14 of the rechargeable battery 10 have similar or identical features, unless otherwise indicated or made clear from the context and, for the sake of efficient description, these are not described separately for each negative electrode.
• the negative electrode 14 shall be referred to hereinafter as “the iron negative electrode 14” and all such references shall be understood to be intended to encompass references to other types of active metals described herein and to other negative electrodes described herein (e.g., to the negative electrode 102), unless otherwise specified or made clear from the context.
• the iron negative electrode 14 may include a bed 201 of a powder blend 202 having porosity through which an electrolyte (e.g., the electrolyte 20 in FIG. IB) may infiltrate the bed 201 iron negative electrode 14 to support the flow of ions as iron active material of the negative electrode 14 undergoes oxidation and reduction during operation of an electrochemical cell (e.g., the rechargeable battery 10).
• the powder blend 202 may include a first powder 204 and a second powder 206. As described in greater detail below, the first powder 204 may include an iron active material.
• the second powder 206 may include discrete granules 208 including agglomerated particles 210 including at least one metal sulfide.
• the iron active material may be greater than about 70% of the combined weight of the first powder 204 and the second powder 206, as may be useful balancing competing considerations associated with performance (e.g., capacity utilization of the iron active material), cost, and size of an electrochemical cell (e.g., the rechargeable battery 10) including the iron negative electrode 14.
• the discrete granules 208 of the agglomerated particles 210 overcome significant challenges of particle size matching, dry powder processing, and floataway/fallout risk, as compared to the use of a powder of loose particles of a solid-state additive in an iron negative electrode.
• the second powder 206 including the discrete granules 208 of the agglomerated particles 210 including the additive material may facilitate overcoming design challenges typically associated with particle size mismatches between the active material and the additive material in iron negative electrodes. Specifically, to achieve cost- effective production at scale, many solid-state additive powders are formed using manufacturing techniques that produce small particle sizes.
• small particle sizes may be useful for achieving dissolution rates of certain types of solid-state additives (e.g., manganese sulfide, tin-containing additives, and zinc sulfide) in an electrolyte in an iron negative electrode
• these small particle sizes are generally incompatible with the large particle sizes of the iron active material, with such large particle sizes needed to achieve packing and flow properties required for efficient performance of an iron negative electrode.
• the powder mixes used in iron negative electrodes may attain higher packing densities than desired, with the smaller particles of the sold-state additive packing into the interstitial spaces of the larger particles of the iron active material due to purely geometric effects.
• the particles of the solid-state additive can act as “flow enhancers” or “packing enhancers” by lowering interparticle friction.
• Such higher packing densities may result in iron negative electrodes with low porosities, leading to poor performance of the resultant iron negative electrode.
• such poor performance may be attributable to at least one or more of rate capability, attainable areal loading, specific capacity, and voltage efficiency.
• rate capability attainable areal loading
• specific capacity attainable areal loading
• voltage efficiency attainable areal loading
• the use of agglomeration of particles to form the granules 208 the second powder 206 facilitates overcoming the particle size mismatch between loose particles of solid-state additives and iron powders for use in powder mixes for iron negative electrodes.
• the use of agglomeration of particles to form the discrete granules 208 of an additive decouples the geometry of the particles of the solid-state additive from the performance of the solid-state additive in the iron negative electrode 14 - facilitating independent control of specific surface area of the additive material, additive chemistry, size of particles of the additive in the powder blend 202 in the bed 201, or any combination thereof.
• the second powder 206 including the discrete granules 208 of the agglomerated particles 210 facilitates the use of dry powder processing to form the iron negative electrode 14.
• electrode areal loadings and thicknesses are much higher than in other battery electrode contexts.
• lithium-ion electrodes commonly used for shorter duration energy storage technologies
• the iron negative electrode 14 may have an active layer strata that is greater than about 8 mm to less than about 50 mm in thickness.
• the thickness of the active layer strata refers to the thickness of the layer of the iron negative electrode 14 containing the first powder 204 including the ironactive material (and, thus, also containing the second powder 206 as part of the powder blend 202).
• Wet, slurry-based processing and slurry rheology are commonly used in the production of lithium-ion electrodes to maintain a homogeneous mix of electrode active materials, additives, and binders, throughout the process of creating an active layer.
• the drying time of a wet-processed electrode increases super-linearly with increasing thickness of the active layer material, making the use of wet processing impractical in instances in which the iron negative electrode 14 has a dramatically thicker format than lithium-ion electrodes. While dry powder processing offers advantages over wet processing with respect to fabrication time, the effects of powder rheology and attendant segregation tendencies can be much more severe in dry powder processing than in wet electrode processing.
• the second powder 206 including discrete granules 208 of the agglomerated particles 210 may be relevant to any processing route
• the second powder 206 may be particularly useful in the context of dry-processing to form the powder blend 202 of the iron negative electrode 14. That is, dry -processing the second powder 206 to form the powder blend 202 may facilitate simultaneously meeting the performance-based requirements of surface area and dispersion of the additive material within the iron negative electrode 14 while also meeting the processing-based requirements of particle size matching and segregation minimization.
• the second powder 206 including the discrete granules 208 of the agglomerated particles 210 including the additive material may facilitate mitigating floataway/fallout risk of solid-state additives in iron-negative electrodes. That is, a specific risk associated with using solid-state additives in iron negative electrodes is that these the particles of such solid-state additives may adhere to or otherwise be bound or dragged by bubbles produced during electrochemical cycling (by, e.g. hydrogen evolution or oxygen evolution), causing loss of the loose particles of the solid state additive from the iron negative electrode.
• a first factor that affects floataway/fallout risk is particle size. While it is generally lowest cost to procure the solid-state additives in small sizes (e.g. 5 microns), interactions of solid-state additives with bubbles can be severe at these length scales. Additionally, or instead, a porosity of an iron negative electrode itself may act like a “filter” for a solid-state additive if the particle size of the discrete granules 208 of the at least one metal sulfide is on the order of the pore size of the iron negative electrode 14 or greater than the pore size of the iron negative electrode 14.
• the second powder 206 of discrete granules 208 including the agglomerated particles 210 of the solid-state additive may mitigate the risk of losing particles of solid-state additive material. That is, discrete granules 208 of the agglomerated particles 210 are significantly larger than each of the individual particles and, therefore, may be more resistant to drag forces by bubbles or other forces acting to remove the solid-state additive from the iron negative electrode 14.
• the first powder 204 of the powder blend 202 in the iron negative electrode 14 may include any one or more types of iron active material suitable for use in any one or more of the various different electrochemical cells described herein.
• the iron active material of the first powder 204 may include one or more iron-bearing compounds, which may be in any one or more of various different shapes (e.g., pelletized, briquetted, pressed, or sintered) in the first powder 204.
• the one or more iron-bearing compounds may range from highly reduced forms of iron (more metallic) to highly oxidized forms of iron (more ionic).
• the size of the iron active material of the first powder 204 relative to the size of the discrete granules 208 may be tuned to facilitate dry powder processing to form the iron active electrode 14 and/or to achieve target porosity of the iron active electrode 14.
• the discrete granules 208 of the second powder 206 and the iron active material of the second powder may have similar particle sizes such that the first powder 204 and the second powder 206 have similar flow characteristics.
• the average particle size of the discrete granules 208 that minimizes segregation from the first powder 204 may be close to, but not necessarily identical to, the average particle size of the first powder 204.
• the discrete granules 208 may have a first average apparent density
• the particles that form the agglomerated particles 210 include a second average apparent density
• the first average apparent density is less than the second average apparent density.
• the first average apparent density may be greater than 1.0 grams per cubic centimeter and less than 2.1 grams per cubic centimeter.
• the lower apparent density of the discrete granules 208 relative to the apparent density of the particles forming the agglomerated particles 210 may facilitate exposing a large amount of surface area of the at least one metal sulfide to an electrolyte in an electrochemical cell.
• the zinc sulfide may be in the lower-temperature sphalerite structure (e.g., greater than 60% by weight of the zinc sulfide may be in the lower-temperature sphalerite structure), as determined by x-ray diffraction.
• the lower temperature sphalerite structure of zinc sulfide may be useful for certain types of agglomeration (e.g., sintering) that may be used to form the agglomerated particles 210 in instances in which the at least one metal sulfide includes zinc sulfide.
• the one or more metal sulfides of the discrete granules 208 may additionally or alternatively include any one or more of iron sulfide (e.g., FeS, FesS4, Fe2Ss and/or other forms), tin sulfide (SnS), bismuth sulfide E ⁇ Ss), aluminum sulfide (AI2S3), antimony(III) sulfide (Sb2S3), antimony(V) sulfide (Sb2Ss), manganese sulfide (MnS), molybdenum(IV) sulfide (M0S2), iron disulfide, iron-copper sulfide, tin sulfide, copper sulfide, cadmium sulfide, silver sulfide, titanium disulfide, lead sulfide, nickel sulfide, antimony sulfide, including polymorphs of these.
• the discrete granules 208 may additionally include a non-metal sulfide compound. Further, or instead, the discrete granules 208 may further include include tin oxide (SnCh), tin (Sn), bismuth (Bi), iron selenide (FeSe), tin selenide (SnSe), zinc selenide (ZnSe), potassium hydroxide (KOH), sodium hydroxide (NaOH), or combinations thereof.
• SnCh tin oxide
• Sn tin
• Bi bismuth
• FeSe iron selenide
• SnSe tin selenide
• ZnSe zinc selenide
• KOH potassium hydroxide
• NaOH sodium hydroxide
• the discrete granules 208 may further include particles of a pore former 212 to impart strength to the discrete granules 208, even as the discrete granules 208 are porous.
• the mean size of the particles of the pore former 212 may be selected based on geometric considerations related to the initial size of the particles of the at least one metal sulfide forming the agglomerated particles 210 and geometric considerations related to the final intended size of the discrete granules 208 after the particles of the at least one metal sulfide form the agglomerated particles 210.
• the particles forming the agglomerated particles 210 of the at least one metal sulfide may have a first mean particle size on a weight percentage basis
• the particles of the pore former 212 may have a second mean particle size on a weight percentage basis
• the second mean particle size may be greater than or equal to the first mean particle size. That is, the pore former 212 may be sized to impart more porosity to the discrete granules 208 of the second powder 206 than may be achievable using only the particles forming the agglomerated particles 210.
• the particles of the pore former 212 may be soluble in an alkaline electrolyte such that the particles of the pore former 212 dissolve (e.g., quickly or over time) and leave behind porosity in the powder blend 202 of the iron negative electrode 14.
• the particles of the pore former 212 may include any one or more different types of materials useful as spaceholders that are low cost and easy to remove.
• the particles of the pore former 212 may include potassium oxide (K2O), lithium oxide (LiO), sodium oxide (ISfeO), potassium hydroxide (KOH), lithium hydroxide (LiOH), sodium hydroxide (NaOH), sodium sulfate (NaiS), potassium sulfate (K2S), sodium carbonate (NazCOs), potassium carbonate (K2CO3), sodium stannate (Na2[Sn(OH)e]), potassium stannate (K2[Sn(OH)e]), or combinations thereof.
• Friability of less than about 15% (e.g., less than 10%, less than 5%) is acceptable for use in the second powder 206, with small variations allowable for testing tolerances.
• the starting material was a powder with a particle size of 150-500 microns. Due to the finer particle size, of the starting material, a dry particle size analyzer (Camsizer X2 with 30 kPa dispersion pressure) was used to take a particle size distribution from the material and quantify the difference in the particle size distribution before and after the material was shaken in the friability tester. A second mode was found in the particle size distribution at finer particle sizes after shaking in the friability tester; this was interpreted as originating from particle breakdown.
• a particle size may be selected that separates the fines mode from the original mode(s) in the particle size distribution. This is usually chosen as the local minimum in q3 as a function of particle size. This particle size is called the cutoff size.
• friability of less than about 10 % weight loss of the original sample as fines according to European Pharmacopoeia 2.9.41. -2 may represent suitable resistance to disintegration useful for using the second powder 206 reliably through handling to form the iron negative electrode 14 and in use in the iron negative electrode 14.
• FIG. 2C is an image showing a powder of discrete granules (e.g., the second powder 206 of the discrete granules 208 in FIGS. 2A and 2B) mixed with a powder of iron active material (e.g., the first powder 204 in FIGS. 2A and 2B).
• a powder of discrete granules e.g., the second powder 206 of the discrete granules 208 in FIGS. 2A and 2B
• a powder of iron active material e.g., the first powder 204 in FIGS. 2A and 2B
• the powder of the discrete granules is light colored
• the powder of iron active material is dark colored.
• solid state additive (ZnS) was granulated with poly(vinyl alcohol) and carboxymethylcellulose. Both binders worked to produce agglomerates. The process resulted in particles with sizes similar to iron active material in some cases.
• the selective sulfidation of ZnO without sulfidation of Fe-containing species may be achieved by, e.g., controlling the ratio of the partial pressures of H2S and H2.
• Such a controlled sulfidation reaction may limit the total amount of sulfur added to the powder mix - this is advantageous for electrochemical performance and durability. Too high of starting sulfur concentrations can lead to sulfate accumulation in the electrolyte and therefore to sulfate precipitation.
• the reaction of ZnO with H2S may occur at fairly low temperatures, including as low as 250°C, with conversion timescales on the order of several (4 to 9) hours.
• the sulfidation reaction of ZnO by H2S may be combined with a high temperature processing step for the iron material.
• a sintered or hot pressed iron negative electrode e.g., iron negative electrode 14, etc.
• H2S may be added to the cooling gas stream so that the ZnO converts into ZnS in-situ in the powder bed.
• Such an in- situ sulfidation step may usefully take advantage of the part already being hot, and may further usefully avoid the direct reduction of ZnS by metallic Fe.
• the direct reduction of ZnS by metallic Fe is undesirable as it leads to loss of ZnS and therefore increased cost of resulting Fe electrodes.
• the Na2S could be dissolved on exposure to an appropriate solvent, which could then facilitate reaction of the sulfide with the ZnO to form ZnS in the electrode.
• ZnO agglomerates could be introduced to the electrode prior to processing.
• the electrode could then be exposed to an electrolyte containing sulfide (e.g., dissolved Na2S, K2S, soluble sulfides, or mixes thereof).
• the sulfide ions are then known to exchange to form ZnS in place of the ZnO.

Landscapes

• Chemical & Material Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Inorganic Chemistry (AREA)
• Battery Electrode And Active Subsutance (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=90608998

Family Applications (1)

Country Status (4)

Family Cites Families (4)

• 2023
  • 2023-10-02 CN CN202380078856.8A patent/CN120188282A/zh active Pending
  • 2023-10-02 WO PCT/US2023/075744 patent/WO2024076932A1/en not_active Ceased
  • 2023-10-02 EP EP23875664.7A patent/EP4599488A1/de active Pending
  • 2023-10-03 TW TW112137978A patent/TW202429736A/zh unknown

Also Published As

Similar Documents

Legal Events