WO2024041992A2 - Procédé de transport d'un matériau actif d'électrode pour batteries - Google Patents

Procédé de transport d'un matériau actif d'électrode pour batteries Download PDF

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Publication number
WO2024041992A2
WO2024041992A2 PCT/EP2023/072784 EP2023072784W WO2024041992A2 WO 2024041992 A2 WO2024041992 A2 WO 2024041992A2 EP 2023072784 W EP2023072784 W EP 2023072784W WO 2024041992 A2 WO2024041992 A2 WO 2024041992A2
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WO
WIPO (PCT)
Prior art keywords
active material
container
electrode active
range
valve
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
Application number
PCT/EP2023/072784
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English (en)
Other versions
WO2024041992A3 (fr
Inventor
Klaus Kuehling
Elena SIZIKOV-KOEHNSEN
Nadine RUDOLPH
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2024041992A2 publication Critical patent/WO2024041992A2/fr
Publication of WO2024041992A3 publication Critical patent/WO2024041992A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D88/00—Large containers
    • B65D88/26—Hoppers, i.e. containers having funnel-shaped discharge sections
    • B65D88/30—Hoppers, i.e. containers having funnel-shaped discharge sections specially adapted to facilitate transportation from one utilisation site to another
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D90/00—Component parts, details or accessories for large containers
    • B65D90/22—Safety features
    • 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 is directed towards a process for the transportation of an electrode active material for batteries, said process comprising the following steps:
  • Batteries and electrochemical cells are devices for storage of energy.
  • lithium-ion secondary batteries are modern devices for storing energy.
  • Many application fields have been and are contemplated, from small devices such as mobile phones and laptop computers through car batteries and other batteries for e-mobility.
  • Various components of the batteries have a decisive role with respect to the performance of the battery such as the electrolyte, the electrode materials, and the separator.
  • Particular attention has been paid to the cathode materials.
  • Several materials have been suggested, such as lithium iron phosphates, lithium cobalt oxides, and lithium nickel cobalt manganese oxides. Thanks to extensive research activities, marketing has begun, and the number of lithium-ion batteries is increasing.
  • FIBC flexible intermediate bulk containers
  • the electrode active material particles should be safe against breakage - both during the commute and during charging or discharging of the vessel. In addition, they must not create any dusting problems since many electrode active materials, for example nickel metal hydride or cathode active materials for lithium ion batteries contain significant amounts of nickel. Dusting may constitute a problem especially during discharging in embodiments where big bags are used as transportation container of the electrode material. In addition, electrode active materials should not be exposed to air that contains water (moisture) and carbon dioxide. Again, charging and discharging of big bags may create problems.
  • inventive process comprises step (a), step (b), step (c) and step (d), in brief also (a), (b), (c) and (d), respectively. Steps (a) to (d) are described in more detail below.
  • an electrode active material in particulate form is provided, for example immediately after production or after production and storage.
  • Said electrode active material may be a cathode active material, hereinafter also cathode active material (A), or an anode active material.
  • Said electrode active material may be provided with or preferably without conductive carbon.
  • Said electrode active material may also be referred to as electrode active material (A).
  • Suitable anode active materials are TiC>2 and LTO (lithium titanium oxide), for example lithium titanate spinel of the formula Li4Ti50i2 up to Li 7 Ti 5 0i2.
  • LTO lithium titanium oxide
  • Li4Ti50i2 up to Li 7 Ti 5 0i2.
  • Other examples are those of the system Li2O-TiO2, for example Li2TiOa.
  • cathode active materials are nickel metal hydride (“NiMH”), non-doped or preferably doped.
  • said cathode active material (A) is suitable for a lithium-ion battery.
  • examples are LCO (LiCoCh), NCA (lithiated nickel-cobalt aluminum oxide), LNO (Li NiO2) having a layered crystal structure, spinel of general formula Li(Ni t Mn2-t)O4 with t being in the range of from zero to 0.5, high-lithium materials Lii +x iTM’i- x iO2 with x1 being in the range of from zero to 0.33, preferably 0.1 to 0.3, and TM containing a combination of Mn and Ni and, optionally, further metals such as Co, Al, Ti, Zr, and NCM of the formula Lii +X 2TM”i.
  • X 2O2 with x1 being in the range of from zero to 0.1 , preferably 0.01 to 0.05, and wherein TM” is a combination of Ni, Co and Mn that may additionally include one or more metals selected from Mg, Al, Ti, Zr, Nb, Ta, and Mo.
  • TM is a combination of Ni, Co and Mn that may additionally include one or more metals selected from Mg, Al, Ti, Zr, Nb, Ta, and Mo.
  • NCA lithiated nickel-cobalt-aluminum oxide.
  • a cathode active material (A) that has the general formula Lii +x TMi. x O2 wherein x is in the range of from -0.03 to +0.3 and TM is a combi- nation of metals that contains at least 90 mol-% of Ni, Co or Mn or at least 90 mol-% of a combination of at least two of Ni, Co and Mn.
  • TM is a combination of metals according to general formula (I)
  • b + c zero.
  • Cathode active material (A) provided in step (a) may be non-coated or coated, for example with an oxide compound of B, of Co or of W.
  • Oxide compounds of B include B2O3, UBO2 and U2B4O7.
  • Oxide compounds of Co include CO2O3, CO3O4, UCOO2, sub-lithiated lithium cobalt oxide.
  • Oxide compounds of W include WO3, U2WO4 and the like.
  • Cathode active material (A) as provided in step (a) is a particulate material, with an average particle diameter (D50) in the range of from 2 to 20 pm, preferably 3 to 16 pm, more preferably 4 to 14 pm, determined by LASER diffraction.
  • said cathode active materials (A) have a particle size distribution, expressed by a span [(D90) - (D10)] divided by (D50) is in the range of from 0.2 to 2, preferably from 0.25 to 0.5 or from 0.8 to 1.4, determined by LASER diffraction.
  • (D10), (D50) and (D90) refer to the respective median with respect to the volume based value.
  • the particle size distribution may be mono-modal or bi-modal or multimodal.
  • the shape of the particles is preferably spherical. In many embodiments, and even when the formation of fines is reduced during manufacture, it is observed that a certain amount of fines is formed, for example 0.1 to 2% by weight. Such fines are defined as having a particle diameter of 10% or less of the average diameter (D50).
  • the amount of cathode active material to be shipped may be in the range of from 3 to 34 metric tons, preferably 10 to 25 metric tons, more preferably 15 to 20 metric tons.
  • Step (b) includes transferring said electrode active material (A) and preferably said cathode active material into a container (B) that has a total length in the range of from 10 to 40 feet (3.3 to 15 meters), preferably 4 to 9.5 meters.
  • the length refers to the total length and includes valves and further additive parts, if applicable.
  • the base may be circular shaped or rectangular or square. It is preferred to use containers that are transported by truck, more preferred standalone containers that can be loaded onto a chassis, e.g., a truck, a ship, a trailer or a freight flat wagon.
  • Container (B) is equipped with at least one valve for charging/discharging, hereinafter also referred to as intake valve.
  • such container (B) contains another valve for controlling the atmosphere in container (B), for example for inert gas pressure.
  • said electrode active material (A) cathode active material is transferred into a container that is selected from silos for transportation of cement.
  • a container that is selected from silos for transportation of cement.
  • they Preferably, they have a conically shaped outlet at the bottom to facilitate discharging the container.
  • a conical design of the container outlet is beneficial.
  • other container designs may be preferred that for steep cone shapes.
  • One example of a flat container design is an udder silo as depicted below.
  • Interchangeable containers are typically 4 to 9.5 m in total height, 1.5 to 2 m and preferably 2.5 m in diameter and 1.5 to 7 m, more preferred 2 to 4 m in cylinder length. They are equipped with mounting fittings so that they can be connected to and loaded onto transport cars by changing systems, in the context of the present invention also referred to as “connector to changing systems”.
  • the cathode active material may be freshly synthesized. However, it is advantageous to make sure that the freshly synthesized cathode active material has cooled to ambient temperature before transferring it to the container.
  • the container does not contain any big bag so the transportation is big bag-free.
  • Containers are preferably made from steel, for example weathering steel, for example corten steel or stainless steel.
  • Step (b) is performed under an atmosphere free from moisture and CO2.
  • free from moisture and CCh shall mean that the moisture and CO2 content is 0.01 % by volume or less.
  • the carbon dioxide content may be detected by IR spectroscopy.
  • the container is pressurized with a pressure of up to 2 atm between steps (b) and (c), preferably with up to 0.5 atm.
  • the container then has a positive pressure even if the temperature decreases during transport due to weather conditions, and access of moisture and carbon dioxide is difficult.
  • Dust formation may be prevented by technical provisions.
  • said discharging spout is centered onto a charging intake of the receiving station (C) with very low or zero dead volume.
  • C receiving station
  • More preferred is a self-centering system that automatically minimizes the dead volume between the discharge valve and the intake valve.
  • suitable valves are cone valves and butterfly valves.
  • butterfly valves are concentric butterfly valves, doubly eccentric butterfly valves and triply-eccentric butterfly valves.
  • the principle of self-centering valves applies to at least two valves of the container (B), i.e., intake and discharge on container as well as equipment installed in production plant (for filling) and receiving plant (for accepting). Further devices for pre-alignment preferred, e.g., skids which center when put on top of each other.
  • Step (c) includes moving one or more containers filled with cathode active material over a distance in the range of from 5 km to 2500 km, preferably 10 to 800 km.
  • said one or more containers are moved by ship, truck, train or a combination thereof.
  • Particularly advantageous are so-called interchangeable containers that are lifted onto a transport chassis by automated changing systems.
  • step (d) the cathode active material is discharged at the destination in a receiving station (C) that is protected against moisture and CO2 access.
  • the receiving station is connected to container (B) via a direct link through which the cathode active material (A) is transferred from the container (B) to the receiving station (C) and any dust formation is prevented.
  • a discharge station that allows for the self-centering docking of the container discharge unit is preferred.
  • Such a unit may be a self-centering valve.
  • the valves on both sides, the container as well as the discharge station, are designed to minimize the dead volume after docking.
  • the low dead volume between the valves is flushed with dry and CCh-free gas to optimize the transfer conditions.
  • valves in the inventive set-up i.e., intake and discharge on container as well as equipment installed in production plant (for filling) and receiving plant (for accepting).
  • the transfer preferably happens by force of gravity.
  • Other technical solutions like powder feeding systems or screw feeders and alike can also be applied.
  • technical devices to improve the fluidization of the powder can be applied, for example knockers, or inert gas introduction in the discharging area of the container.
  • the low (or preferably zero) dead volume design of the docking station allows for low contamination of the electrode active material.
  • the dead volume should be minimized as far as possible, for example by the application of a self-centering valve.
  • dust formation which poses a critical risk of FIBC handling, charging and discharging, can be minimized.
  • a further aspect of the present invention is directed towards a set-up in which
  • container (B) is located on a vehicle (D) selected from a truck, a ship, a trailer or a freight flat wagon.
  • electrode active material (A) is a cathode active material.
  • electrode active material (A) is a cathode active material of the general formula Lii +x TMi-xO2 wherein x is in the range of from -0.03 to +0.3 and TM is a combination of metals that contains at least 90 mol-% of Ni, Co or Mn or at least 90 mol-% of a combination of at least two of Ni, Co and Mn.
  • Container (B) preferably has a cylindrical shape. Said shape refers to the main body.
  • container (B) preferably has a conical bottom that mounts into a valve for charging/discharging. Even ore preferably, container (B) contains another valve for controlling the atmosphere in container (B), for example for inert gas overpressure.
  • container (B) refers to the main body, thus, without any conical bottom, if applicable.
  • the inventive set-up comprises a receiving station
  • (C) that preferably comprises a self-centering valve.
  • a particular advantage of the inventive set-up is that due to the horizontal position of container (B) during transport and the vertical positioning of container (B) before discharging, potential agglomeration of particles of electrode active material (A) are put under moderate mechanical shear, and the fluidization is improved.
  • CCS connector for changing system
  • CCS connector for changing system
  • IC interchangeable container containing electrode active material
  • Figure 3 Truck with udder container
  • VCS actual valve cross section to be opened (shaded dark)
  • cathode active material (A.1), formula Lii.oi(Nio.8oCoo.i5Alo.o5)o.9902, coated with 0.3% by weight boric acid and subsequent heating to 325 °C for 3 hours, average particle diameter 5 pm, determined by electroacoustic methods, span of particle size distribution 1.07, were provided, step (a.1).
  • Cathode active material (A.1) had a moisture content of 200 ppm by weight, determined by Karl-Fischer-titration.
  • the span is defined as [(D90) - (D10)]/D50, determined by LASER diffraction.
  • a container (B.1) according to Figure 1 dimensions: height 7.04 m, diameter 2.5 m, length of cylinder 3.75 m, volume 23 m 3 , was charged with said cathode active material (A.1), through the valve, step (b.1).
  • Step (c.1) The full container (B.1) was mounted on a truck, and the truck was driven over 20 km over a road with bumps and potholes, followed by a period of four days to allow cathode active material (A.1 ) to settle inside container (B.1).
  • Step (d.1) The truck was moved to a discharge station (C.1) protected against moisture and CO2 access and discharged. A breakage of particles of cathode active material (A.1) was not detected by, e.g., a particle size distribution determination before and after the transport. In addition, no skimming up of bigger particles could be detected.

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

Abstract

L'invention concerne un procédé de transport sans grands sacs d'un matériau actif d'électrode pour batteries, ledit procédé comprenant les étapes suivantes : (a) fournir un matériau actif d'électrode (A) sous forme particulaire, par exemple, un matériau actif de cathode, (b) transférer ledit matériau actif d'électrode (A) dans un récipient (B) qui a une longueur totale dans la plage de 10 à 40 pieds (6 à 15 mètres) et est équipé d'au moins une soupape pour le chargement/déchargement, (c) déplacer un ou plusieurs récipients (B) remplis de matériau actif d'électrode (A) sur une distance dans la plage de 5 km à 2500 km, (d) décharger le récipient dans une station de réception (C) qui est protégée contre l'accès d'humidité et de CO2.
PCT/EP2023/072784 2022-08-26 2023-08-18 Procédé de transport d'un matériau actif d'électrode pour batteries Ceased WO2024041992A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP22020410.1 2022-08-26
EP22020410 2022-08-26

Publications (2)

Publication Number Publication Date
WO2024041992A2 true WO2024041992A2 (fr) 2024-02-29
WO2024041992A3 WO2024041992A3 (fr) 2024-08-15

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Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4212331A (en) * 1978-12-01 1980-07-15 Victor Benatar Pressurized apparatus for discharging powdered reagent from a shipping container
US4850506A (en) * 1986-12-17 1989-07-25 Connelly Containers, Inc. Container for fluent material
WO2017136547A1 (fr) * 2016-02-05 2017-08-10 Warwick Mills, Inc. Conteneur d'expédition résistant aux températures élevées
CN108145859A (zh) * 2017-11-06 2018-06-12 三汽车制造有限公司 一种搅拌站、搅拌站粉料罐及其制造方法
US11453542B2 (en) * 2019-06-07 2022-09-27 James M Kennedy Shipping container to mitigate external fire risks
US11542091B2 (en) * 2020-07-23 2023-01-03 Cellblock Fcs, Llc Shipping package for lithium battery

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Publication number Publication date
WO2024041992A3 (fr) 2024-08-15

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