WO2022075846A1

WO2022075846A1 - Integrated manufacturing of core-shell particles for li-ion batteries

Info

Publication number: WO2022075846A1
Application number: PCT/NL2021/050607
Authority: WO
Inventors: Jan Rudolf Van Ommen
Original assignee: Technische Universiteit Delft
Priority date: 2020-10-07
Filing date: 2021-10-06
Publication date: 2022-04-14
Also published as: NL2026635B1

Abstract

The invention provides a method for providing coated particles (20), the method comprising: (a) a particle generation process comprising feeding a starting material (5) to a particle generation zone (1100) to generate particles (10); wherein the particle generation process comprises a spray process; (b) feeding with a fluid flow the particles (10) generated in the particle generation zone (1100) from the particle generation zone (1100) to a coating zone (1200); and (c) a particle coating process comprising coating the particles (10) while flowing in the coating zone (1200) to provide the coated particles (20); wherein the particle coating process comprises a vapor deposition process.

Description

Integrated manufacturing of core-shell particles for Li-ion batteries

FIELD OF THE INVENTION

The invention relates to a method for providing coated particles. Further, the invention relates to an apparatus for providing such coated particles. Yet further, the invention also relates to a material, or an electrode, comprising such coated particles. The invention also relates to a battery comprising such electrode.

BACKGROUND OF THE INVENTION

Plasma processing methods for producing a metastable material are known in the art. US20120313269A1, for instance, describes a far-from-equilibrium plasma processing method, for selectively producing a metastable material comprising the steps of: feeding a precursor material into a shrouded plasma flame; controlling a reaction zone where pyrolysis, melting or vaporization of the precursor material occurs; quenching the reaction products to selectively form either one of metastable nano- and micron-sized particles; and collecting the reaction product in the form of a metastable powder, coating, deposit or perform. The plasma flame is enclosed or shrouded in a tube of heat-resistant material, thus transforming the system into a hot-wall tubular reactor, internally maintained at a high surface temperature by intense radiation from the plasma.

US2011/236575 describes a reactor for conducting vapor phase deposition process is disclosed. The reactor includes a reactive precursor reservoir beneath a powder reservoir and separated from it by valve means. A reactive precursor is charged into the reactive precursor reservoir and a powder is charged into the powder reservoir. The pressures are adjusted so that the pressure in the reactive precursor reservoir is higher than that of the powder reservoir. The valve means is opened, and the vapor phase reactant fluidized the powder and coats its surface. The powder falls into the reactive precursor reservoir. The apparatus permits vapor phase deposition processes to be performed semi-continuously.

WO2018/156607 describes in claim 1 a composition, comprising: a material having a formula (Lil+a(NiqMrCol_q_r)02)x(Lil+a(NisMntCol_s_t)02)l-x, wherein: M is Mn and/or Al; x is a numerical value inclusively ranging from 0.70 to 0.95; a is a numerical value inclusively ranging from 0.01 to 0.07; q is a numerical value inclusively ranging from 0.80 to 0.96; r is a numerical value inclusively ranging from 0.01 to 0.10; s is a numerical value inclusively ranging from 0.34 to 0.70; t is a numerical value inclusively ranging from 0.20 to 0.40; 1-q-r is greater than 0; and 1-s-t is greater than 0.

US2014/0072874 describes a composite cathode active material comprising: a core capable of intercalating and deintercalating lithium; and a crystalline coating layer disposed on at least part of a surface of the core, wherein the coating layer comprises a metal oxide.

EP2292557 describes a continuous process for preparing carbon-coated lithium- iron-phosphate particles, wherein the carbon-coated lithium-iron-phosphate particles have a mean (d50) particle size of 10 to 150 nm, and wherein the carbon-coating is an acetylene-black coating, comprising performing in a reactor a flame-spray pyrolysis step (i) in a particle formation zone of the reactor, and a carbon-coating step (ii) in a carbon-coating zone of the reactor, wherein in (i) a combustible organic solution containing a mixture of lithium or a lithium compound; iron or an iron compound; and phosphorus or a phosphorous compound in an organic solvent, is fed through at least one nozzle where said organic solution is dispersed, ignited and combusted, to give a flame spray thereby forming an aerosol of lithium iron phosphate particles; (ii) acetylene gas is injected into said aerosol thereby forming an acetylene-black coating on the lithium iron phosphate particles; (iii) the coated particles are cooled by an inert quench gas and collected on a filter.

US2019/0006697 describes a method for producing a battery cell, the method comprising providing, in a coating step, material particles having a first coating, and, in a deposition step, accelerating the material particles having the first coating toward a substrate in such a way that the first coating of the material particles bonds on impact on the substrate with the first coating of further material particles so that a first layer is formed.

SUMMARY OF THE INVENTION

In a wide range of fields, exciting applications are promised for nanostructured particles, such as selective catalysts without noble metals, self-healing materials, personalized medicine, and cost-effective batteries. Nano structured particles are solid grains which may consist of multiple materials and/or multiple elements, in which at least one of the elements may have a nanoscale dimension.

Nanoscale dimensions may be defined as within the range of 0.1-100 nm.

Nanostructured particles may exhibit extraordinary and/or tunable properties compared to bulk solid objects. Many of the advantageous properties of nanostructured materials may be based on their large proportion of interfaces, as well as phase separation, non- equilibrium phases, residual stresses, and/or other defects. Thus, some nanostructured materials may be far from their equilibrium state. Therefore, it may be a challenge to keep them as they are.

Thermal or chemical activation can enhance diffusion, relaxation, grain growth, and homogenization processes resulting in partial or total annihilation of nanostructure and loss of the associated properties. In a number of cases, coating at the nanoscale appears to be a way to drastically improve the stability of metastable nanostructures. For example, a coating may be used to prevent contact of the nanostructured particles with reactive species in the surroundings. In this way the morphology of the nanostructured particle may be preserving.

A challenge when creating nanostructured particles may be to achieve consistency. It may be desirable to ensure that variations in the properties (diameter, coating thickness, composition) are relatively limited. A good example are quantum dots: core-shell particles that emit specific photons depending on their size. For quantum dots to emit well- defined photons, it is desirable that the standard deviation in their size is less than about 5%. This may correspond to a precision of a single consistent atom layer throughout the relevant range of 1-15 nm. A high level of control over morphology may thus in certain applications be relevant. While this is already demanding for small amounts of particles, it may often become daunting when trying to make larger amounts, as may be required for practical applications.

At lab-scale, nanostructured materials may often be synthesized in small-scale, ultra-fast processes in the liquid phase, using practices from colloidal chemistry to keep the materials stable. This may generate samples for research. However, there may be no clear route to a scalable process for industrial applications.

Gas-phase synthesis of nanoparticles may have the advantage of good scalability. Diffusion is faster in the gas phase - which may make it easier to avoid concentration gradients - and the amount of helping agents required may typically be much lower. This may make the processes relatively cleaner.

Advantageously, it appears that a gas phase synthesis may also enable integration with gas phase coating techniques. In this way, a wide range of materials may be deposited.

For producing particles at the nano scale or micron scale, which may serve as core particles for nanostructured particles (see also below), amongst others, two gas-phase techniques may be applied: spray drying for organic particles and flame spray synthesis for inorganic particles. Spray drying may, amongst others, be used for making organic particles that may e.g. not be able to withstand high temperatures. A solution or dispersion (typically waterbased) of the materials that should be turned into particles is sprayed into droplets, typically under mild heating, and the subsequent evaporation of the droplets leads to the formation of particles. Spray drying may be used in application areas such as food, pharma, and detergents. In embodiments, micron-sized particles (typically 5-100 pm) or agglomerates of such particles may be made. Even, spray drying equipment may allow production of particles having a size equal to or smaller than 1 pm. To make the droplets small enough to end up with nanoparticles, in embodiments acoustic nozzles may be used. As will be further discussed below, using supercritical CO2 as the main solvent may be useful in the present invention.

Flame synthesis is also process to produce inorganic nanoparticles (and slightly larger particles, around 1 pm) such as carbon black, fumed silica, or titania, on an industrial scale. In this process a volatile precursor may be vaporized and fed into a flame in the reaction chamber. Here the precursor molecules in the gas react to nanoparticles (especially by nucleation, coagulation, aggregation, and agglomeration).

In embodiments, reactors for synthesizing nanoparticles using a liquid precursor may be used. Such reactors may be based on spray pyrolysis. Especially, in embodiments flame spray pyrolysis (FSP) may be used. In this process, the flame may be created by the direct combustion of droplets of a highly energetic precursor without any pre-processing. FSP may feature short residence times, high process temperatures, and a large temperature gradient. This may lead to highly crystalline nanoparticles with a narrow size distribution.

In (alternative) embodiments, plasma spray pyrolysis (PSP) may be applied for the synthesis of metastable nanoparticles, which may e.g. not be obtainable with the high temperatures involved in FSP. In this approach, an aqueous solution of the precursor may be sprayed in a plasma to form the desired particles.

To stabilize the obtained particles or to enable additional functionalities, a subsequent coating step may be desirable.

For growing ultrathin films on substrates in a versatile way, it appears that especially chemical vapor deposition (CVD) or atomic layer deposition (ALD) are useful gasphase techniques that can be used to apply a variety of (ultrathin) coatings around particles of nano-size to micrometer-size. An approach for these two (reactive) gas-phase techniques may especially rely on two reactants. In specific embodiments, the (reactive) gas-phase techniques may especially rely on three reactants. In yet further embodiments, e.g. in CVD applications, there may be - in specific embodiments - only one reactant. As indicated below, also molecular layer deposition (MLD) may be applied.

In CVD, these two reactants may in embodiments be fed simultaneously, and the contact time may especially determine the thickness of the coating.

In ALD, a stage two reactants may be fed alternatingly, and such stage can be repeated a number of times. The number of repetitions may especially determine the coating thickness. As a result, ALD may have a higher degree of control than CVD, yet it may be slower than CVD. It may depend on the application to determine which of the two may be used. ALD and CVD may be used to make a very wide range of different materials.

Especially, when applied to large-area surfaces such as a collection of particles, ALD and CVD cannot always be seen as strictly separated. For example, for low-temperature coating of alumina with an ALD approach, the CVD mechanism plays an important role. Nevertheless, high-quality films can be obtain with a high level of precision.

Note that the reactants used in ALD and CVD may be highly reactive: they may not be compatible with a high temperature and/or a humid environment in a gas-phase production of particles, such as spray drying or flame spray pyrolysis.

Hence, it is an aspect of the invention to provide an alternative method for providing coated particles, which preferably further at least partly obviates one or more of above-described drawbacks. Yet further, it is an aspect of the invention to provide an alternative material comprising such coated particles, which preferably further at least partly obviates one or more of above-described drawbacks. Yet, it is also an aspect of the invention to provide an alternative electrode and/or battery, comprising such material (comprising such coated particles), which preferably further at least partly obviates one or more of abovedescribed drawbacks. The present invention may have as object to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative.

It appears that known methods do not allow the direct integration of particle creation and coating for a broad class of materials, while this would be very valuable to have, especially in embodiments to turn metastable materials into stabilized, nanostructured particles. Here below, two examples are described of a method that can be deployed to a much wider range of applications.

A first example is related to e.g. pharmaceutical products applications. Molecular complexity of drugs has significantly increased over the last decades, often causing poor solubility in water and thus poor bio-availability. By turning the material into nanoparticles, the solubility may be increased. An even further improvement of solubility may in embodiments be achieved by making metastable amorphous nanoparticles. However, many materials may have a very high propensity to crystallize. Hence, it may be challenging to produce amorphous structures. This is typically not possible via a precipitation from solution route to create such metastable amorphous organic into nanoparticles. With this method, crystallization is typically much faster than termination of the precipitation reaction, and the resultant nanoparticles are crystalline.

A way to make amorphous nanoparticles instead may be to form droplets from the solution through spray-drying. In this case, nanoparticles start to form when the solute concentration exceeds its saturation concentration and amorphous nanoparticles can be obtained. However, it may be relatively difficult to keep in the amorphous, metastable state. Amorphous particles can degenerate in a matter of day, which seems relatively very impractical for a pharmaceutical. A potential way to strongly extend the lifetime of the amorphous particles may be to provide them with a protective coating, e.g. to shield them from moisture. Such a coating can also have another advantage as such coating may be used to control the rate of dissolution, such as e.g. described in WO2010/110664. While a drug should preferably be wellsoluble in water, a high rate of dissolution may in embodiments be undesirable, as it may lead to a sudden peak concentration in the patient which could lead to undesired side-effects. Hence, coating of the particles can be used to obtain this desired controlled-release behavior.

However, since the water may be used as a solvent in the particle production, such solvent seems at least partly incompatible with e.g. the ALD process. This may also apply to the CVD process.

A second example is directed to electrode, especially cathode, materials for Li- ion batteries. As an example of inorganic nanostructured particles here below embodiments of cathode particles for Li-ion batteries are discussed.

In these batteries, which are widely used in e.g. electric vehicles, the cathode may make up for the largest part of the costs. Currently, the most widely applied class of materials are the ternary materials Li[Nii-x-yCo_xMn_y]O2, wherein x is selected from the range of 0-0.5, and wherein y is selected from the range of 0-0.5. Especially, one or both of x and y are larger than 0. A common abbreviation for such materials is NMC or NCM with numbers indicating the decimals of the elements (e.g. NCM523: LiNio.5Coo.2Mno.3O2). Features associated with the end members are higher capacity (nickel), better rate capability (cobalt) and improved safety (manganese). Strongly reducing the cobalt-content may make Li-ion batteries more sustainable. However, reducing the Co content may lead to a one or more problems: higher chance of gas formation; cation missing and spinel formation; cracks in the grain boundaries. In summary, Co may be necessary to keep batteries stable during operation.

As also indicated above, liquid-phase production methods of these materials may give low yields as they involve multiple steps and laborious processes, each bearing a risk of introducing impurities into the final product, creating batch-wise inconsistencies in the process. Further, they may require relatively long reaction times (12-24 h), and it appears to be challenging to control the size and composition of mixed metal oxide nanoparticles. As indicated above, this may be a key parameter for the properties and performance of these materials.

Coating of the (cathode) particles might address many of the challenges arising from instability at the electrode/electrolyte surface. However, a possible process including production in the liquid phase, drying of the particles, and subsequent coating, may lead to the formation of e.g. (highly) metastable material that would degenerate before a coating could be applied. Flame spray pyrolysis to produce (cathode) materials might be an option, but as indicated above, in embodiments the relatively very high temperatures involved may also lead to unfavorable particle composition. Further, an easy and fast integration with a coating method, like ALD, seems impossible. An alternative option might be plasma processing. This might reduce the temperature issue and might solve the stability problem. However, an aqueous based approach may be incompatible with a subsequent coating method, such as ALD (see also the above example of pharmaceutical particles).

Hence, in a first aspect the invention provides a method for providing coated particles. Especially, the method may comprise a particle generation process and a particle coating process. The particles may be produced and coated while flowing through a reactor. In embodiments, the particle generation process may comprise feeding a starting material to a particle generation zone to generate particles. Especially, in embodiments the particle generation process comprises a spray process. The method may further comprise feeding with a fluid flow the particles generated in the particle generation zone from the particle generation zone to a coating zone. Especially, in embodiments the particle coating process may comprise coating the particles while flowing in the coating zone to provide the coated particles. Especially, in embodiments the particle coating process may comprise a vapor deposition process. Therefore, especially the invention provides in embodiments method for providing coated particles, the method comprising: (i) a particle generation process comprising feeding a starting material to a particle generation zone to generate particles; wherein the particle generation process comprises a spray process; (ii) feeding with a fluid flow the particles generated in the particle generation zone from the particle generation zone to a coating zone; and (iii) a particle coating process comprising coating the particles while flowing in the coating zone to provide the coated particles; wherein the particle coating process comprises a vapor deposition process.

With such method it may be possible to provide particles, such as nanoparticles, with a coating. Further, with such method it may be possible to control the thickness of the coating relatively good. Yet further, with such method it may be possible to provide coated particles in essentially a single process flow and/or in a single setup, without e.g. intermediate filtration. Also, with such method it may be possible to control the particle size of the cores. Yet further, it may be possible to provide metastable nanoparticles. Further, with the present process it may be possible to provide coated particles at relatively low temperatures and at relatively moderate pressures. Such method may be a continuous process (or continues method)(for providing particles with a coating).

As indicated above, the method may be used to provide coated particles. Hence, in embodiments the particles may be of the type core-shell. As will be further discussed below, the particles may comprise a single shell or a plurality of shells, with at least two shells having different chemical compositions.

The method may comprise two stages (though further stages are not excluded). In a first stage, which may essentially comprise the particle generation process, from a starting material particles are generated. In a second stage, the generated particles may be coated, to provide the coated particles. The particle generation may be executed in a first zone, such as a first zone of a reactor. Hence, the method may comprise the particle generation process comprising feeding a starting material to a particle generation zone to generate particles; wherein the particle generation process comprises a spray process. The particle coating process may be executed in a second zone, such as a second zone of the reactor, which second zone may not overlap or (at least) partly overlap with the first zone. Hence, the method may comprise a particle coating process comprising coating the particles while flowing in the coating zone to provide the coated particles. The particles formed in the first zone may move to the second zone. Especially, in embodiments the particles, i.e. the cores, may be entrained with a fluid flow, such as a gas flow. Therefore, the method may also comprise in embodiments feeding with a fluid flow the particles generated in the particle generation zone from the particle generation zone to a coating zone.

As indicated above, the particle generation process comprises a spray process. In this spray process, primary particles may be formed which may be the spray particles. These may be subjected to a conversion process into the core particles (secondary particles). For instance, this may be done with a flame spray pyrolysis (FSP). Hence, in embodiments the spray process may comprise a flame spray pyrolysis. Especially, in embodiments the spray process may comprise a plasma spray pyrolysis process (SPP). With the latter process, the temperature can be relatively low. This may be beneficial, e.g. in view of creating metastable particles. The plasma spray pyrolysis process may also be indicated as solution precursor plasma spray (SPPS).

Flame spray pyrolysis, and variants thereon, may be used to produce metal oxide powders from highly volatile gaseous metal compounds, such as metal chlorides or metal nitrates or metalloorganic materials, that are decomposed/oxidized in hydrogen-oxygen flames to form (nano) oxide powders. Hence, optionally, e.g. metal carboxylates or metal alkoxides, may be applied.

In relation to plasma spray pyrolysis, it is noted that DC torches may generate arc which heats working gases to form plasma jets. The jet’s temperature, in a conventional plasma torch, reaches 14 000 K and its velocity on the nozzle exit reaches 800 m/s. The torches used in SPPS process: (i) conventional, one cathode one having radial introduction of solution, (ii) three-cathode torch having axial introduction of solution; and (iii) segmented anode torches. The injection of solution can be made by an atomizer or by a nozzle. The working gases used to generate the plasma is usually argon with a molecular gas such as hydrogen or nitrogen (see also: https://hal-unilim.archives-ouvertes.fr/hal-01102762v2/document). The temperature of the plasma in the SPPS may be much lower than in conventional plasma torches.

Hence, in specific embodiments the method may comprise executing the plasma spray pyrolysis process at a temperature selected from the range of up to 600 °C, such as especially up to about 550 °C, such as even more especially up to about 500 °C. However, even lower temperatures may be possible, such as up to about 450 °C, such as even equal to or lower than 400 °C, like up to about 350 °C, such as even up to only about 150°C. Here, the temperature may be the temperature at which the particles (of the spray) may escape from a nozzle.

Hence, the droplets generated may be generated in a particle generation zone wherein in at least part thereof, such as in the plasma, the temperature may be selected from the range of up to 600 °C, such as especially up to about 550 °C, such as even more especially up to about 500 °C. However, even lower temperatures may be possible, such as up to about 450 °C, such as even equal to or lower than 400 °C, like up to about 350 °C, such as even up to only about 150°C. In specific embodiments, the temperature may be at least room temperature, such as at least about 50°. When using a flame spray process, the temperatures may be higher.

Further, the spray may be generate at a pressure relatively close to ambient pressure. In embodiments, the method may comprise executing the plasma spray pyrolysis process at a pressure selected from the range of 0.2-5 bar, especially 0.5-2 bar, such as at about 0.75-1.5 bar, like especially at atmospheric pressure, i.e. about 1 bar. The pressure may especially refer to the pressure of a space (such as at least part of the particle generation zone) wherein the droplets are provided.

Hence, the droplets generated may be generated in a particle generation zone wherein in at least part thereof, the pressure may be selected from the range of 0.2-5 bar, especially 0.5-2 bar, such as at about 0.75-1.5 bar, like especially at atmospheric pressure, i.e. about 1 bar. Hence, the core particles may be generated at such pressures. Note that a pressure in a nozzle from which the droplets may escape may be higher than e.g. atmospheric pressure.

The fact that moderate temperature and moderate pressure can be applied when using the plasma spray pyrolysis, allows a relatively easy coupling with the vapor deposition process, especially one of the ALD type. Hence, in embodiments the vapor deposition process comprises atomic layer deposition.

As indicated above, in the spray process, primary particles may be formed which may be the spray particles. These may be subjected to a conversion process into the core particles (secondary particles). In specific embodiments, the spray process may comprises generating droplets have dimensions selected from the range of 0.5-500 pm, such as especially 0.5-300 pm. Note that due to the flame or plasma process, these primary droplets are converted into secondary droplets, which will in general be smaller. In specific embodiments, the spray process may comprises generating droplets have dimensions selected from the range of 1-100 pm, such as 1-50 pm.

Herein, especially of interest are core-shell particles with a core of 5 nm to 10 pm, with a coating (shell) of 0.5-10 nm. Hence, the conditions may be chosen such that the secondary particles may have particle dimensions selected from the range of 5 nm to 10 mm.

The term “particle dimension” may refer to one or more of length, width, height, and diameter of the particle. Especially, it may refer to an equivalent spherical diameter of the particle.

The equivalent spherical diameter (or ESD) of an (irregularly) shaped object is the diameter of a sphere of equivalent volume. Hence, the equivalent spherical diameter (ESD) of a cube with a side a is 2 * a * ^3/(4 * n). Would a sphere in an xyz-coordinate system with a diameter D be distorted to any other shape (in the xyz-plane), without changing the volume, than the equivalent circular diameter of that shape would be D. Dimensions may be determined with methods known in the art, like one or more of optical microscopy, SEM and TEM. Dimensions may be number averaged, as known in the art. For instance, at least 50 % of the total number of measured particles may comply with the herein indicated dimensions (including ratios), such as at least 75 %, like at least 85 %.

The starting material may especially comprise the component(s) that are necessary for the core of the coated particles to be formed. Such component(s) may e.g. be solved and/or dispersed in a liquid. Especially, such component s) may be solved. Hence, the droplets may comprise liquid droplets, with the starting component(s).

In view of the subsequent vapor deposition process, it appears useful to use substantially, even more especially, essentially aqueous free liquids. It appears that water in the vapor deposition process, especially in larger amounts and/or uncontrolled amounts may have undesirable, if not detrimental, effects on the coating of the core particles. Hence, in specific embodiments the starting material comprises one or more liquids, especially wherein at least 95 vol.% of the one or more liquids is non-aqueous. Even more especially, at least 98 vol.% of the one or more liquids is non-aqueous. In yet further specific embodiments, at least 99 vol.% of the one or more liquids is non-aqueous, such as at least 99.5 vol.%, like at least 99.9%. In embodiments, less than 500 ppm water may be available in the starting material. Hence, the starting material may comprise liquids, such as CO2, and at least 95 vol% of the liquids may be non-aqueous liquids.

As indicated above, the liquid may comprise a non-aqueous solvent. Therefore, in specific embodiments the starting material comprises a solvent (for e.g. the lithium comprising core material (see further below)), wherein the solvent may comprise a nonaqueous solvent. In yet further specific embodiments, the one or more liquids comprise one or more non-aqueous solvents. For instance, in specific embodiments, at least 99 vol.% of the one or more liquids may comprise a non-aqueous solvent. Hence, the starting material may comprise one or more liquids, especially one or more solvents.

Therefore, the starting material may comprise one or more liquids, wherein the one or more liquids comprise the solvent. Especially, at least 95 vol.% of the one or more liquids is non-aqueous. Further, in embodiments at least 90 vol.% of the one or more liquids consist of the non-aqueous solvent.

An especially useful liquid may be supercritical CO2. Supercritical CO2, alone, or in combination with additives (see also below), may be a solvent for the material that is used for the core (“core forming material” or “core precursor” or “core precursor material”). Hence, in specific embodiments the solvent may comprise supercritical CO2. Additives may be used to assist solvation of materials, like e.g. inorganic salts. Such additives may also be indicated as “entrainers”. Useful materials may be e.g. methanol, ethanol or ammonia.

Hence, in specific embodiments the starting material may comprise one or more of methanol, ethanol and ammonia. Alternatively or additionally, the starting material may comprise a diol, especially selected from the group consisting of methane-diol, ethane-diol, and propane-diol. Diols may also be useful in view of a later ALD processing.

Therefore, in specific embodiments the starting material may comprise (i) supercritical CO2 and (ii) one or more of methanol, ethanol and ammonia. In yet other embodiments, the starting material may comprise (i) supercritical CO2 and (ii) one or more of methanol, ethanol, ammonia, methane-diol, ethane-diol, and propane-diol.

Additives, e.g. for improving solvation of core forming material, may e.g. be available up to about 10 wt%, such as up to about 5 wt%, relative to the total volume of the liquid(s). As indicated above, in embodiments the additives may be selected from the group consisting of methanol, ethanol, ammonia, methane-diol, ethane-diol, and propane-diol. For instance, in the range of 0.1-10 wt%, such in the range of 0.2-5 wt%, relative to the total volume of the liquid(s), may be comprise an additive. In specific embodiments, water may be an additive. In such instance, in the range of about 0.1-5 wt% water, such as 0.1-2 wt%, may be available, relative to the total volume of the liquid(s).

In specific embodiments, one or more of methanol, ethanol, ammonia, methane- diol, ethane-diol, and propane-diol may be used as solvent as such. Hence, in addition to or alternative to supercritical CO2, one or more of methanol, ethanol, ammonia, methane-diol, ethane-diol, and propane-diol may be comprised by the starting material.

The starting material may especially comprise a liquid and a material that will form at least part of the core. The latter may e.g. be an inorganic salt; the former may e.g. be a solvent for the inorganic salt. Additionally, as indicated above the starting material may comprise additives, like one or more of methanol, ethanol and ammonia, though other additives are not excluded (see also above).

As indicated above, the staring material may comprise a core forming material. Due to the flame or plasma process, the core forming material may be converted into core material. For instance, as salt, available in the liquid, may be converted into an oxide. Hence, in specific embodiments the starting material comprises an inorganic material. The term “inorganic material” may also refer to a plurality of different inorganic materials. Especially, in embodiments the starting material comprises a salt.

As indicated above, the invention may provide battery materials. In specific embodiments, the battery materials may require the presence of lithium. Therefore, in specific embodiments the starting material may comprises a lithium comprising (core forming) material, such as a lithium salt. Suitable examples are lithium nitrate or lithium chloride or lithium oxalate, etc.. Especially, lithium nitrate may be useful.

Additionally or alternatively, the core material may desirably comprise another metal, such as especially one or more of manganese, nickel and cobalt.

Hence, in specific embodiments the starting material comprises a manganese comprising (core forming) material. Suitable examples are manganese nitrate or manganese chloride or manganese oxalate, etc.. Especially, manganese nitrate may be useful.

Alternatively or additionally, the starting material may comprise a cobalt comprising (core forming) material. Suitable examples are cobalt nitrate or cobalt chloride or cobalt oxalate, etc.. Especially, cobalt nitrate may be useful.

Alternatively or additionally, the starting material may comprise a nickel comprising (core forming) material. Suitable examples are nickel nitrate or nickel chloride or nickel oxalate, etc.. Especially, nickel nitrate may be useful.

In specific embodiments, the starting material comprises the lithium comprising (core forming) material and the manganese comprising (core forming) material. Yet further, in embodiments, the starting material comprises the lithium comprising (core forming) material and the manganese comprising (core forming) material and the cobalt comprising (core forming) material.

Hence, in specific embodiments the starting material may comprise a lithium comprising material, and the starting material may comprise one or more of a manganese comprising material, a cobalt comprising material, a nickel comprising material, and an iron comprising material.

In this way NCM may be formed as core material in the spray process. As indicated above, such spray process may provide Li[Nii-x-yCoxMn_y]O2, wherein x is selected from the range of 0-0.5, and wherein y is selected from the range of 0-0.5.

In specific embodiments, the starting material comprises cobalt and lithium, having an atom ratio 0<Co/Li<0.05. In yet other embodiments, 0.005<Co/Li<0.05. Further, in embodiments 0.5<Co/Mn<2, such as 0.75<Co/Mn<1.25. Alternatively or additionally, the starting material may comprise an iron comprising (core forming) material. Suitable examples are iron nitrate or iron chloride or iron oxalate, etc.. Especially, iron nitrate may be useful.

In specific embodiments, the starting material comprises the lithium comprising (core forming) material and the iron comprising (core forming) material. In this way LiFePCh may be formed as core material.

Hence, the starting material may comprise (i) one or more of lithium comprising (core forming) material, a manganese comprising (core forming) material, a cobalt comprising (core forming) material, a nickel comprising (core forming) material, and an iron comprising (core forming) material.

The term “(core forming) material” and similar terms may refer to those materials that may be converted in particle generation zone into core material. Hence, this term may also refer to a precursor. Therefore, terms like “lithium comprising (core forming) material”, a “manganese comprising (core forming) material”, a “cobalt comprising (core forming) material”, a “nickel comprising (core forming) material”, and an “iron comprising (core forming) material”, and similar terms, may thus also be indicated as lithium precursor material”, a “manganese precursor material”, a “cobalt precursor material”, a “nickel precursor material”, and an “iron precursor material”.

As indicated above, the particle coating process may comprise a vapor deposition process. Especially, in embodiments the vapor deposition process may comprise one or more of chemical vapor deposition (CVD), molecular layer deposition (MLD), and atomic layer deposition (ALD).

Chemical vapor deposition (CVD) is a (vacuum) deposition method used to produce e.g. coatings. In typical CVD, the materials, such as particles, may be exposed to one or more volatile precursors, which react and/or decompose on the substrate surface to produce the desired deposit. Frequently, volatile by-products may be also produced, which may be removed by a gas flow. Many types of CVD are known, like APCVD (atmospheric pressure CVD), LPCVD (low-pressure CVD), UHVCVD (ultra-high pressure CVD), SACVD (sub- atmospheric pressure CVD), AACVD (aerosol assisted CVD), DLICVD (direct liquid injection CVD), MPCVD (microwave plasma-assisted CVD), PECVD (plasma-enhanced CVD), RPECVD (remote plasma-enhanced CVD), LEPECVD (low-energy plasma-enhanced CVD), CCVD (combustion CVD), HPCV (hot filament CVD), MOCVD (metalorganic CVD), RTCVD (rapid thermal CVD), PICVD (photo-initiated CVD), and LCVD (laser CVD), and may be used herein. In specific embodiments, pulsed CVD may be applied. MLD is a thin-film growth technique developed during the early 1990s for the deposition of molecular fragments on the surface of an active material, and has been an attractive method for the deposition of a variety of organic polymers and more recently hybrid organic-inorganic polymers. In a typical MLD process, molecular fragments of the bifunctional precursors are deposited on the surface of an active substrate. This process involves two different reactions: the first between the surface active group of the substrate and precursor-1; the other reaction is between precursor-1 and precursor-2. It is the self-terminating nature of these reactions which enables the deposition of ultra-thin layers on the surface of the substrate.

Atomic layer deposition is a thin-film deposition technique based on the sequential use of a gas phase chemical process. The majority of ALD reactions use two chemicals called precursors (also called "reactants"). These precursors react with the surface of a material one at a time in a sequential, self-limiting, manner. In embodiments through the repeated exposure to separate precursors, a thin film is slowly deposited.

Note that also hybrid methods may be applied herein, such as e.g. described in Valdesueiro, D., Meesters, G., Kreutzer, M. & Van Ommen, J. 2015. Gas-Phase Deposition of Ultrathin Aluminium Oxide Films on Nanoparticles at Ambient Conditions. Materials, 8, 1249- 1263. Hence, also an ALD-like CVD process may be applied. Hence, in embodiments, the process may be carried out with insufficient purging time to remove all reactant A before adding reactant B (or vice versa). This can lead to physisorption of multiple monolayers of A on the surface instead of chemisorption of a sub-monolayer which is formed in regular ALD with sufficient purging. As a consequence, the behavior is no longer (fully) self-limiting, but a faster growth rate can be achieved. Herein, irrespective of scientific theoretical consideration, for the sake of describing and claiming the ALD-like CVD process may be indicated as an ALD process, even though it may not considered a pure ALD process, or as a combination of an ALD and CVD process.

In specific embodiments, a specific type of reactor may be applied to execute the one or more of chemical vapor deposition, molecular layer deposition, and atomic layer deposition, such as ALD. Hence, in specific embodiments the method may comprise depositing a coating onto particles being pneumatically transported in a tube, said process comprising: (i) providing a tube having an inlet opening and an outlet opening; (ii) feeding a carrier gas entraining particles into the tube at or near the inlet opening of the tube to create a particle flow through the tube; (iii) injecting a first reactant into the tube via an injection point downstream from the inlet opening of the tube for deposition on the surface of the particles in the particle flow, especially in a self-terminating reaction; and (iv) injecting a second reactant into the tube via a further injection point downstream from the injection point of the first reactant for deposition on the surface of the particles in the particle flow, especially in a self-terminating reaction, such as described in US13/254,854, (US2012/0009343) which is herein incorporated by reference. Hence, in embodiments the method may comprise executing the particle coating process in a pneumatic transport reactor. In yet further specific embodiments, the method may comprise a process for depositing a coating onto particles being pneumatically transported in a tube, said process comprising the steps of: (i) providing a tube having an inlet opening and an outlet opening; (ii) feeding a carrier gas entraining particles into the tube at or near the inlet opening of the tube to create a particle flow through the tube; and (iii) injecting a first selfterminating reactant into the tube via at least one injection point downstream from the inlet opening of the tube for reaction with the particles in the particle flow, as described in US2012/0009343.

In specific embodiments, the method may comprise: executing the vapor deposition process at a pressure selected from the range of 0.5-2 bar, especially at atmospheric pressure). Alternatively or additionally, in specific embodiments, the method may comprise: executing the vapor deposition process at a temperature selected from the range of up to 500 °C, such as for ALD, or even up to about 800 °C for CVD. For MLD, also temperatures up to e.g. may be 500 °C applied. Further, some CVD processes may also be applied at temperatures such as up to about 500 °C.

The vapor deposition process may be used to provide the shell to the core (core particles). This may be comprise a partial coating of the core, are an essentially full coating of the core. In specific embodiments, the shell may be porous. In yet other embodiments, the shell may essentially conformally enclose the core. The shell may comprise a single type of material or may comprise different types of material. The shell may comprise a single shell comprising a single material or may comprise a single shell comprising a plurality of different material. In specific embodiments, the shell may comprise a plurality of layers, of which two have different chemical compositions.

When there is a single shell on the core, or when there are a plurality of shell layers, the single shell, or the first shell adjacent to the core, respectively, especially differ from the core in chemical composition. For instance, an alumina layer or a carbon layer may be a shell layer on the core essentially consisting of e.g. Li[Nii-x-yCo_xMn_y]O2 or LiFePC

Hence, in specific embodiments the vapor deposition process may comprise a deposition process of a carbon comprising shell material. Hence, there may be a single shell comprising carbon, or there may be a plurality of shells of which at least one shell comprises a carbon shell. A carbon shell may especially be applied with a CVD process. Hence, in embodiments the vapor deposition process may comprise the deposition of a carbon shell, and wherein the vapor deposition process comprises a CVD process.

Alternatively or additionally, the vapor deposition process may comprise a deposition process of a phosphate comprising shell material. Hence, there may be a single shell comprising a phosphate comprising shell material, or there may be a plurality of shells of which at least one shell comprises a phosphate comprising shell material. In specific embodiments, the core may comprise Li[Nii-x-yCo_xMn_y]O2 and the shell may comprise LiFePC .

Yet alternatively or additionally, the vapor deposition process may comprise a deposition process of an oxide comprising shell material. Hence, in the deposition process, especially an oxide comprising shell material coating may be provided to the particles. Hence, in embodiments the vapor deposition process comprises a deposition process of an oxide comprising shell material. The oxide comprising shell material especially comprises a metal oxide and may be a pure metal oxide, a combination of different metal oxides, and may also be a mix metal oxide (or mixed oxide). Further, the oxide comprising shell material may be a single layer or may comprise an oxide comprising shell material layer. Especially, the layer(s) are essentially conformal and entirely enclose the core. However, optionally also porous layers may be possible.

The shell layer(s) may be relatively thin. In specific embodiments, the layer thickness may be selected from the range of 0.5-5 nm.

In embodiments, the oxide comprising shell material may comprise one or more oxides comprising one or more materials selected from the group consisting of an aluminum comprising shell material, a cerium comprising shell material, a cobalt comprising shell material, a niobium comprising shell material, a silicon comprising shell material, and a titanium comprising shell material.

In specific embodiments, the oxide comprising shell material may comprise one or more oxide comprising one or more materials selected from the group consisting of alumina, ceria, cobalt oxide, niobium oxide, silica, and titania.

In specific embodiments the shell at least comprises an alumina layer.

Alternatively or additionally, in specific embodiments the shell at least comprises a cobalt oxide layer. Hence, in embodiments the oxide comprising shell material comprises a cobalt oxide. In specific embodiments, a shell layer may comprise alumina and carbon. The addition of carbon may increase the electrical conductivity. Further, carbon may not only be added to alumina, but may also be added to other oxides, as indicated above. With a vapor deposition process, it may be relatively easy to provide an oxide coating including carbon, such as by adding an organic compound in the vapor deposition process of the oxide, which organic compound may decompose and form carbon. For instance, in embodiments an organo- aluminum compound may be used as a first reactant and a diol may be used as a second reactant. Especially, in embodiments e.g. tri-methyl aluminum, and ethane-diol may be uses as first and second reactant, respectively.

For different purposes, different layers may be provided. For instance, a cobalt layer, especially directly on the core, may stabilize a metastable core material. An alumina layer, or a titania layer, or a silica layer, may provide a protective coating. A carbon dopant, or a carbon layer may increase conductivity. Thin carbon coatings are known in the art, as e.g. described by Liang-Jun Yin et al., The Journal of Physical Chemistry C 2016 120 (4), 2355- 2361, DOI: 10.1021/acs.jpcc.5bl0215. Therefore, in embodiments the vapor deposition process may comprise a multi-layer deposition process.

In specific embodiments, the vapor deposition process may comprise an oxide comprising shell material multi-layer deposition process.

Especially, in embodiments a first shell layer comprises cobalt oxide, and wherein a second shell layer, further away from a core than the first shell layer, comprises alumina.

In embodiments wherein cobalt is comprised by a shell layer, the core may comprise cobalt or may not comprise cobalt. Especially, in embodiments when the shell layer comprises cobalt, the core does essentially not comprise cobalt. In specific embodiments, the particles may comprise a shell layer comprising cobalt oxide, wherein the (cobalt oxide) shell layer has a layer thickness selected from the range of 0.5-5 nm.

As indicated above, it may be desirable to include some cobalt in the particle, either in the core and/or in a shell. In specific embodiments, the coated particles may comprise cobalt with a weight percentage in the range of up to 10 wt%, such as especially up to about 5 wt% (relative to the total weight of the particles). Though there may in embodiments be no cobalt at all, especially in embodiments there may be at least 0.1 wt%, such as at least 0.5 wt% cobalt comprised by the coated particles. Therefore, in embodiments the coated particles comprise cobalt with a weight percentage in the range of 0.1-5 wt%. In a specific embodiment, the invention provides a method for providing coated particles, the method comprising: (i) feeding a starting material to a particle generation zone to generate particles, (ii) feeding with a fluid flow the particles generated in the particle generation zone from the particle generation zone to a coating zone, and (iii) coating the particles while flowing in the coating zone to provide the coated particles; wherein in the particle generation zone a plasma spray pyrolysis process is executed, and wherein in the coating zone a vapor deposition process is executed, wherein: (a) the vapor deposition process comprises one or more of chemical vapor deposition (CVD) and atomic layer deposition (ALD); (b) the plasma spray pyrolysis process is executed at a pressure selected from the range of 0.5-2 bar (especially at atmospheric pressure), and wherein the plasma spray pyrolysis process is executed at a temperature selected from the range of up to 500 °C; and (c) the starting material comprises a lithium material and a solvent for the lithium material, wherein the solvent comprises supercritical CO2.

In yet a further aspect, the invention also provides an apparatus, which may especially be configured to execute the herein described method. Such apparatus may comprise a first zone, wherein the core particles are generated and a second zone wherein the coating on the core particles is provided. Especially, in embodiments this may be executed in a single reactor, wherein the reactor comprises these two zones. Note that more zones may be available.

Hence, in an aspect the invention also provides an apparatus for providing coated particles. Especially, the apparatus may comprise a particle generation zone and a coating zone. The coating zone is especially configured downstream of the particle generation zone. In embodiments, in an operational mode the apparatus may especially be configured to: (i) feed with a fluid flow (the) particles generated in the particle generation zone from the particle generation zone to the coating zone, and (ii) to coat the particles while flowing in the coating zone to provide coated particles. In specific embodiments, the particle generation zone may comprise a spray system configured to generate particles. Further, in specific embodiments, the coating zone may comprise a vapor deposition system configured to provide a coating (also indicated as shell) to particles thereby providing the coated particles. Therefore, in embodiments the invention provides an apparatus for providing coated particles, the apparatus comprising a particle generation zone and a coating zone, configured downstream of the particle generation zone, wherein in an operational mode the apparatus is configured to: (i) feed with a fluid flow the particles generated in the particle generation zone from the particle generation zone to the coating zone, and (ii) to coat the particles while flowing in the coating zone to provide coated particles; wherein the particle generation zone comprises a spray system configured to generate particles, and wherein the coating zone comprises a vapor deposition system configured to provide a coating to particles thereby providing the coated particles.

As indicated above, the invention thus also provides an apparatus for providing coated particles. In embodiments, the apparatus may comprise a particle generation zone and a coating zone, configured downstream of the particle generation zone. The zones may be two parts of a reactor. However, in alternative embodiments two reactors may be functionally coupled, wherein one reactor comprises the particle generation zone and a second reactor comprises the coating zone. There may be a flow of gas from the particle generation zone to the coating zone, to transport the core particles formed in the particle generation zone to the coating zone. Hence, the coating zone is indicated as being configured downstream of the particle generation zone. Therefore, during operation there may be a gas flow from the particle generation zone to the coating zone. Hence, the particle generation zone and the coating zone may be fluidly connected.

Especially, in embodiments the apparatus may (thus) be configured (in an operational mode) to: (i) feed with a fluid flow the particles generated in the particle generation zone from the particle generation zone to the coating zone, and (ii) to coat the particles while flowing in the coating zone to provide coated particles.

In embodiments, the particle generation zone may comprise a spray system configured to generate particles. The spray system may, as indicated above, in embodiments comprise a flame spray pyrolysis (FSP) system. Especially, however, the spray system may comprise a plasma spray pyrolysis. As indicated above, the spray system may generate primary particles, that are converted to the core particles. The core particles are transported to the coating zone, where the particles may be coated. Especially, the coating zone may comprise a vapor deposition system configured to provide a coating to particles thereby providing the coated particles.

The system, or apparatus, or device may execute an action in a “mode” or “operation mode” or “mode of operation”. Likewise, in a method an action or stage, or step may be executed in a “mode” or “operation mode” or “mode of operation” or “operational mode”. The term “mode” may also be indicated as “controlling mode”. This does not exclude that the system, or apparatus, or device may also be adapted for providing another controlling mode, or a plurality of other controlling modes. Likewise, this may not exclude that before executing the mode and/or after executing the mode one or more other modes may be executed.

In specific embodiments, the vapor deposition system is configured to execute a vapor deposition process, wherein the vapor deposition process comprises one or more of chemical vapor deposition (CVD), molecular layer deposition (MLD), and atomic layer deposition (ALD).

In embodiments, the vapor deposition system may be configured to execute the vapor deposition process at a pressure selected from the range of 0.5-2 bar, such as especially at atmospheric pressure. Alternatively or additionally, in embodiments the vapor deposition system may be configured to execute the vapor deposition process at a temperature selected from the range of up to 500 °C, though higher temperatures may also be possible (such as for CVD).

As indicated above, especially, in embodiments the spray system comprises a plasma spray pyrolysis system configured to execute a plasma spray pyrolysis process. Also for such embodiments it may apply that the spray system may be configured to execute the plasma spray pyrolysis process at a pressure selected from the range of 0.5-2 bar, especially at atmospheric pressure, and, especially, the spray system may be configured to execute the plasma spray pyrolysis process at a temperature selected from the range of up to 500 °C. In embodiments, the spray system may be configured to generate droplets having dimensions selected from the range of 0.5-300 pm.

The apparatus may be functionally coupled to a supply of the starting material, or to one or more of the starting materials. Such supply may also be comprised by the apparatus in embodiments. For instance, in embodiments the apparatus may further comprise a supercritical CO2 supply.

In embodiments, the vapor deposition system may be configured to provide a multi-layer coating to the particles, thereby providing the coated particles comprising a multilayer coating.

In specific embodiments, the vapor deposition system may comprise a pneumatic transport reactor (see also above). In specific embodiments, the apparatus may comprise: (a) a tube having an inlet opening and an outlet opening; (b) a feeder device for feeding a carrier gas entraining the particles into the tube; and (c) at least one injection point downstream from the inlet opening for introducing a reactant into the tube; wherein the apparatus is arranged to perform the particle coating process, as described herein, which may in further specific embodiments comprise a process for depositing a coating onto particles being pneumatically transported in a tube, said process comprising the steps of (i) providing a tube having an inlet opening and an outlet opening; (ii) feeding a carrier gas entraining particles into the tube at or near the inlet opening of the tube to create a particle flow through the tube; and (iii) injecting a first self-terminating reactant into the tube via at least one injection point downstream from the inlet opening of the tube for reaction with the particles in the particle flow, as also described above. For such embodiments, it is further referred to US2012009343, which is herein incorporated by reference.

The apparatus may further comprise a control system or may be functionally coupled to a control system, especially configured to control the spray system and the vapor deposition system.

The term “controlling” and similar terms especially refer at least to determining the behavior or supervising the running of an element. Hence, herein “controlling” and similar terms may e.g. refer to imposing behavior to the element (determining the behavior or supervising the running of an element), etc., such as e.g. measuring, displaying, actuating, opening, shifting, changing temperature, etc.. Beyond that, the term “controlling” and similar terms may additionally include monitoring. Hence, the term “controlling” and similar terms may include imposing behavior on an element and also imposing behavior on an element and monitoring the element. The controlling of the element can be done with a control system, which may also be indicated as “controller”. The control system and the element may thus at least temporarily, or permanently, functionally be coupled. The element may comprise the control system. In embodiments, the control system and element may not be physically coupled. Control can be done via wired and/or wireless control. The term “control system” may also refer to a plurality of different control systems, which especially are functionally coupled, and of which e.g. one control system may be a master control system and one or more others may be slave control systems. A control system may comprise or may be functionally coupled to a user interface.

The control system may also be configured to receive and execute instructions form a remote control. In embodiments, the control system may be controlled via an App on a device, such as a portable device, like a Smartphone or I-phone, a tablet, etc.. The control system may thus not be necessarily coupled to the apparatus, but may be (temporarily) functionally coupled to the apparatus.

However, in embodiments a control system may be available, that is adapted to provide at least the controlling mode. Would other modes be available, the choice of such modes may especially be executed via a user interface, though other options, like executing a mode in dependence of a sensor signal or a (time) scheme, may also be possible. The operation mode may in embodiments also refer to a system, or apparatus, or device, that can only operate in a single operation mode (i.e. “on”, without further tunability). Hence, in embodiments, the control system may control in dependence of one or more of an input signal of a user interface, a sensor signal (of a sensor), and a timer. The term “timer” may refer to a clock and/or a predetermined time scheme.

In yet a further aspect, the invention also provides a first material comprising coated particles. Especially, the coated particles may comprise a core and a shell, enclosing at least part of the core. In embodiments, the core comprises a core material. In specific embodiments, the core material may comprise a lithium comprising core material. Further, in specific embodiments the shell may comprise a shell material. In specific embodiments, the shell material comprises an oxide comprising shell material (though other materials are not excluded, see also below). Especially, in embodiments the (oxide comprising) shell material may comprise one or more (oxide comprising) materials selected from the group consisting of an aluminum comprising shell material, a cerium comprising shell material, a cobalt comprising shell material, a niobium comprising shell material, a silicon comprising shell material, and a titanium comprising shell material. However, as further indicated below, also other materials may be possible. Therefore, especially the invention further provides in embodiments a first material comprising coated particles, wherein the coated particles comprise a core and a shell, enclosing at least part of the core, wherein the core comprises a core material, wherein the core material comprises a lithium comprising core material, and wherein the shell comprises a shell material, wherein the shell material comprises an oxide comprising shell material, wherein the shell material comprises one or more materials selected from the group consisting of an aluminum comprising shell material, a cerium comprising shell material, a cobalt comprising shell material, a niobium comprising shell material, a silicon comprising shell material, and a titanium comprising shell material.

As indicated above, in specific embodiments the oxide comprising shell material comprises one or more materials selected from the group consisting of alumina, ceria, cobalt oxide, niobium oxide, silica, and titania.

In yet further specific embodiments, the coated particles comprise cobalt with a weight percentage in the range of up to 5 wt%. Especially, in embodiments the coated particles comprise cobalt with a weight percentage in the range of 0.1-5 wt%.

In yet further embodiments, the core material comprises a manganese comprising core material. Alternatively or additionally, in embodiments the core material comprises a cobalt comprising core material. Alternatively or additionally, in embodiments the core material comprises a nickel comprising core material. Alternatively or additionally, in embodiments the core material comprises an iron comprising core material. In specific embodiments, the core material comprises cobalt and lithium, having an atom ratio 0<Co/Li<0.05. In further specific embodiments, 0.005<Co/Li<0.05.

In specific embodiments, the core material may comprises Li[Nii-x-yCo_xMn_y]O2, wherein x is selected from the range of 0-0.5, and wherein y is selected from the range of 0- 0.5.., and/or the core material may comprise LiFePC .

In specific embodiments, the shell material comprises a phosphate comprising shell material. Alternatively or additionally, in embodiments the shell comprises a shell layer, wherein the shell layer is a carbon layer. Alternatively or additionally, in embodiments the shell material comprises a cobalt oxide.

In specific embodiments, the shell material may comprise multi-layer. Especially, in embodiments the shell material comprises an oxide comprising shell material multi-layer. The term “an oxide comprising shell material multi-layer” may refer to a multilayer comprise an oxide comprising shell material.

Especially, in embodiments a first shell layer may comprise a cobalt oxide, and wherein a second shell layer, further away from a core than the first shell layer, may comprise alumina.

In specific embodiments of an alumina shell layer, the shell may comprise a shell layer (220,222) comprising alumina and carbon.

In specific embodiments of an cobalt material comprising shell, the shell may comprise a shell layer comprising cobalt oxide, wherein the shell layer may have a layer thickness selected from the range of 0.5-5 nm.

The material LiFePCU may further comprise dopants, such as one or more selected from Mg, Al, Zr, Nb, Co, Mn, and Ni. Such dopants may in embodiments be incorporated in the crystal lattice. Further, such dopants may be available in the material up to about 2 mole%, such as up to about 1 mole% (for all the dopants in total). As indicated above, this material may be applied as core material or as shell material.

Hence, in embodiments, the invention provides a first material comprising coated particles, wherein the coated particles comprise a core and a shell, enclosing at least part of the core, wherein the core comprises a core material. In specific embodiments, the core material comprises a lithium comprising core material, and the core material may comprise one or more of a manganese comprising core material, a cobalt comprising core material, a nickel comprising core material, and an iron comprising core material. Further, in embodiments the shell comprises a shell material, wherein the shell material may comprise one or more materials selected from the group consisting of an aluminum comprising shell material, a cerium comprising shell material, a cobalt comprising shell material, an iron comprising shell material, a niobium comprising shell material, a silicon comprising shell material, a titanium comprising shell material, and a carbon comprising shell material.

In embodiments, the shell material may comprise phosphor, like e.g. a phosphate layer. Hence, in embodiments the shell material may comprise a phosphate comprising shell material.

Especially, in embodiments the core material has a chemical composition different from a chemical composition of the shell material closest to the core material. Hence, a shell layer directly adjacent to the core and in physical and/or chemical contact therewith may have another chemical composition than the core material. This does not exclude the presence of a shell layer having the same chemical composition as the core, wherein between the core and the shell layer having the same chemical composition is at least one other shell layer having a different chemical composition.

For instance, in embodiments the core material may comprise LiFePCU, and a shell on the core material does not consist of LiFePCh. Or, in embodiments the core material may comprise LiFePO4, and a shell layer on the core material does not consist of LiFePO4. Hence, in specific embodiments the shell material may comprise LiFePO4, and a shell layer consisting of LiFePO4, is not on a core consisting of LiFePO4. However, a shell layer consisting of LiFePO4 may be configured on a core consisting of e.g. Li[Nii-x-yCo_xMn_y]O2.

As indicated above, in embodiments the coated particles may comprise cobalt with a weight percentage in the range of 0-5 wt%, or larger than 0 wt% (see also above).

Therefore, in an aspect the invention also provides a first material comprising coated particles, wherein the coated particles comprise a core and a shell, enclosing at least part of the core, wherein the core comprises a core material, wherein the core material comprises a lithium comprising core material, and wherein the core material comprises one or more of a manganese comprising core material, a cobalt comprising core material, a nickel comprising core material, and an iron comprising core material; and wherein the shell comprises a shell material, wherein the shell material comprises one or more materials selected from the group consisting of an aluminum comprising shell material, a cerium comprising shell material, a cobalt comprising shell material, an iron comprising shell material, a niobium comprising shell material, a silicon comprising shell material, a titanium comprising shell material, and a carbon comprising shell material, wherein the core material has a chemical composition different from a chemical composition of the shell material closest to the core material, wherein the coated particles comprise cobalt with a weight percentage in the range of 0-5 wt%. As indicated above, the shell material may in embodiments comprise an oxide comprising shell material.

In yet a further aspect, the invention also provides an electrode comprising the first material as defined herein. Especially, in embodiment the electrode comprises a cathode. In yet a further aspect, the invention also provides a battery comprising the electrode as defined herein. Especially, the electrode may be configured as cathode.

The invention is not only related to lithium comprising particles, but may also relate to other types of particles, such as based on iron only, or based on other metals or metal oxides. For instance, the invention may also be applied for providing catalyst particles or luminescent particles, or other types of functional particles, like magnetic particles. Optionally, the invention may be applied for creating radioactive particles. In embodiments, the particles may be used in self-healing materials.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the invention will now be described, by way of example only, with reference to the accompanying schematic drawings in which corresponding reference symbols indicate corresponding parts, and in which: Figs, la-lc schematically depict some aspects and embodiments; Fig. 2 schematically depicts an embodiment; and Figs. 3a-3b schematically depict some further aspects. The schematic drawings are not necessarily to scale.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Fig. 1 schematically depicts an embodiment of an apparatus 1000 for providing coated particles 20. The apparatus 1000 comprises a particle generation zone 1100 and a coating zone 1200, configured downstream of the particle generation zone 1100. In an operational mode the apparatus is configured to: feed with a fluid flow the particles 10 generated in the particle generation zone 1100 from the particle generation zone 1100 to the coating zone 1200, and to coat the particles 10 while flowing in the coating zone 1200 to provide coated particles 20. The particle generation zone 1100 comprises a spray system 100 configured to generate particles 10. The coating zone 1200 comprises a vapor deposition system 200 configured to provide a coating 22 to particles 10 thereby providing the coated particles 20.

In embodiments, the vapor deposition system 200 is configured to execute a vapor deposition process, wherein the vapor deposition process comprises one or more of chemical vapor deposition CVD, molecular layer deposition MLD, and atomic layer deposition ALD. Especially, the vapor deposition system 200 is configured to execute the vapor deposition process at a pressure selected from the range of 0.5-2 bar, more especially at atmospheric pressure. Further, in embodiments the vapor deposition system 200 is configured to execute the vapor deposition process at a temperature selected from the range of up to 500 °C.

In embodiments, the spray system 100 comprises a plasma spray pyrolysis system configured to execute a plasma spray pyrolysis process. Especially, in embodiments the spray system 100 is configured to execute the plasma spray pyrolysis process at a pressure selected from the range of 0.5-2 bar, more especially at atmospheric pressure. Further, in embodiments the spray system 100 is configured to execute the plasma spray pyrolysis process at a temperature selected from the range of up to 500 °C.

In embodiments, the spray system 100 may be configured to generate droplets having dimensions selected from the range of 0.5-300 pm. Droplets are indicated with reference 1.

In embodiments, the apparatus may further comprise a supercritical CO2 supply 2.

In specific embodiments, the vapor deposition system 200 is configured to provide a multi-layer coating to the particles, thereby providing the coated particles 20 comprising a multi-layer coating. Especially, in embodiments the vapor deposition system 200 comprises a pneumatic transport reactor 250.

Fig. lb very schematically shows the generation of droplets 1 or primary particles, which are converted by e.g. the plasma or a flame, into core particles 10, comprising core material or core 21. Subsequently, the core particles 10 / cores 21 are coated with a coating or shell 22, thereby providing core-shell particles 20.

Fig. 1c schematically depict a number of embodiments, with embodiment I showing a single shell 22 or coating. Embodiment II shows a shell 22 comprising two layers 220, indicated as first layer 221 and second layer 222. More shell layers 220 may be available. Embodiments III shows schematically a version with three shell layers 220 comprised by the shell 22, with the shell layers being indicated as 221, 222, and 223. The material composition of layer 222 and layer 221 or layer 222 and layer 223 are different. The material composition of layers 221 and 223 may be different or may be the same.

The invention relates to a continuous process or method for depositing sequential layers onto particles being pneumatically transported in a tube, said process comprising the steps of (i) providing a tube having an inlet opening and an outlet opening; (ii) feeding a carrier gas entraining particles into the tube at or near the inlet opening of the tube; injecting a reactant into the tube via at least one injection point downstream from the inlet opening of the tube.

The process is suitable for depositing layers by an atomic layer deposition process and/or a molecular layer deposition process. The particles may include agglomerates formed by smaller particles. Such agglomerates allow for pneumatic transport of very small particles, while the surface of these very small particles remain available for reaction with the reactant. Throughout the description, the term “particles” may refer to both particles and agglomerates formed by these particles.

In a preferred embodiment of the process, the particles travel through the tube in substantially a plug flow. Although the term “plug flow” may suggest that the particles travel at the same linear velocity as the carrier gas, for larger particles this is not the case. With particles larger than several micrometers there is a certain amount of slippage between the carrier gas and the entrained particles, such that the carrier gas travels at a greater velocity than do the particles. Under those circumstances, due to this slippage, the reactor is essentially self- purging: unreacted reactants and reaction products are removed from the particles by carrier gas overtaking and passing the particles.

This self-purging aspect of the process of the invention contributes to the ability of the process to be operated in a continuous mode, which makes the process attractive for conducting atomic or molecular layer deposition reaction cycles. As, in general, it is desirable to deposit more than one layer onto the particles, a preferred embodiment of the process uses a plurality of injection points downstream of the inlet opening of the tube.

This self-purging effect is not present when the particle size is too small for any significant slippage to take place. The process of the invention can be used even under these circumstances for depositing a small number of layers. For example, when preparing catalyst particles it is oftentimes sufficient to deposit only one layer.

Even for depositing a larger number of layers onto small particles the process of the invention is useful. For this embodiment of the process it may be desirable to provide the tube with purge ports for removing reaction by-products and unreacted reactants.

In traditional chemical vapor deposition each reactant injection point corresponds to the deposition of a layer onto the particle. This layer is not necessarily a monolayer. For example, the process may be used for depositing a metal, such as Ni, Fe, or Co, whereby a corresponding organometallic compound is injected into the first reactant injection point. The tube may be kept at a temperature sufficiently high to cause decomposition of the organometallic compound. In general, temperatures in the range of 100 to 320° C. are suitable, the lower limit being governed by the decomposition temperature of the organometallic compound. Alternatively, a plasma could be used to activate the reaction.

Upon entering the tube the organometallic compound decomposes, and the metal is deposited onto the particles entrained by the carrier gas. The organic compound produced in the decomposition reaction of the organometallic compound is removed from the particles by the carrier gas. The deposition cycle is repeated upon injection of organometallic compound at the second injection point, whereby a second layer of metal is deposited onto the particle. In general, when the process is used in traditional chemical vapor deposition, the number of layers deposited onto the particles is identical the number of injection points receiving organometallic compound.

The term “traditional chemical vapor deposition” as used herein generally refers to single-reactant chemical vapor deposition or multiple reactants added at the same time, in which the reaction is not self-terminating. Atomic Layer Deposition (“ALD”) can be considered a specific embodiment of chemical vapor deposition. In ALD, only one atomic layer is deposited in each reaction cycle. In particular, the term “Atomic Layer Deposition” or “ALD”, as used herein, refers to a chemical vapor deposition process in which a reactant is deposited onto the surface of the particles in a self-terminating reaction. In many cases the process cycle comprises a second reaction step, in which a second reactant is contacted with the particle surface. The term ALD as used herein is, however, not limited to this dual reactant process, as other means may be used to activate the surface of the particle for a subsequent reaction with the first reactant.

Importantly, depending on the specific reactants, the “atomic” layer being deposited may in fact be a molecular layer. The term ALD as used herein encompasses also molecular layer deposition.

The ALD process will be explained with reference to a dual reactant ALD reaction cycle. The first reactant is injected into the first injection point. This first reactant is a precursor of the atom or molecule to be deposited onto the surface of the particles. The first reactant interacts with the particles to form a chemisorption monolayer onto the surface of the particles. If gas/particle slippage occurs, unreacted first reactant and reaction by-products are removed from the particles by the self-purging mechanism described above.

The second reactant is injected into the second injection point. Upon entering the tube, the second reactant comes into contact with the particles, which are covered with a monolayer of (a reaction product of) the first reactant. The second reactant reacts with the chemisorbed (reaction product of) the first reactant to form the atom or molecule layer of the desired coating material. If gas/particle slippage occurs, unreacted second reactant and reaction by-products are removed from the particles by the self-purging mechanism.

A second ALD layer may be deposited by injecting the first reactant into a third injection point, and the second reactant into a fourth reaction point, and so on. In general, a large number of layers can be deposited by providing a large number of injection points along the tube. The first reactant is injected into injection points 1, 3, 5, etc. (counting from the inlet opening and going downstream); the second reactant is injected into injection points 2, 4, 6, etc. In general, the first reactant is injected into the odd-numbered injection points, and the second reactant is injected into the even-numbered injection points.

The self-purging mechanism described above is an idealized model, which is generally met only in tubes having a single injection point. Particles located at a second injection point are purged by a carrier gas comprising small quantities of unreacted reactant and/or reaction by-products from the first reaction point. In general these contaminants are sufficiently diluted not to cause problems. In particular if the tube contains a large number of injection points, it may be desirable to provide one or more flush points for removing reaction products and/or unreacted reactants.

Desirably, the carrier gas is an inert gas, for example nitrogen or a noble gas, in particular helium.

The linear velocity of the carrier gas is selected to be high enough to cause entertainment of the particles. Accordingly, the lower limit of this linear velocity is largely determined by factors such as the mean particle size, the particle density, and the aspect ratio of the particles. It will be understood that the particle size increases as the particles travel through the tube, as a result of the coating layers being deposited onto the particles. The linear velocity of the carrier gas should be sufficient for entraining the particles after deposition of the desired number of coating layers. For this purpose, the linear velocity may be increased along the tube. In some embodiments such velocity increase is at least partially obtained by the subsequent reactant injections.

In an alternate embodiment of the process the tube is provided with one or more flush points, which are used not only to flush the carrier gas, but also to increase the carrier gas flow rate by introducing more carrier gas than is being flushed out. As a result the linear velocity of the carrier gas is increased downstream from the flush point, to compensate for the increase in weight and size of the particles. The upper limit of the linear velocity of the carrier gas is determined primarily be the desire to operate the tube under plug flow conditions. The principles of plug flow are well known to those skilled in the art. The conditions for plug flow for a tube similar to the one used in the process of the invention are disclosed in Helmsing et al., “Short Contact Time Experiments in a Novel Benchscale FCC Riser Reactor”, Chemical Engineering Science, Vol. 51, No. 11, pp 3039-3044 (1996), the disclosures of which are incorporated herein by reference.

The linear velocity is preferably chosen so as to obtain completion of the selfterminating reaction before the next injection point is encountered. In general, the linear velocity of the carrier gas is in the range of from 0.02 to 30 m/s, preferably in the range of from 0.1 to 10 m/s.

The tube is kept at a temperature suitable for the reaction cycles being carried out within the tube. In general, the temperature is in the range of from 0 to 1000° C (but may in the present invention be much lower; see also above, especially for ALD). In ALD the first and second reactions of a reaction cycle may require different reaction temperatures. In a preferred embodiment of the invention different parts of the tube may be kept at different temperatures. Specifically, tube segments downstream from odd-numbered injection points and upstream to even-numbered injection points are kept at a first temperature, corresponding to the reaction temperature of the first reaction of the ALD reaction cycle. Likewise, tube segments from even numbered injection points to odd numbered injection points are kept at a second temperature, corresponding to the reaction temperature of the second reaction of the ALD reaction cycle.

Optionally, before reaching an injection point, particles in the tube may be preconditioned. Particle pre-conditioning can be particularly useful before particles are brought into contact with the first reactant, i.e. upstream the first injection point. Pre-conditioning may include heating of the particles upstream an injection point to a desired temperature, preferably a temperature corresponding or close to the reaction temperature of the reaction planned downstream the injection point. Pre-heating of particles upstream the injection point may limit development of a temperature gradient in the tube downstream of the injection point. The presence of such temperature gradient is undesirable as it may induce different reaction rates in different portions of the tube. A substantially constant temperature at different portions of the tube provides a more constant reaction rate, which simplifies reaction control and apparatus design. Additionally, or alternatively, reactants injected in the tube may also be preheated to a suitable temperature before they are injected into the tube for similar reasons as discussed above with respect to the pre-heating of the particles.

Tube segments from even-numbered injection points to odd-numbered injection points may be made of a different material than tube segments from odd-numbered injection points to even-numbered injection points to accommodate reactions at different temperatures and/or cope with different reactants and/or gaseous reactant products. For example, some tube segments may be made of Teflon, while others may be made of stainless steel. The selection of a suitable tube material may be based on finding an optimum in chemical resistance and heat conduction properties. For example, if keeping a constant temperature throughout the tube is of importance, a tube material with a sufficiently high heat conduction coefficient is desirable. Additionally, it may be desirable that the reaction between particles and injected reactants is not disturbed by chemical reactions with binding groups in the tube walls. Therefore, if such reactions are likely to occur due to the use of a specific type of reactants, a material with sufficient resistance against such chemical reactions is desirable.

The process is suitable for depositing coatings onto particles of a broad range of mean particle sizes, from about 2 nm to 1 mm. An important advantage of the process of the invention, as compared to fluidized bed processes of the prior art, is its ability to coat particles having a particle size well below 1 mm.

Another aspect of the present invention is an apparatus for carrying out the above-described process. In its broadest aspect this aspect relates to an apparatus for a continuous process for atomic layer deposition onto particles while said particles are subjected to pneumatic transport, said apparatus comprising (i) a tube having an inlet opening and an outlet opening; (ii) a feeder device for feeding a carrier gas entraining the particles into the tube; and (iii) at least one injection point downstream from the inlet opening for introducing a reactant into the tube.

In a preferred embodiment the tube has a plurality of injection points downstream from the inlet opening. Desirably the injection points are spaced apart along at least a portion of the length of the tube. Preferably the injection points are spaced along substantially the length of the tube.

A preferred embodiment of the apparatus comprises at least one flush point for removing reaction by-products from the tube. The term “reaction by-products” in this context includes unreacted reactants. The tube has an internal diameter in the range of from 0.02 to 300 mm. The actual diameter may be selected within this range in function of the mean diameter of the particles to be coated within the apparatus, the desired linear velocity of the carrier gas, and like such factors. In most cases a suitable tube inner diameter is in the range of from 0.1 mm to 100 mm, preferably in the range of from 1 mm to 20 mm.

If there is more than 1 injection point, the distance between two adjoining injection points is preferably determined by the time required for the reaction to self-terminate, and the distance traveled by the carrier gas during that time. The reactions involved are generally more or less instantaneous, but some time needs to be allowed for the reactants to travel from the injection point to the particles. In general, subsequent injection points are from 10 mm to 5000 mm apart, preferably from 10 mm to 100 mm apart.

The length of the tube is determined primarily by the number of injection points required. Accordingly, the length of the tube is in the range of from 0.1 m to 500 m. In many cases the length of the tube is in the range of from 5 m to 50 m.

In order to limit the physical space requirements of the apparatus the tube may be folded or coiled. Suitably, the tube is contained in a chamber provided with means for heating and/or cooling. The actual design of the chamber, and the specifications of the heating and/or cooling means, may be based on the desired operating temperature. The operating temperature may be in the range of from 0° C. to 1000° C.

FIG. 1 is a schematic representation of an embodiment of the apparatus of the invention for deposing a number of layers onto particles entrained in a flow of gas. Stating material 5 is fed into spray system 100 where they are fluidized by inert gas 7, e.g. nitrogen, and entrained into a coiled tube 252. At first injection point 2512A the first reactant of an atomic layer deposition cycle is introduced into the coiled tube. At second injection point 2512B the second reactant of the ALD cycle is introduced into the coiled tube. At injection point 2513 A a second dose of the first reactant is introduced, and at injection point 2513B the coiled tube receives a second dose of the second reactant. The cycle is repeated at injection point pairs 2514A/2514B; 2515A/2515B; and 2516A/2516B. A separation device 25200 separates the coated particles 2518 from the gas flow 2517, which may now not only comprise the inert gas, but also gaseous reaction products, and unreacted reactants. The separation device 25200 may be any suitable separation device, for example a cyclone separator.

Optionally, as denoted by the dashed arrows, one or more flush points 2512- 2516C, 2512-2516D are arranged along the tube to remove gaseous reaction products from the gas flow. In particular, flush points 2512C, 2513C, 2514C, 2515C and 2516C may predominantly remove gaseous reaction products related to the first reactant. Similarly, flush points 2512D, 2513D, 2514D, 2515D, and 2516D may predominantly remove gaseous reaction products related to the second reactant. The flush points may comprise a suitable filter to allow reaction products to be removed while keeping particles in the tube 252.

Optionally, the temperature of the different reactions may be set by temperature control units 2521, 2522, for example heat exchangers or other types of devices for heating and/or cooling known to a person skilled in the art. The temperature control units 2521 may be arranged to control the temperature in parts of the tube reserved for reaction with the first reactant, i.e. downstream injection points of the first reactant and upstream injection points of the second reactant. For example, the temperature control units 2521 may be arranged to keep the temperature in these tube parts at a first temperature. Similarly, the temperature control units 2522 may be arranged to control the temperature in tube parts reserved for reaction with the second reactant, e.g. by keeping the temperature in these parts at a second temperature.

Optionally, a pre-conditioning unit 2523 is arranged for pre-conditioning the particles in the particle flow. Such pre-conditioning may include heating particles to a temperature close to a desirable reaction temperature with the first reactant provided via injection point 2512A. Although not explicitly shown, more pre-conditioning units may be used in the apparatus, for example to pre-heat particles upstream further injection points.

It will be understood that the representation is a schematic one. The depicted number of injection point pairs (numbering 5 in FIG. 2) represents a plurality of injection point pairs which, in reality, may range from just 1 to several hundreds or even thousands.

Reference 1201 and 1202 indicate an inlet and an outlet, respectively, of the vapor deposition system 200. Gas may flow from the inlet 1201 to the outlet 1202. Reference 7 indicates an influx of gas, such as e.g. helium (see also above). For instance in this way, particles may be pneumatically transported.

Fig. 3a schematically depicts an embodiment of an electrode 2000 comprising the first material 1. Reference 2010 indicates a support, which may be electrically conducting. The support 2010 may e.g. be a graphite support or graphite layer. In alternative embodiments, the support 2010 may e.g. be aluminum. In embodiments, the electrode 2000 may comprise a cathode.

Fig. 3b schematically depicts an embodiment of a battery 3000 comprising the electrode 2000. In embodiments, the electrode 2000 may be configured as cathode. Reference 3010 indicates a second electrode.

The term “plurality” refers to two or more. The terms “substantially” or “essentially” herein, and similar terms, will be understood by the person skilled in the art. The terms “substantially” or “essentially” may also include embodiments with “entirely”, “completely”, “all”, etc. Hence, in embodiments the adjective substantially or essentially may also be removed. Where applicable, the term “substantially” or the term “essentially” may also relate to 90% or higher, such as 95% or higher, especially 99% or higher, even more especially 99.5% or higher, including 100%.

The term “comprise” also includes embodiments wherein the term “comprises” means “consists of’.

The term “and/or” especially relates to one or more of the items mentioned before and after “and/or”. For instance, a phrase “item 1 and/or item 2” and similar phrases may relate to one or more of item 1 and item 2. The term "comprising" may in an embodiment refer to "consisting of but may in another embodiment also refer to "containing at least the defined species and optionally one or more other species".

Furthermore, the terms first, second, third and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.

The devices, apparatus, or systems may herein amongst others be described during operation. As will be clear to the person skilled in the art, the invention is not limited to methods of operation, or devices, apparatus, or systems in operation.

It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the appended claims.

In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim.

Use of the verb "to comprise" and its conjugations does not exclude the presence of elements or steps other than those stated in a claim. Unless the context clearly requires otherwise, throughout the description and the claims, the words “comprise”, “comprising”, and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to”.

The article "a" or "an" preceding an element does not exclude the presence of a plurality of such elements. The invention may be implemented by means of hardware comprising several distinct elements, and by means of a suitably programmed computer. In a device claim, or an apparatus claim, or a system claim, enumerating several means, several of these means may be embodied by one and the same item of hardware. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.

The invention also provides a control system that may control the device, apparatus, or system, or that may execute the herein described method or process. Yet further, the invention also provides a computer program product, when running on a computer which is functionally coupled to or comprised by the device, apparatus, or system, controls one or more controllable elements of such device, apparatus, or system.

The invention further applies to a device, apparatus, or system comprising one or more of the characterizing features described in the description and/or shown in the attached drawings. The invention further pertains to a method or process comprising one or more of the characterizing features described in the description and/or shown in the attached drawings.

The various aspects discussed in this patent can be combined in order to provide additional advantages. Further, the person skilled in the art will understand that embodiments can be combined, and that also more than two embodiments can be combined. Furthermore, some of the features can form the basis for one or more divisional applications.

Claims

37 WO 2022/075846 PCT/NL2021/050607 CLAIMS:

1. A method for providing coated particles (20), the method comprising: a particle generation process comprising feeding a starting material (5) to a particle generation zone (1100) to generate particles (10); wherein the starting material (5) comprises a lithium comprising material, and wherein the starting material comprise one or more of a manganese comprising material, a cobalt comprising material, a nickel comprising material, and an iron comprising material; wherein the starting material (5) comprises a solvent, wherein the solvent comprises a non-aqueous solvent; wherein the particle generation process comprises a spray process, wherein the spray process comprises a plasma spray pyrolysis process; feeding with a fluid flow the particles (10) generated in the particle generation zone (1100) from the particle generation zone (1100) to a coating zone (1200); and a particle coating process comprising coating the particles (10) while flowing in the coating zone (1200) to provide the coated particles (20); wherein the particle coating process comprises a vapor deposition process.

2. The method according to claim 1, comprising: executing the plasma spray pyrolysis process at a pressure selected from the range of 0.5-2 bar, and executing the plasma spray pyrolysis process at a temperature selected from the range of up to 500 °C; and wherein the starting material (5) comprises one or more liquids, wherein the one or more liquids comprise the solvent, wherein at least 95 vol.% of the one or more liquids is non-aqueous; and wherein the vapor deposition process comprises one or more of chemical vapor deposition, molecular layer deposition, and atomic layer deposition.

3. The method according to any one of the preceding claims, wherein the solvent comprises supercritical CO2.

4. The method according to any one of the preceding claims, wherein the starting material comprises (i) supercritical CO2 and (ii) one or more of methanol, ethanol, ammonia, methanediol, ethane-diol, and propane-diol. 38

WO 2022/075846 PCT/NL2021/050607

5. The method according to any one of the preceding claims, wherein the starting material (5) comprises cobalt and lithium, having an atom ratio 0.005<Co/Li<0.05.

6. The method according to any one of the preceding claims, wherein the vapor deposition process comprises a deposition process of a carbon comprising shell material and/or wherein the vapor deposition process comprises a deposition process of a phosphate comprising shell material.

7. The method according to any one of the preceding claims, wherein the vapor deposition process comprises a deposition process of an oxide comprising shell material, wherein the oxide comprising shell material comprises one or more materials selected from the group consisting of an aluminum comprising shell material, a cerium comprising shell material, a cobalt comprising shell material, a niobium comprising shell material, a silicon comprising shell material, and a titanium comprising shell material; and wherein the vapor deposition process comprises atomic layer deposition; wherein the oxide comprising shell material comprises a cobalt oxide.

8. The method according to any one of the preceding claims, wherein a shell layer (220,221) comprises alumina and carbon.

9. The method according to any one of the preceding claims, wherein the vapor deposition process comprises a multi-layer deposition process, wherein a first shell layer (221) comprises cobalt oxide, and wherein a second shell layer (222), further away from a core (21) than the first shell layer (221), comprises alumina.

10. The method according to any one of the preceding claims, wherein the coated particles (20) comprise cobalt with a weight percentage in the range of up to 5 wt%.

11. An apparatus (1000) for providing coated particles (20), the apparatus (1000) comprising a particle generation zone (1100) and a coating zone (1200), configured downstream of the particle generation zone (1100), wherein in an operational mode the apparatus is configured to: (i) feed with a fluid flow particles (10) generated in the particle generation zone (1100) from the particle generation zone (1100) to the coating zone (1200), and (ii) to coat the particles (10) while flowing in the coating zone (1200) to provide coated particles (20); wherein the particle generation zone (1100) comprises a spray system (100) configured to generate the particles (10), and wherein the coating zone (1200) comprises a vapor deposition system (200) configured to provide a coating (22) to particles (10) thereby providing the coated particles (20); wherein the spray system (100) comprises a plasma spray pyrolysis system configured to execute a plasma spray pyrolysis process; wherein the vapor deposition system (200) is configured to execute a vapor deposition process, wherein the vapor deposition process comprises one or more of chemical vapor deposition, molecular layer deposition, and atomic layer deposition.

12. The apparatus according to claim 11, wherein the vapor deposition system (200) is configured to execute the vapor deposition process at a pressure selected from the range of 0.5- 2 bar; and wherein the vapor deposition system (200) is configured to execute the vapor deposition process at a temperature selected from the range of up to 500 °C; wherein the spray system (100) is configured to execute the plasma spray pyrolysis process at a pressure selected from the range of 0.5-2 bar; and wherein the spray system (100) is configured to execute the plasma spray pyrolysis process at a temperature selected from the range of up to 500 °C; the apparatus further comprising a supercritical CO2 supply (2).

13. The apparatus according to any one of the preceding claims 11-12, wherein the vapor deposition system (200) comprises a pneumatic transport reactor (250).

14. A first material (1) comprising coated particles (20), wherein the coated particles (20) comprise a core (21) and a shell (22), enclosing at least part of the core (21), wherein the core (21) comprises a core material, wherein the core material comprises a lithium comprising core material, and wherein the core material comprises one or more of a manganese comprising core material, a cobalt comprising core material, a nickel comprising core material, and an iron comprising core material; and wherein the shell (22) comprises a shell material, wherein the shell material comprises one or more materials selected from the group consisting of an aluminum comprising shell material, a cerium comprising shell material, a cobalt comprising shell material, an iron comprising shell material, a niobium comprising shell material, a silicon comprising shell material, a titanium comprising shell material, and a carbon comprising shell material, wherein the core material has a chemical composition different from a chemical composition of the shell material closest to the core material, wherein the coated particles (20) comprise cobalt with a weight percentage in the range of 0.1-5 wt%.

15. The first material according to claim 14, wherein the shell material comprises an oxide comprising shell material, wherein the oxide comprising shell material comprises one or more materials selected from the group consisting of alumina, ceria, cobalt oxide, niobium oxide, silica, and titania; and wherein the coated particles (20) comprise cobalt with a weight percentage in the range of 0.5-5 wt%.

16. The first material (1) according to any one of the preceding claims 14-15, wherein the core material comprises cobalt and lithium, having an atom ratio 0.005<Co/Li<0.05.

17. The first material (1) according to any one of the preceding claims 14-16, wherein the core material comprises Li[Nii-x-yCo_xMn_y]O2, wherein x is selected from the range of 0-0.5, and wherein y is selected from the range of 0-0.5, and/or wherein the core material comprises LiFePC , and wherein a shell on the core material does not consist of LiFePC .

18. The first material (1) according to any one of the preceding claims 14-17, wherein the shell material comprises a phosphate comprising shell material; wherein the shell material comprises LiFePC , and wherein a shell layer consisting of LiFePC , is not on a core consisting ofLiFePC .

19. The first material (1) according to any one of the preceding claims 14-18, wherein the shell (22) comprises a shell layer (220), wherein the shell layer (220) is a carbon layer or wherein the shell layer (220) comprises alumina and carbon.

20. The first material (1) according to any one of the preceding claims 14-19, wherein the shell material comprises cobalt oxide.

21. The first material (1) according to any one of the preceding claims 14-20, wherein the shell material comprises a multi-layer, wherein a first shell layer (221) comprises cobalt oxide, and wherein a second shell layer (222), further away from a core (21) than the first shell layer (221), comprises alumina.

22. An electrode (2000) comprising the first material (1) according to any one of the preceding claims 14-21.

23. The electrode (2000) according to claim 22, wherein the electrode comprises a cathode.

24. A battery (3000) comprising the electrode (2000) according to any one of the preceding claims 22-23.