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Title:
PROCESS FOR THE TRANSPORTATION OF AN ELECTRODE ACTIVE MATERIAL FOR BATTERIES
Document Type and Number:
WIPO Patent Application WO/2024/041992
Kind Code:
A2
Abstract:
Process for the big bag-free transportation of an electrode active material for batteries, said process comprising the following steps: (a) providing an electrode active material (A) in particulate form, e.g., a cathode active material, (b) transferring said electrode active material (A) into a container (B) that has a total length in the range of from 10 to 40 feet (6 to 15 meters) and is equipped with at least one valve for charging/discharging, (c) moving one or more containers (B) filled with electrode active material (A) over a distance in the range of from 5 km to 2500 km, (d) discharging the container in a receiving station (C) that is protected against moisture and CO2 access.

Inventors:
KUEHLING KLAUS (DE)
SIZIKOV-KOEHNSEN ELENA (DE)
RUDOLPH NADINE (DE)
Application Number:
PCT/EP2023/072784
Publication Date:
February 29, 2024
Filing Date:
August 18, 2023
Export Citation:
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Assignee:
BASF SE (DE)
International Classes:
B65D81/20; B65D85/00; H01M10/052
Attorney, Agent or Firm:
BASF IP ASSOCIATION (DE)
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Claims:
Patent Claims

1 . Process for the big bag-free transportation of an electrode active material for batteries, said process comprising the following steps:

(a) providing an electrode active material (A) in particulate form,

(b) transferring said electrode active material (A) into a container (B) that has a total length in the range of from 10 to 40 feet (3.3 to 15 meters) and is equipped with at least one valve for charging/discharging,

(c) moving one or more containers (B) filled with electrode active material (A) over a distance in the range of from 5 km to 2500 km,

(d) discharging the container(s) (B) in a receiving station (C) that is protected against moisture and CO2 access.

2. Process according to claim 1 wherein the electrode active material (A) is a cathode active material (A).

3. Process according to claim 1 or 2 wherein container (B) has a cylindrical shape.

4. Process according to any of the preceding claims wherein in step (a), a cathode active material (A) is provided that has the general formula Lh+xTMi-xCh 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.

5. Process according to any of the preceding claims wherein receiving station (C) allows for the discharging of container (B) under exclusion of CO2 and moisture by use of a selfcentering valve.

6. Process according to any of the preceding claims wherein container (B) is moved by ship, truck, train or a combination thereof.

7. Process according to any of the preceding claims wherein between steps (b) and (c), the container is pressurized with a pressure of up to 2 atm.

8. Big-bag-free set-up comprising

(A) an electrode active material suitable for a battery, placed in (B) a container with a total length in the range of from 10 to 40 feet equipped with at least one valve for charging/discharging. Set-up according to claim 8 wherein container (B) is located on a vehicle (D) selected from a truck, a ship, a trailer or a freight flat wagon. Set-up according to claim 8 or 9 wherein electrode active material (A) is a cathode active material. Set-up according to any of the claims 8 to 10 wherein electrode active material (A) is a cathode active material of the general formula Lii+xTMi-xO2 wherein x is in the range of from -0.03 to +0.3 and wherein 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. Set-up according to any of the claims 8 to 11 wherein the set-up comprises a receiving station (C). Set-up according to claim 11 or 12 wherein the receiving station (C) comprises a selfcentering valve. Set-up according to any of the claims 8 to 13 wherein container (B) has a cylindrical shape.

Description:
Process for the transportation of an electrode active material for batteries

The present invention is directed towards a process for the transportation of an electrode active material for batteries, said process comprising the following steps:

(a) providing an electrode active material (A) in particulate form,

(b) transferring said electrode active material into a container that has a total length in the range of from 10 to 40 feet (3.3 to 15 meters) and is equipped with at least one valve for charging/discharging,

(c) moving one or more containers filled with electrode active material over a distance in the range of from 5 km to 2500 km,

(d) discharging the container in a receiving station that is protected against moisture and CO2 access.

Batteries and electrochemical cells are devices for storage of energy. In particular, 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.

Investments are made to build so-called giga-plants. They are designed to assemble huge numbers of cells. The respective electrode active materials are usually made somewhere else and need to be shipped in a multi-kilo-ton scale. The safe transport then has various requirements. Not all of them are perfectly met in the current mode of transport that involves flexible intermediate bulk containers (“FIBC”), so-called big bags. Such FIBCs typically contain from 500 to 1 ,300 kg of electrode active material.

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.

It was therefore an objective to provide a method of transportation of electrode active materials that avoids the above shortcomings. It was further an objective to provide a set-up that enables to avoid the above shortcomings during the transportation of electrode active materials.

Accordingly, the process as defined at the outset has been found, hereinafter also referred to as inventive process or process according to the (present) invention. The 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.

In step (a), 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).

Examples of 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. Other examples are those of the system Li2O-TiO2, for example Li2TiOa.

Examples of suitable cathode active materials are nickel metal hydride (“NiMH”), non-doped or preferably doped.

In a preferred embodiment, 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. A further example is so-called NCA, lithiated nickel-cobalt-aluminum oxide.

In a preferred embodiment, in step (a) a cathode active material (A) is provided 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.

In one embodiment of the present invention, TM is a combination of metals according to general formula (I)

(Ni a Co b Mn c )i- d M d (I) a being in the range of from 0.85 to 0.99, b being zero or in the range of from 0.01 to 0.12, c being in the range of from zero to 0.12, and d being zero or in the range of from 0.0025 to 0.05,

M is at least one of Mg, Al, Nb, Ti and Zr, and a + b + c = 1.

Preferably, 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.

In one embodiment of the present invention, 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. Preferably, such container (B) contains another valve for controlling the atmosphere in container (B), for example for inert gas pressure.

In another embodiment, said electrode active material (A) cathode active material is transferred into a container that is selected from silos for transportation of cement. Preferably, they have a conically shaped outlet at the bottom to facilitate discharging the container.

A conical design of the container outlet is beneficial. For flat cone shapes 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.

One preferred example of a container design with a steep conical outlet is an interchangeable silo. 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”.

Particularly advantageous are containers with fork-lift pockets and containers with gooseneck tunnels. 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. In the context of the present invention, “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.

In one embodiment of the present invention, 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. For example, in embodiments wherein the container is equipped with a discharging spout, said discharging spout is centered onto a charging intake of the receiving station (C) with very low or zero dead volume. More preferred is a self-centering system that automatically minimizes the dead volume between the discharge valve and the intake valve. Examples for suitable valves are cone valves and butterfly valves. Examples of butterfly valves are concentric butterfly valves, doubly eccentric butterfly valves and triply-eccentric butterfly valves.

In one embodiment of the present invention, 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. In one embodiment, 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.

In step (d), the cathode active material is discharged at the destination in a receiving station (C) that is protected against moisture and CO2 access.

In the course of step (d), 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.

Said transfer is accomplished under an atmosphere free from moisture and CO2. 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. In one preferred technical embodiment the low dead volume between the valves is flushed with dry and CCh-free gas to optimize the transfer conditions.

In one embodiment of the present invention, self-centering valves are applied.

Principle of self-centering valves applies to all 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 application of further devices for pre-alignment is preferred, like skids which center when put on top of each other.

The transfer preferably happens by force of gravity. Other technical solutions like powder feeding systems or screw feeders and alike can also be applied.

Depending on the flow properties of the product powder, 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.

After transfer of the product 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. Thus, 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

(A) an electrode active material suitable for a battery, placed in

(B) a container with a total length in the range of from 10 to 40 feet equipped with at least one valve for charging/discharging.

In a further embodiment of the present invention, container (B) is located on a vehicle (D) selected from a truck, a ship, a trailer or a freight flat wagon.

In a further embodiment of the present invention, electrode active material (A) is a cathode active material.

In a further embodiment of the present invention, 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.

The dimensions of container (B) refer to the main body, thus, without any conical bottom, if applicable.

In one embodiment of the present invention, 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.

The invention is further illustrated by drawings and a working example. Brief description of the drawings:

Figure 1 : Interchangeable containers

CCS: connector for changing system

Cy: main cylinder containing electrode active material

F: valve for charging (intake valve)

Co: cone

D: discharge valve

S: Skid for transport and storage

Figure 2 : Truck with interchangeable container

CCS: connector for changing system

IC: interchangeable container containing electrode active material

T : Truck

Figure 3 : Truck with udder container

F: valves for charging (intake valves)

Cy: main cylinder containing electrode active material

Co: cone

D: valve for discharging, “discharge valve”

T : Truck

Figure 4: principle of self-centering docking station

Abbreviations of the container vide supra, S1 : Skid for transport and storage

Docking Station:

S2: Skid of docking station, with centering devices

In: Intake valve with self-centering devices

CP: Connection to plant equipment

Figure 5: principle of a self-centering valve

D: Discharge Valve

SF: Sealing Surface

H: Holes to take up the spikes and thus center the two valve parts

Sp: Spike to center the discharge and the intake valve

VCS: actual valve cross section to be opened (shaded dark)

In: Intake Valve Working example:

18 tons of a 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.