Lithium hydroxide-based powders for lithium composite oxides, and a method for manufacture said lithium hydroxide-base powders

Abstract

The present disclosure relates to a lithium hydroxide-based powder for preparing a lithium composite oxide for lithium-ion batteries. More specifically, the present disclosure relates to a lithium hydroxide-based powder with high bulk density. The present disclosure also relates to a method for manufacturing said lithium hydroxide-based powder. The present disclosure also relates to a composition comprising the lithium hydroxide-based powder and a transition-metal hydroxide or oxyhydroxide.

Description

Lithium hydroxide-based powders for lithium composite oxides, and a method for manufacture said lithium hydroxide-based powdersTECHNICAL FIELD

[0001] The present disclosure relates to a lithium hydroxide-based powder for preparing a lithium composite oxide for lithium-ion batteries. More specifically, the present disclosure relates to a lithium hydroxide-based powder with high bulk density. The present disclosure also relates to a method for manufacture said lithium hydroxide-based powder. The present disclosure also relates to a composition comprising the lithium hydroxide-based powder and a transition-metal hydroxide or oxyhydroxide.BACKGROUND ART

[0002] Modern batteries require high energy density as well as long cycle life, especially for automotive applications. Currently, lithium composite oxides, such as NMC (lithium-nickel-manganese-cobalt oxide) or NMA (lithium-nickel-manganese-aluminum oxide), are the most promising cathode active materials used in batteries for electric vehicles or hybrid electric vehicles.

[0003] A general method for manufacture a cathode active material usually involves the step of mixing a mixed-metal precursor (transition-metal hydroxide or oxyhydroxide) and a lithium source to obtain a first mixture, known as blend or blend mixture. Then blend mixture is then loaded onto industrial trays and subjected to high-temperatures, generally exceeding 1000 °C, to yield a lithium mixed-metal oxide. The efficiency of this process is influenced by the tray loading, as higher loadings correlate with increased production throughput. However, excessive tray loading might compromise the uniformity of the thermal treatment, leading to inhomogeneous material and deterioration of the electrochemical performance of the resulting cathode active material.

[0004] The physicochemical properties of the mixed-metal precursor and lithium source, such as median particle size distribution, span, and sphericity, may play a crucial role in the electrochemical properties of the resulting cathode active material and, ultimately, in the performance of the lithium-ion battery. For instance, the use of a lithium source exhibiting high span (greater than 5.0) is associated with excessive crystal growth during the formation of the lithium mixed-metal oxide, leading to particle agglomeration and adversely impacting the electrochemical properties of the lithium-ion battery. Additionally, a lithium source with excessive bulk density (greater than 0.70 grams per cubic centimeter) is associated with the formation of a non-homogeneous blend material.

[0005] Cathode active materials comprising particles with a narrow span may exhibit a uniform particle distribution, providing a higher tap density and a more robust structure. Accordingly, a cathode active material comprising particles with narrow span might have higher reversible capacity, improved stability and higher capacity retention, see Mallick et al, J. Mat. Chem. A, 2023, 11, 3789.

[0006] Cathode active materials comprising high Ni content usually also comprise a higher amount of impurities, see US7648693. Impurities, such as hydroxide or carbonate salts, also known as soluble bases, often remain on the surface of the cathode active material causing gas generation in the cells (bulging), resulting in poor stability, poor cycling performance and raising safety issues.

[0007] Additionally, lithium sources comprising high U2CO3 content might be associated with crystal growth inhibition, affecting the capacity fading of the Li-ion battery.

[0008] Therefore, there is a need to provide a lithium hydroxide-based powder for preparing a lithium composite oxide, which improves the throughput of the manufacturing process of the cathode active material.

[0009] Additionally, there is a need for a method for manufacture said lithium hydroxide-based powder.

[0010] There is also a need for a composition comprising the lithium hydroxide-based powder and a transition-metal hydroxide or oxyhydroxide.SUMMARY

[0011] The present disclosure provides a lithium hydroxide-based powder, for preparing a lithium composite oxide, wherein the lithium hydroxide-based powder comprises particles having a span lower than 5.0, a median particle size distribution D50 between 19.0 and 70.0 pm, a bulk density between 0.12 and 0.70 grams per cubic centimeter, and comprises lithium carbonate in a content lower than 2.0 wt% relative to the total weight of the lithium hydroxide-based powder.

[0012] The lithium hydroxide-based powder according to this disclosure may increase the tray loading without compromising the integrity or homogeneity of the blended material. Consequently, the manufacturing process of the cathode active material benefits from enhanced throughput, further optimizing production efficiency while maintaining or improving the electrochemical properties of the corresponding lithium-ion battery. Additionally, thecorresponding cathode active material may have high tap density and improved capacity retention.

[0013] The present disclosure also provides a method for manufacture said lithium hydroxide-based powder, comprising the following steps:drying a lithium containing compound in a vacuum oven, or in an oven under a carbon dioxide-free atmosphere to obtain a dried material; and- jet milling the dried material under a carbon-dioxide free atmosphere to obtain the lithium hydroxide-based powder.

[0014] The present disclosure also provides a composition for a cathode active material, comprising said lithium hydroxide-based powder and a transition-metal hydroxide or oxyhydroxide, comprising M, wherein M comprises:Ni in an atomic content x, wherein 0.50 < x < 0.98 relative to M;Mn in an atomic content y, wherein 0.005 < y < 0.50 relative to M;Co in an atomic content z, wherein 0.0 < z < 0.50 relative to M;Al in an atomic content a, wherein 0.0 < a < 0.50 relative to M,wherein x, y, z and a measured by ICP-OES, x+y+z+a is 1, and wherein the Li / M atomic ratio of the composition is between 0.8 to 1.5.BRIEF DESCRIPTION OF THE FIGURESFigure 1 shows an image of a blend mixture comprising the lithium hydroxide-based precursor EX2, and Nio.8oMno.ioCoo.io(OH)2, obtained as described in the Examples section.Figure 2 shows an image of a blend mixture comprising the lithium hydroxide-based precursor CEX1, and Nio.8oMno.ioCoo.io(OH)2, obtained as described in the Examples section.DETAILED DESCRIPTION

[0015] In the following detailed description, preferred embodiments are described in detail to enable practice of the present invention. Although the present invention is described with reference to these specific preferred embodiments, it will be understood that the present invention is not limited to these preferred embodiments. In contrast, the present invention includes numerous alternatives, modifications and equivalents as will become apparent from consideration of the following detailed description.

[0016] The following terms are intended to have the meaning presented below and are useful in understanding the description and intended scope of this disclosure.

[0017] The term "comprising", as used herein and in the claims, should not be interpreted as being restricted to the means listed thereafter; it does not exclude other elements or steps. It needs to be interpreted as specifying the presence of the stated features, integers, steps, or components as referred to, but does not preclude the presence or addition of one or more other features, integers, steps or components, or groups thereof. Thus, the scope of the expression "a composition comprising components A and B" should not be limited to compositions consisting only of components A and B. It means that with respect to the present disclosure, the only relevant components of the composition are A and B. Accordingly, the terms "comprising" and "including" encompass the more restrictive terms "consisting essentially of" and "consisting of".

[0018] The term "cathode active material" (also known as CAM or positive electrode active material) refers to a material which is electrochemically active in a positive electrode or cathode. By active material, it must be understood to be capable of capturing and releasing Li ions when subjected to a voltage change over a predetermined period.

[0019] In the framework of the present disclosure, the content of a particular element of the periodic table signifies atomic percentage. The at% or "atomic percent" of a given element expression of a concentration means how many percent of all atoms in the concerned compound are atoms of said element. The designation at% is equivalent to mol% or "molar percent".

[0020] The term "median particle size D50", as defined herein, can be interchangeably used with the terms "D50" or "d50" or "median particle size" or "a median particle size (d50 or D50)". D50 is defined as the particle size at 50% of the cumulative volume% distributions. D50 is typically determined by laser diffraction particle size analysis. D10 and D90 are defined as particle sizes at 10% and 90% of cumulative volume% distribution when measured by laser scattering method as described in this specification, respectively.

[0021] The term "span", as used in the text, is defined as (D90-D10) divided by D50; i.e. (D90-D10) / D50. The term "narrow span" stands for a span equal to or lower than 5.0.

[0022] As used herein, a range of values "between X and Y" include the endpoints of X and Y.Lithium Hydroxide-based Powder

[0023] In a first aspect, the present disclosure relates to a lithium hydroxide-based powder for preparing a lithium composite oxide, wherein the lithium hydroxide-based powder comprises particles having a span lower than 5.0, a median particle size distribution D50 between 19.0 and 70.0 pm, a bulk density between 0.12 and 0.70 grams per cubic centimeter, and further comprises lithium carbonate in a content lower than 2.0 wt% relative to the total weight of the lithium hydroxide-based powder.

[0024] In one embodiment, the lithium hydroxide-based powder according to the first aspect of this disclosure comprises particles having a span lower than 4.0. In another embodiment, the span is lower than 3.0. In another embodiment, the span is lower than 2.5. For example, the span is lower than 2.5, 2.4, 2.3, 2.2 or 2.1.

[0025] In one embodiment, the lithium hydroxide-based powder according to the first aspect of this disclosure, comprises lithium carbonate in a content lower than 1.8 wt% relative to the total weight of the lithium hydroxide-based powder. In another embodiment, the lithium carbonate content is lower than 1.5 wt%. In another embodiment, the lithium carbonate content is lower than 1.0 wt%. In another embodiment, the lithium carbonate content is lower than 0.8 wt%. In another embodiment, the lithium carbonate content is lower than 0.7 wt%. In another embodiment, the lithium carbonate content is lower than 0.6 wt%. In another embodiment, the lithium carbonate content is lower than 0.5 wt%. In another embodiment, the lithium carbonate content is lower than 0.45 wt%. In another embodiment, the lithium carbonate content is lower than 0.43 wt%.

[0026] In one embodiment, the lithium hydroxide-based powder according to the first aspect of this disclosure, comprises lithium hydroxide in a content equal to or higher than 90 wt% relative to the total weight of the lithium hydroxide-based powder. In another embodiment, the lithium hydroxide content is equal to or higher than 95 wt%. In another embodiment, the lithium hydroxide content is equal to or higher than 98 wt%. In another embodiment, the lithium hydroxide content is equal to or higher than 99 wt%. In another embodiment, the lithium hydroxide-based powder consists of lithium hydroxide.

[0027] In one embodiment, the lithium hydroxide-based powder according to the first aspect of this disclosure, comprises particles having a median particle size distribution D50 between 20.0 pm and 70.0 pm. In another embodiment, the median particle size distribution D50 is between 25.0 and 50.0 pm. In another embodiment, the median particle size distribution D50 is between 25.0 and 40.0 pm. In another embodiment, the median particle size distribution D50 is between 25.0 and 35.0 pm. For example, the median particle size distribution D50 is 25.0, 26.0, 27.0, 28.0, 29.0, 30.0, 31.0, 32.0, 33.0, 34.0 or 35.0 pm.

[0028] In one embodiment, the lithium hydroxide-based powder according to the first aspect of this disclosure, comprises particles having a median particle size distribution DIO higher than 7.0 pm. In another embodiment, the median particle size distribution DIO is higher than 9.0 pm. In another embodiment, the median particle size distribution DIO is higher than 10.0 pm. In another embodiment, the median particle size distribution D10 is between 10.0 and 15.0 pm. In another embodiment, the median particle size distribution D10 is 10.0, 11.0, 12.0, 13.0, 14.0 or 15.0 pm.

[0029] In one embodiment, the lithium hydroxide-based powder according to the first aspect of this disclosure, comprises particles having a median particle size distribution D90 between 50.0 and 100.0 pm. In another embodiment, the median particle size distribution D90 is between 60.0 and 100.0 pm. In another embodiment, the median particle size distribution D90 is between 65.0 and 95.0 pm. In another embodiment, the median particle size distribution D90 is between 70.0 and 90.0 pm. For example, the median particle size distribution D90 is 70.0, 71.0, 72.0, 73.0, 74.0, 75.0, 76.0, 77.0, 78.0, 79.0, 80.0, 81.0, 82.0, 83.0, 84.0, 85.0, 86.0, 87.0, 88.0, 89.0 or 90.0 pm.

[0030] In one embodiment, the lithium hydroxide-based powder according to the first aspect of this disclosure, comprises particles having a bulk density between 0.13 and 0.70 grams per cubic centimeter. In another embodiment, the bulk density is between 0.16 and 0.50 grams per cubic centimeter. In another embodiment, the bulk density is between 0.16 and 0.60 grams per cubic centimeter. In another embodiment, the bulk density is between 0.16 and 0.50 grams per cubic centimeter. In another embodiment, the bulk density is between 0.16 and 0.40 grams per cubic centimeter. In another embodiment, the bulk density is between 0.16 and 0.30 grams per cubic centimeter. In another embodiment, the bulk density is between 0.17 and 0.30 grams per cubic centimeter. For example, the bulk density is 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29 or 0.30 grams per cubic centimeter.Method for Manufacture Lithium Hydroxide-based Powder

[0031] In a second aspect, the present disclosure relates to a method for manufacture the lithium hydroxide-based powder according to the first aspect of this disclosure, wherein the method comprises the following steps:drying a lithium containing compound in a vacuum oven, or in an oven under a carbon dioxide-free atmosphere to obtain a dried material; and- jet milling the dried lithium containing compound under a carbon-dioxide free atmosphere to obtain the lithium hydroxide-based powder.

[0032] The lithium hydroxide-based powder according to the first aspect of the present disclosure may be obtained by a method according to the second aspect of the present disclosure. In detail, the technical features of the first aspect of the present disclosure, e.g., the specific composition of the lithium hydroxide-based powder, median particle size distribution, span, impurities content, bulk density, tap density may be achieved by the method according to the second aspect of the present disclosure.

[0033] The drying step is performed to reduce the moisture content in the lithium source material because water might inhibit the reaction between lithium and the transition-metal hydroxide or oxyhydroxide. Also, the drying step is performed in a vacuum oven or in an oven under a carbon dioxide-free atmosphere such that lithium in the lithium source material should not uptake carbon to generate lithium carbonate during the step of drying.

[0034] In one embodiment of the method according to the second aspect of this disclosure, the drying step is performed in a temperature of at least 70 °C. In another embodiment, the temperature is at least 100 °C. In another embodiment, the temperature is at least 150°C. In another embodiment, the temperature is between 170 °C and 300 °C. In another embodiment, the temperature is at most 280 °C. In another embodiment, the temperature is at most 240 °C. In another embodiment, the temperature is at most 210 °C.

[0035] In one embodiment of the method according to the second aspect of this disclosure, the drying step is performed for at least 30 minutes. In another embodiment, for at least 40 minutes. In another embodiment, for a time between 50 minutes and 90 minutes. In another embodiment, it is at most 80 minutes. In another embodiment, it is at most 70 minutes.

[0036] In one embodiment of the method according to the second aspect of this disclosure, the jet milling step comprises a pulverizing step where mechanical energy is applied to reduce the dried lithium-containing compound. In another embodiment, the pulverizing step comprises pulverizing the dried lithium containing compound in its dry state, / .e., in the absence of a liquid medium.

[0037] In one embodiment of the method according to the second aspect of this disclosure, the jet mill step is a pulverizing step, which reduces particle size by using a jet of a compressed gas to impact particles into one another or the walls of the jet mill, thereby pulverizing the particles. In another embodiment, carbon dioxide-free gas is injected into the jet mill as a compressed gas such that lithium in the lithium source material should not uptake carbon to generate lithium carbonate. Also, a volume flow rate of the carbon dioxide-free gas ranges preferably from 0.1 to 20.0 m3 / min, more preferably from 1 to 15 m3 / min; a grinding pressure ranges preferably from 1 to 10 bar, more preferably from 3 to 7 bar; and a feedingrate of the dried lithium containing compound ranges preferably from 20 to 60 kg / hr, more preferably from 30 to 50 kg / hr.

[0038] In one embodiment of the method according to the second aspect of this disclosure, the carbon dioxide-free gas during at least one of the steps of drying and pulverizing is nitrogen, or CCh-free dry air.

[0039] In one embodiment of the method according to the second aspect of this disclosure, the CO2-free dry air in the pulverizer has a relative humidity of at most 1%, and / or less than 20 ppm of CO2.

[0040] In one embodiment of the method according to the second aspect of this disclosure, the milling step is fluidized-bed jet milling step with a grinding pressure between 3 and 6 bars, and screening speed control below 1000 rpm, using CCh-free dry air or nitrogen. In another embodiment, the screening speed control is between 600 and 1000 rpm. In another embodiment, the screening speed control is between 600 and 900 rpm, using CCh-free dry air or nitrogen.

[0041] In one embodiment of the method according to the second aspect of this disclosure, the milling step is a spiral jet milling step with a grinding pressure of 6.5 bar and milling pressure of 5.5 bar, using CCh-free dry air or nitrogen.Composition for a cathode active material

[0042] In a third aspect, the present disclosure relates to a composition for a cathode active material, comprising the lithium hydroxide-based powder according to the first aspect of this disclosure, and a transition-metal hydroxide or oxyhydroxide, comprising M, wherein M comprises:Ni in an atomic content x, wherein 0.50 < x < 0.98 relative to M;Mn in an atomic content y, wherein 0.005 < y < 0.50 relative to M;Co in an atomic content z, wherein 0.0 < z < 0.50 relative to M;Al in an atomic content a, wherein 0.0 < a < 0.50 relative to M;wherein x, y, z and a are measured by ICP-OES, and x+y+z+a is 1, and wherein the Li / M atomic ratio of the composition is between 0.8 to 1.5.

[0043] In one embodiment, the composition according to the third aspect of this disclosure, comprises the lithium hydroxide-based powder according to the first aspect, and a transitionmetal hydroxide or oxyhydroxide comprising M, wherein the composition has a Li / M atomic ratio between 0.9 and 1.5. In another embodiment, the Li / M atomic ratio is between 0.95 and 1.2. In another embodiment, the Li / M atomic ratio is 0.98 to 1.02. For example, the Li / M atomic ratio is 0.98, 0.99, 1.00, 1.01 or 1.02.

[0044] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide comprising Ni in an atomic content x, wherein 0.60 < x < 0.95 relative to M. In another embodiment, 0.70 < x < 0.90 relative to M. In another embodiment, 0.75 < x < 0.85 relative to M. For example, x is 0.75, 0.76, 0.77, 0.78, 0.79. 0.80, 0.81, 0.82, 0.83, 0.84 or 0.85, relative to M.

[0045] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide comprising Mn in an atomic content y, wherein 0.01 < y < 0.40 relative to M. In another embodiment, 0.02 < y < 0.30 relative to M. In another embodiment, 0.05 < y < 0.15 relative to M. For example, y is 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14 or 0.15 relative to M.

[0046] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide comprising Co in an atomic content z, wherein 0.01 < z < 0.40 relative to M. In another embodiment, 0.02 < z < 0.30 relative to M. In another embodiment, 0.05 < z < 0.15 relative to M. For example, z is 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14 or 0.15 relative to M.

[0047] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide comprising Al in an atomic content a, wherein 0.0 < a < 0.30 relative to M. In another embodiment, 0.0 < a < 0.15 relative to M. In another embodiment, 0.0 < a < 0.10 relative to M. For example, a is 0.0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 or 0.10, relative to M. In another embodiment a is 0 relative to M.

[0048] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide comprising Ni in an atomic content x, wherein 0.60 < x < 0.95 relative to M, Mn in an atomic content y, wherein 0.01 < y < 0.40 relative to M, Co in an atomic content z, wherein 0.01 < z < 0.40 relative to M, and Al in an atomic content a, wherein 0.0 < a < 0.30 relative to M, wherein x+y+z+a is 1.

[0049] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide comprising Ni in an atomic content x, wherein 0.70 < x < 0.90 relative to M, Mn in an atomic content y, wherein 0.02 < y < 0.30 relative to M, Co in an atomic content z, wherein 0.02 < z < 0.30 relative to M, and Al in an atomic content a, wherein 0.0 < a < 0.15 relative to M, wherein x+y+z+a is 1.

[0050] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide comprising Ni in an atomic contentx, wherein 0.75 < x < 0.85 relative to M, Mn in an atomic content y, wherein 0.05 < y < 0.15 relative to M, Co in an atomic content z, wherein 0.05 < z < 0.15 relative to M, and Al in an atomic content a, wherein 0.0 < a < 0.10 relative to M, wherein x+y+z+a is 1.

[0051] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide comprising Ni in an atomic content x, wherein 0.70 < x < 0.90 relative to M, Mn in an atomic content y, wherein 0.02 < y < 0.30 relative to M, Co in an atomic content z, wherein 0.0 < z < 0.10 relative to M, and Al in an atomic content a, wherein 0.0 < a < 0.10 relative to M, wherein x+y+z+a is 1.

[0052] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide comprising Ni in an atomic content x, wherein 0.70 < x < 0.80 relative to M, Mn in an atomic content y, wherein 0.15 < y < 0.30 relative to M, Co in an atomic content z, wherein z is 0 relative to M, and Al in an atomic content a, wherein 0.005 < a < 0.05 relative to M, wherein x+y+z+a is 1.

[0053] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide according to the formula (I) NixiMnyiCoziAlaiO?, wherein 0.50 < xl < 0.98; 0.005 < yl < 0.50; 0.0 < zl < 0.50; 0.0 < al < 0.50; wherein xl, yl, zl and al are measured by ICP-OES, and xl+yl+zl+al is 1.

[0054] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide according to the formula (I), wherein 0.60 < xl < 0.95. In another embodiment, 0.70 < xl < 0.90. In another embodiment, 0.75 < xl < 0.85. For example, xl is 0.75, 0.76, 0.77, 0.78, 0.79. 0.80, 0.81, 0.82, 0.83, 0.84 or 0.85.

[0055] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide according to the formula (I), wherein 0.01 < yl < 0.40. In another embodiment, 0.02 < yl < 0.30. In another embodiment, 0.05 < yl < 0.15. For example, yl is 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14 or 0.15.

[0056] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide according to the formula (I), wherein 0.01 < zl < 0.40. In another embodiment, 0.02 < zl < 0.30. In another embodiment, 0.05 < zl < 0.15. For example, zl is 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14 or 0.15.

[0057] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide according to the formula (I), wherein 0.0 < al < 0.30. In another embodiment, 0.0 < al < 0.15. In another embodiment, 0.0 < al < 0.10. For example, al is 0.0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 or 0.10. In another embodiment al is 0.

[0058] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide according to the formula (I), wherein 0.60 < xl < 0.95; 0.01 < yl < 0.40; 0.01 < zl < 0.40; 0.0 < al < 0.30, wherein xl+yl+zl+al is 1.

[0059] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide according to the formula (I), wherein 0.70 < xl < 0.90; 0.02 < yl < 0.30; 0.02 < zl < 0.30; 0.0 < al < 0.15, wherein xl+yl+zl+al is 1.

[0060] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide according to the formula (I), wherein 0.75 < xl < 0.85; 0.05 < yl < 0.15; 0.05 < zl < 0.15; 0.0 < al < 0.10, wherein xl+yl+zl+al is 1.

[0061] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide according to the formula (I), wherein 0.75 < xl < 0.85; 0.05 < yl < 0.15; 0.05 < zl < 0.15; al is 0, wherein xl+yl+zl+al is 1.

[0062] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide according to the formula (I), wherein 0.70 < xl < 0.90; 0.02 < yl < 0.30; 0.0 < zl < 0.10; 0.0 < al < 0.10; wherein xl+yl+zl+al is 1.

[0063] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide according to the formula (I), wherein xl is 0.80; yl is 0.10; zl is 0.10; and al is 0.0; wherein xl+yl+zl+al is 1.

[0064] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide or oxyhydroxide according to the formula (I), wherein 0.70 < xl < 0.80; 0.15 < yl < 0.30; zl is 0; 0.005 < al < 0.05; wherein xl+yl+zl+al is 1.

[0065] In one embodiment, the composition according to the third aspect of this disclosure, comprises a transition-metal hydroxide according to the formula (I), wherein xl is 0.75; yl is 0.24; zl is 0.0; and al is 0.01; wherein xl+yl+zl+al is 1.

[0066] In one embodiment, the composition according to the third aspect of this disclosure, comprises particles having a tap density higher than 2.5 grams per cubic centimeter. In another embodiment, the tap density is between 2.7 and 4.0 grams per cubic centimeter. In another embodiment, the tap density is between 2.75 and 3.0 grams per cubic centimeter. For example, the tap density is 2.75, 2.80, 2.85, 2.90 or 2.95 grams per cubic centimeter.

[0067] In one embodiment, the composition according to the third aspect of this disclosure, comprises particles having a bulk density between 0.67 and 0.95 grams per cubic centimeter. In another embodiment, the bulk density is between 0.70 and 0.90 grams per cubic centimeter. In another embodiment, the bulk density is between 0.75 and 0.85 grams per cubic centimeter. For example, the bulk density is 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84 or 0.85 grams per cubic centimeter.

[0068] In one embodiment, the composition according to the third aspect of this disclosure, is obtained by mixing the lithium hydroxide-based powder according to the first aspect of this disclosure and the transition-metal hydroxide or oxyhydroxide comprising M.Battery

[0069] In another aspect, the present disclosure further provides a battery comprising the positive electrode active material powder as described herein. The present disclosure also provides the use of the battery according to this disclosure, in an electrically powered device or system selected from the group consisting of: a portable computer, a tablet, a mobile phone, a telecommunication device, a power tool, mobile machinery, a robotic device, an energy storage system, an uninterruptible power supply system, an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an extended-range electric vehicle, a fuel cell electric vehicle, a two-wheeler transportation system, a rail vehicle, a marine vessel, an aircraft, an aerospace system, a defense system, and a medical device.

[0070] As appreciated by a person skilled in the art, all embodiments directed to the cathode active material according to the first aspect may apply mutatis mutandis to the second, third and fourth aspect of the present disclosure. Additionally, this disclosure is intended to cover the combination of all embodiments listed above.EXPERIMENTAL ANALYSIS USED IN THE EXAMPLES

[0071] The following methods are used to analyze the Examples and Comparative Examples.A) Inductively Coupled Plasma - Optical Emission Spectrometry (ICP-OES) analysis

[0072] The amount of Li, Ni, Co and Mn in the cathode active material powder is measured with the ICP-OES method by using an Agilent ICP 720-ES (Agilent Technologies). 2 grams of powder sample are dissolved into 10 mL of high purity hydrochloric acid (at least 37 wt% of HCI with respect to the total weight of solution) in an Erlenmeyer flask. The flask is covered by a glass and heated on a hot plate at 380 °C until complete dissolution of the powder. After cooling to room temperature, the solution of the Erlenmeyer flask is poured into a 250 mL volumetric flask. Afterwards, the volumetric flask is filled with deionized water up to the 250 mL mark, followed by complete homogenization.B) Carbon analysis

[0073] The content of carbon of the positive electrode active material powder is measured by Horiba Emia-Expert carbon / sulfur analyzer. 1 gram of the positive electrode active material powder is placed in a ceramic crucible in a high frequency induction furnace. 1.5 grams of tungsten and 0.2 grams of tin are added into the crucible as accelerators. The powder is heated at a programmable temperature wherein gases produced during the combustion are then analyzed by Infrared detectors. The analysis of CO2 and CO determines the carbon concentration.C) Titration analysis

[0074] To measure the total base content present in a sample by pH titration, two steps are performed:(a) the reparation of solution, and(b) pH titration. The detailed explanation of each step is as follows:

[0075] Step (a): The preparation of solution: 4 grams of cathode active material powder is mixed within 100 mL of deionized water and stirred for 10 min in a sealed glass flask. After stirring, the powder suspension is filtered to obtain the solution.

[0076] Step (b) : pH titration : 90 mL of the solution prepared in step (a) is used for pH titration by using 0.1M HCI. The flow rate is 0.5 mL / min and the pH value is recorded every 3 seconds. The pH titration profile (pH value as a function of added HCI) shows two clear equivalence (or inflection) points. The first equivalence point (corresponding to a HCI quantify of EPl) at around pH 7.4 results from the reaction of OH-and COs2-with H+. The second equivalence point (corresponding to a HCI quantify of EP2) at around pH 4.7 results from the reaction ofHCOs’ with H+. It is assumed that the dissolved base in deionized water is either LiOH (with a quantify 2x(EPl-EP2)) or U2CO3 (with a quantify 2x(EP2-EPl)). The obtained values for LiOH and U2CO3 are the result of the reaction of the surface with deionized water.

[0077] The following definitions are used for data analysis: LiOH (wt%) is the weight percentage of the amount of LiOH over the amount of sample. Li2COs (wt%) is the weight percentage of the amount of Li2COs over the amount of sample. Total base content (pmol / g) is the amount of LiOH and Li2COs over a gram of sample, i.e. the amount of micro mol of HCI needed to neutralize the base of 1 gram of cathode active material.D) Particle size distribution (PSD) analysis

[0078] The PSD is measured using a Malvern Mastersizer 3000 with Hydro MV wet dispersion accessory after dispersing examples as described herein below of positive electrode active material powders in an aqueous medium. To improve the dispersion of the positive electrode active material powder examples, sufficient ultrasonic irradiation and stirring are applied, and an appropriate surfactant is introduced. D10, D50, and D90 are defined as the particle size at 10%, 50%, and 90% of the cumulative volume% distributions, respectively. Span is defined as (D90-D10) / D50.E) Scanning electron microscopy energy-dispersive X-ray spectroscopy (SEM-EDS) analysis

[0079] The SEM field of view is of at least 45 pm x at least 60 pm (i.e. of at least 2700 pm2), optionally of at least 100 pm x 100 pm (i.e. of at least 10,000 pm2). Standalone particles in the image should be well distributed, therefore avoiding overlap between particles. This can be achieved by pouring a small amount of the CAM powder sample to an adhesive attached on a SEM sample holder and blowing air to remove an excess of powder.

[0080] The content of Ni, Mn and Co based on a total amount of the transition metals of the cathode active material are analyzed by a scanning electron microscopy energy-dispersive X-ray spectroscopy (SEM-EDS) technique. The SEM-EDS is performed on a JEOL JSM 7100F SEM equipment with a 50mm2X-MaxNEDS sensor from Oxford instruments. The particles in the image should be well distributed, therefore avoiding overlapping between particles. This can be achieved by pouring a small amount of powder sample to the adhesive attached on the SEM sample holder and blowing air to remove the excess powder.F) Tap density measurement

[0081] The tap density (TD) is measured with the standard method (ASTM-B527) by using Dual Autotap of Quantachrome. A graduated measuring cylinder (100 mL) containing a specific amount (W) of the positive electrode active material powder is mechanically tappedfor 5,000 times with the frequency of 235 to 265 tap / min, wherein the specific amount (W) is between 50 grams and 100 grams. The volume (V) of the powder after tapping is measured and then the TD is calculated from the equation TD=W[g] / V[mL].G) Bulk density measurement

[0082] The bulk density (BD) of the powder is measured by Scott Volumeter method. A powder is added into the top funnel to flow through the apparatus into the receiving cup until it overflows. To remove the excess powder from the receiving cup, move the edge of the spatula blade smoothly along the top surface of the cup and back again. It is important to keep the level of the spatula at all times to prevent packing or pulling out of the powder. After the leveling operation, lightly tap the side of the receiving cup to settle the powder to avoid spilling while transferring the cup to balance for weighing. The bulk density of the powder is obtained according to the equation below.mp (g / cm ) = —p (g / cm3) = bulk density of the powderm (g) = powder weightV (cm3)=the volume of the receiving cupH) Coin cell analysisHl) Coin cell preparation

[0083] For the preparation of a positive electrode, a slurry that contains a cathode active material powder, conductor (Super P, Timcal), binder (KF#9305, Kureha) - with a formulation of 96.5:1.5:2.0 by weight - in a solvent (NMP, Mitsubishi) is prepared by a high-speed homogenizer. The homogenized slurry is spread on one side of an aluminum foil using a doctor blade coater with a 170 pm gap. The slurry coated foil is dried in an oven at 120 °C and then pressed using a calendaring tool. Then it is dried again in a vacuum oven to completely remove the remaining solvent in the electrode film. A coin cell is assembled in an argon-filled glovebox. A separator (Celgard 2320) is located between a positive electrode and a piece of lithium foil used as a negative electrode. IM LiPFe in EC / DMC (1:2) is used as electrolyte and is dropped between separator and electrodes. Then, the coin cell is completely sealed to prevent leakage of electrolyte.H2) Testing method

[0084] The testing method is a conventional "constant cut-off voltage" test. The conventional coin cell test in the present disclosure follows the schedule shown in Table I. Each cell is cycled at 25 °C using a Toscat-3100 computer-controlled galvanostatic cycling station (from Toyo).

[0085] The schedule uses a 1C current definition of 220 mA / g in the 4.3 V to 3.0 V / Li metal window range. The capacity fading rate (QF) is obtained according to an equation below wherein DQ1 is the discharge capacity at the first cycle.QF (% / 100 cycles) = 100 x (1 - x x 100Table I: Cycling schedule for coin cell testing methodCharge DischargeEnd V / Li End V / Li Cycle Rest RestC Rate current metal C Rate current metal (min) (min)(C) (V) (C) (V) 1 0.1 - 30 4.3 0.1 - 30 3.0 2 0.25 0.05 10 4.3 0.20 - 10 3.0 3 0.25 0.05 10 4.3 0.50 - 10 3.0 4 0.25 0.05 10 4.3 1.00 - 10 3.0 5 0.25 0.05 10 4.3 2.00 - 10 3.0 6 0.25 0.05 10 4.3 3.00 - 10 3.0 7 0.25 0.1 10 4.3 0.10 - 10 3.0 8 0.25 0.1 10 4.3 1.00 - 10 3.0 9-33 0.50 0.1 10 4.3 1.00 - 10 3.0 34 0.25 0.1 10 4.3 0.10 - 10 3.0 35 0.25 0.1 10 4.3 1.00 - 10 3.0EXAMPLES

[0086] The present disclosure is further illustrated by the following Examples.Example 1

[0087] A lithium hydroxide-based powder, further called EXI is obtained through the protocol described below:1) Drying LiOH-l-hO (LiOH = 57 wt%, D50> 250 pm, span> 1.3) in a paddle dryer with a flow of carbon dioxide free dry air with relative humidity < 1%. The drying temperature is 180 to 200 °C and drying time is around 1 hour. The injection air flow is around 15 m3 / h.2) Milling the dried material in a fluidized-bed jet mill with a grinding pressure of 3 to 6 bar, screening speed control between 600 and below 1000 rpm, using CCh-free dry air (with <20 ppm of CO2). The resulting lithium hydroxide-based powder EXI has a median particle size distribution D50 around 27.5 pm, a span around 2.06, and a bulk density around 0.16 grams per cubic centimeter.

[0088] A cathode active material, further called EX1-C, is obtained through the following steps:1) Co-precipitating a transition metal hydroxide precursor with a metal composition of Ni0.80Mn0.10Co0.10 in a large-scale continuous stirred tank reactor (CSTR) by mixing nickel manganese cobalt sulfates, sodium hydroxide, and ammonia.2) Mixing the mixed metal precursor prepared from Step 1) with EXI as Li source in an industrial blender to obtain a first mixture having a Li / (Ni, Mn, and Co) ratio of about 1.0, and a bulk density around 0.70 grams per cubic centimeter.3) Heating the first mixture at 830 °C for 8 hours under an oxygen atmosphere followed by sieving and grinding to obtain EX1-C.Example 2

[0089] A lithium hydroxide-based powder, further called EXI is obtained through the protocol described below:1) Drying LiOH.H?© (LiOH = 57 wt%, D50> 250 pm, span> 1.3) in a vacuum dryer under 0.8 atm of vacuum atmosphere. The drying temperature is 180 to 200°C and drying time is around 14 hours.2) Milling the dried material in a spiral jet mill with a grinding pressure of 6.5 bar and milling pressure of 5.5 bar, using nitrogen. The resulting lithium hydroxide-based powder EX2 has a median particle size distribution D50 around 32.4 pm, a span around 1.62, and a bulk density around 0.21 grams per cubic centimeter.

[0090] A cathode active material, further called EX2-C, is obtained through the following steps:1) Co-precipitating a transition metal hydroxide precursor with a metal composition of Ni0.80Mn0.10Co0.10 in a large-scale continuous stirred tank reactor (CSTR) by mixing nickel manganese cobalt sulfates, sodium hydroxide, and ammonia.2) Mixing the mixed metal precursor prepared from Step 1) with EX2 as Li source in an industrial blender to obtain a first mixture having a Li / (Ni, Mn, and Co) ratio of about 1.0, and a bulk density around 0.81 grams per cubic centimeter.3) Heating the first mixture at 830 °C for 8 hours under an oxygen atmosphere followed by sieving and grinding to obtain EX2-C.Example 3

[0091] A lithium hydroxide-based powder, further called EX3 is obtained through the protocol described below:1) Drying LiOH-H2O (LiOH = 57 wt%, D50> 250 pm, span> 1.3) in a paddle dryer with a flow of CO2-free dry air with relative humidity < 1%. The drying temperature is 180 to 200 °C and drying time is around 1 hour. The injection air flow is around 15 m3 / h.2) Milling the dried material in a jet mill with a grinding pressure of 3 to 6 bar, screening speed control above 1000 rpm using CO2-free dry air. The resulting lithium hydroxide-based powder EX3 has a median particle size distribution D50 around 20.2 pm, a span around 2.01, and a bulk density around 0.13 grams per cubic centimeter.

[0092] A cathode active material, further called EX3-C, is obtained through the following steps:1) Co-precipitating a transition metal hydroxide precursor with a metal composition of Ni0.80Mn0.10Co0.10 in a large-scale continuous stirred tank reactor (CSTR) by mixing nickel manganese cobalt sulfates, sodium hydroxide, and ammonia.2) Mixing the mixed metal precursor prepared from Step 1) with CEX1 as Li source in an industrial blender to obtain a first mixture having a Li / (Ni, Mn, and Co) ratio of about 1.0, and a bulk density around 0.65 grams per cubic centimeter.3) Heating the first mixture at 830 °C for 8 hours under an oxygen atmosphere followed by sieving and grinding to obtain EX3-C.Comparative Example 1

[0093] A lithium hydroxide-based powder, further called CEX1 is obtained through the protocol described below:1) Drying LiOH.H?© (LiOH = 57 wt%, D50> 250 pm, span> 1.3) in a paddle dryer with a flow of carbon dioxide free dry air with relative humidity < 1%. The drying temperature is 180 to 200 °C and drying time is around 1 hour. The injection air flow is around 15 m3 / h. The resulting lithium hydroxide-based powder CEX1 has a median particle size distribution D50 around 488.0 pm, a span of about 1.62, and a bulk density of about 0.57 grams per cubic centimeter.

[0094] A cathode active material, further called CEX1-C, is obtained through the following steps:1) Co-precipitating a transition metal hydroxide precursor with a metal composition of Ni0.80Mn0.10Co0.10 in a large-scale continuous stirred tank reactor (CSTR) by mixing nickel manganese cobalt sulfates, sodium hydroxide, and ammonia.2) Mixing the mixed metal precursor prepared from Step 1) with CEX2 as Li source in an industrial blender to obtain a first mixture having a Li / (Ni, Mn, and Co) ratio of 1.00, and a bulk density around 1.10 grams per cubic centimeter.3) Heating the first mixture at 830 °C for 8 hours under an oxygen atmosphere followed by sieving and grinding to obtain CEX1-C.RESULTSTable II: Median particle size distributions, span, bulk density, lithium carbonate content and lithium hydroxide content of the Examples and Comparative Examples.D10 D50 D90 Bulk density Li2COs LiOH Example ID Span(pm) (pm) (pm) (g / cc) (wt%) (wt%) EXI 12.7 27.5 69.2 2.06 0.16 0.37 98.5 EX2 10.9 32.4 87.2 2.36 0.21 0.42 99.5 EX3 10.0 20.2 50.6 2.01 0.13 0.57 99.8 CEX1 178.0 488.0 966.0 1.62 0.57 - -

[0095] As can be observed, Examples 1-2 present high bulk density. Lithium hydroxide-based powders with a higher bulk density may increase the tray loading and improve the throughput of the process for manufacturing a cathode active material. In particular, EX2 presents higher bulk density compared to Example 1 and 3.

[0096] Comparative example 1 presents an excessively high bulk density. The blend mixture between CEX1 and a mixed-metal hydroxide precursor presents poor homogeneity, see Figure 2.

[0097] Example 1 to 3 present a low content of Li2COs. Therefore, a cathode active material obtainable using a lithium source according to this disclosure, might contain less soluble bases, suffer less bulging, and might have an improved electrochemical performance.Table III: Chemical composition, tap density, DQ1 and Qirr of the Examples and Comparative Examples.Ni Mn Co Tap density DQ1 Qirr Example ID(mol%) (mol%) (mol%) (g / cc) (mAh / g) (%) EX1-C 80.5 9.6 9.8 - - - EX2-C 80.5 9.7 9.9 2.79 198.9 12.2 EX3-C 80.4 9.7 9.9 2.72 - - CEX1-C 80.4 9.7 9.9 2.82 194.9 13.0

[0098] As can be observed in Table III, Example 2-C presents the highest tap density between EX2, EX3 and CEX1, and also higher discharge capacity (DQ1) than Comparative Example 1-C.

[0099] Additionally, Example 2-C exhibits a lower irreversible capacity (Qirr) compared to Comparative Example 1-C, indicating improved performance. The poor electrochemicalperformance of Comparative Example 1-C may be associated with the non-homogeneity of the blended mixture (see Figure 2 versus Figure 1).

[0100] Thus, a lithium hydroxide-based powder as disclosed herein may enhance both the manufacturing throughput and the electrochemical performance of the resulting cathode active material.

Claims

CLAIMS1. A lithium hydroxide-based powder for preparing a lithium-composite oxide, wherein the lithium hydroxide-based powder comprises particles having a span lower than 5.0, a median particle size distribution D50 between 19.0 and 70.0 pm, a bulk density between 0.12 and 0.70 grams per cubic centimeter, and comprises lithium carbonate in a content lower than 2.0 wt% relative to the total weight of the lithium hydroxide-based powder.

2. The lithium hydroxide-based powder according to claim 1, wherein the lithium carbonate content is lower than 1.5 wt% relative to the total weight of the lithium hydroxide-based powder.

3. The lithium hydroxide-based powder according to claim 1 or 2, having a bulk density between 0.17 and 0.50 grams per cubic centimeter.

4. The lithium hydroxide-based powder according to any of the claims 1 to 3, wherein the median particle size distribution is D50 between 23.0 and 50.0 pm.

5. The lithium hydroxide-based powder according to any of the claims 1 to 4, comprising particles having a median particle size distribution D10 higher than 10.0 pm, and a median particle size distribution D90 between 70.0 and 100.0 pm.

6. The lithium hydroxide-based powder according to any of the claims 1 to 5, comprising lithium hydroxide in a content of at least 95.0 wt% relative to the total weight of the lithium hydroxide-based powder.

7. A method for manufacture the lithium hydroxide-based powder according to any of the claims 1 to 6, comprising the following steps:-drying a lithium containing compound in a vacuum oven or in an oven under a carbon dioxide-free atmosphere to form a dried material,- jet milling the dried material under a carbon-dioxide free atmosphere to obtain the lithium hydroxide-based powder.

8. A method according to claim 7, wherein the drying step is performed under vacuum, at a temperature higher than 150 °C for a period of time of at least 10 hours.

9. A method according to claim 8, wherein the spiral milling step is performed with a grinding pressure of at least 6 bars, and a milling pressure of at least 5 bars.

10. A method according to claim 8 or 9, wherein the spiral jet milling step is performed under nitrogen atmosphere.

11. A composition for a cathode active material, the composition comprising a lithium hydroxide-based powder according to any of the claims 1 to 6, and a transition-metal hydroxide or oxyhydroxide, comprising M, wherein M comprises:Ni in an atomic content x, wherein 0.50 < x < 0.98 relative to M;Mn in an atomic content y, wherein 0.005 < y < 0.50 relative to M;Co in an atomic content z, wherein 0.0 < z < 0.50 relative to M;Al in an atomic content a, wherein 0.0 < a < 0.50 relative to M;wherein x, y, z and a are measured by ICP-OES, x+y+z+a is 1, and wherein the composition has a Li / M atomic ratio between 0.8 to 1.5.

12. A composition according to claim 11, wherein the Li / M atomic ratio is between 0.95 and 1.2, and wherein 0.60 < x < 0.95 relative to M, 0.01 < y < 0.40 relative to M, wherein 0.01 < z < 0.40 relative to M, and 0.0 < a < 0.30 relative to M.

13. A composition according to claim 11 or 12, wherein the transition-metal hydroxide or oxyhydroxide is according to the formula (I) NixiMnyiCoziAlaiO?, wherein 0.70 < xl < 0.90; 0.02 < yl < 0.30; 0.02 < zl < 0.30; 0.0 < al < 0.15.

14. A battery comprising a cathode active material according to any of the claims 1 to 6.

15. The use of a battery according to claim 14, in an electrically powered device or system selected from the group consisting of: a portable computer, a tablet, a mobile phone, a telecommunication device, a power tool, mobile machinery, a robotic device, an energy storage system, an uninterruptible power supply system, an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an extended-range electric vehicle, a fuel cell electric vehicle, a two-wheeler transportation system, a rail vehicle, a marine vessel, an aircraft, an aerospace system, a defense system, and a medical device.

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