Precursors for lithium transition metal oxide cathode materials for rechargeable batteries

Abstract

A particulate precursor compound for manufacturing a lithium transition metal oxide powder for use as an active positive electrode material in lithium-ion batteries, the precursor having the general formula Ni.sub.xMn.sub.yCo.sub.zA.sub.aO.sub.v(OH).sub.w, wherein 0.15<v<0.30, v+w=2, 0.30x0.75, 0.10y0.40, 0.10z0.40, A being a dopant with a0.05, and x+y+z+a=1, the precursor consisting of a crystal structure having an XRD pattern with twin peaks at 2=380.5, the twin peaks having a left peak having a peak intensity I.sub.L and a right peak having a peak intensity I.sub.R, and a peak intensity ratio R=I.sub.R/I.sub.L with R>0.7, and the XRD pattern being free of peaks belonging to either one or both of a spinel and an oxyhydroxide compound.

Claims

1. A particulate precursor compound for manufacturing a lithium transition metal oxide powder for use as an active positive electrode material in lithium-ion batteries, the precursor compound having a general formula Ni.sub.xMn.sub.yCo.sub.zA.sub.aO.sub.v(OH).sub.w, wherein 0.15<v<0.30, v+w=2, 0.30x0.75, 0.10y0.40, 0.10<z0.40, A being a dopant with a0.05, and x+y+z+a=1, the precursor compound comprising a crystal structure having an XRD pattern with twin peaks at 2=380.5, wherein the twin peaks comprise a left peak having a peak intensity I.sub.L, a right peak having a peak intensity I.sub.R, and a peak intensity ratio R=I.sub.R/I.sub.L with R>0.7, wherein the XRD pattern is free of peaks belonging to one or both of a spinel and an oxyhydroxide compound.

2. The particulate precursor compound of claim 1, wherein the precursor compound has an XRD pattern with twin peaks at 2=380.5, the twin peaks having a left peak and a right peak, wherein the left peak belongs to an XRD pattern of a (II)-Me(OH).sub.2 structure and the right peak belongs to an XRD pattern of an oxidized (II)-Me(OH).sub.2 structure, and wherein the weight % of the (II)-Me(OH).sub.2 structure in the precursor compound is more than 0 wt % and less than 48 wt %.

3. The particulate precursor compound of claim 1, wherein the precursor compound has an XRD pattern with additional twin peaks at 2=330.5 and 520.5.

4. The particulate precursor compound of claim 1, wherein R<+.

5. The particulate precursor compound of claim 2, wherein the weight % of the oxidized (II)-Me(OH).sub.2 structure in the precursor is <95 wt %.

6. The particulate precursor compound of claim 1, having the general formula Ni.sub.xMn.sub.yCo.sub.zO.sub.v(OH).sub.w, wherein 0.30x0.60, 0.20y0.35, 0.20z0.35, and x+y+z=1.

7. A method for preparing the particulate precursor compound of claim 1, comprising: providing a metal salt solution comprising Ni, Mn, Co and A, adding an alkali hydroxide compound to the metal salt solution, thereby precipitating a wet particulate precursor compound comprising a pure hydroxide crystal structure and a quantity of H.sub.2O, drying the wet particulate precursor compound during a heat treatment at a temperature between 130 C. and 160 C. in vacuum, thereby lowering the H.sub.2O content below 1 wt %, continuing to heat treat the dried precursor compound, thereby removing between 0.15 and 0.30 mole H.sub.2 per mole pure hydroxide precursor, and cooling the dried particulate precursor compound to room temperature under vacuum.

8. The method of claim 7, wherein the step of cooling the dried particulate precursor compound to room temperature is performed under dry air.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1: XRD patterns of selected Explanatory Examples;

(2) FIG. 2: XRD patterns of NMC532 precursors in the order of the peak intensity ratio (R);

(3) FIG. 3: Coin cell 1.sup.st cycle 0.1 C discharge capacity for NMC532 products against the peak intensity ratio (R) of the corresponding NMC532 precursors;

(4) FIG. 4: Coin cell rate performance (DQ at 3 C rate over DQ at 0.1 C rate) for NMC532 products against the peak intensity ratio (R) of the corresponding NMC532 precursors;

(5) FIG. 5: XRD patterns of NMC111 precursors (Ex20, Ex21) and NMC622 precursors (Ex22, Ex23);

(6) FIG. 6: 25 C. cycle life (top lines and right axis) and DCR growth (bottom lines and left axis) during cycling for EX2-I, EX2-II, EX10-I and EX10-II;

(7) FIG. 7: 45 C. cycle life (top lines and right axis) and DCR growth (bottom line and left axis) during cycling for EX2-I, EX2-II, EX10-I and EX10-II;

(8) FIG. 8: XRD patterns plotted in Ln(CPS) scale of selected Examples.

DETAILED DESCRIPTION

(9) The precursor in this invention is a particulate (oxy-)hydroxide precursor compound for manufacturing a lithium transition metal oxide powder to be used as an active positive electrode material in lithium-ion batteries, having the general formula
Ni.sub.xCo.sub.yMn.sub.zA.sub.aO.sub.v(OH).sub.wF1
wherein 0.15<v<0.30, v+w=2, 0.30x0.75, 0.10y0.40, and 0.10z0.40, A being a dopant with a0.05, x+y+z+a=1. The precursor comprising Ni, Mn and Co in a molar ratio x:y:z is typically prepared in a mixed form by precipitation reactions, with the following steps: (1) precipitation of mixed hydroxides in a reactor with a flow of NaOH and a flow of mixed metal salt under controlled pH, (2) removal of the precursor suspension and filtration, (3) drying of the filtered wet cake. In step (1) the mixed salt may be a mixed sulfate salt, and the pH typically between 11 and 12. Efficient precursor drying is typically conducted above 100 C. for a certain time to remove most of the moistures. The typical moisture content after drying is below 1 wt %, and can be measured by the well-known Karl Fischer titrimetric method at 250 C. (ASTM D6869). Before drying, the precursor has a pure or ideal hydroxide crystal structure (with space group P-3m1). During drying at a certain temperature, the physically attached moisture evaporates while the precursor also tends to release H.sub.2O from the hydroxide crystal structure, hence forming a precursor with a hydrogen deficiency versus the ideal hydroxide structure (with w<2 in F1), which results in an intimate mixture (at atomic level) of two phases: the ideal hydroxide phase, and an oxidized hydroxide phase, that can clearly be distinguished in an XRD pattern, as will be shown in the Examples.

(10) In the lithiation process that the precursor will undergo, hydrogen in the hydroxide precursor will be removed in the solid state reaction to get the target Li-Me-O.sub.2 transition metal composite oxide. According to the schematic equilibrium reaction here below in F2, one mole pure hydroxide precursor requires 0.25 mole O.sub.2 in the reaction and releases half a mole of CO.sub.2 and one mole of H.sub.2O. The former needs to be obtained from the air flow while the latter two need to be removed. The required amount of gas transportation is actually independent from the lithium source being used, for example Li.sub.2CO.sub.3 or LiOH (see F2-F3). From a kinetic point of view, therefore, less gas transportation practically means less air flow, less firing time, a lower firing temperature and probably more material being lithiated in the firing process. This effect may not be identified for a small scale lithiation, but it will be crucial for cathode mass production, where manufacturers are looking for ways to improve throughput and production efficiency. From a material performance point of view, less gas transportation means easier reactions, and enough time to form a perfect layered structure, enabling a better cathode performance. It can be concluded that removing hydrogen from the precipitated hydroxide precursor before the reaction with the lithium precursor is particularly efficient for the formation of the lithiated metal oxide.

(11) $\begin{array}{cc}{\mathrm{Ni}}_x{\mathrm{Co}}_y{{\mathrm{Mn}}_z\left(\mathrm{OH}\right)}_2+\frac{1}{2}{\mathrm{Li}}_2{\mathrm{CO}}_3+\frac{1}{4}{O}_2.Math.\mathrm{Li}{\mathrm{Ni}}_x{\mathrm{Co}}_y{\mathrm{Mn}}_z{O}_2+\frac{1}{2}{\mathrm{CO}}_2+H_{2}O& \mathrm{F2}\\ {\mathrm{Ni}}_x{\mathrm{Co}}_y{{\mathrm{Mn}}_z\left(\mathrm{OH}\right)}_2+\mathrm{LiOH}+\frac{1}{4}{O}_2.Math.{\mathrm{LiNi}}_x{\mathrm{Co}}_y{\mathrm{Mn}}_z{O}_2+\frac{3}{2}{H}_{2}O& \mathrm{F3}\end{array}$

(12) In the methods according to the invention, the drying of the hydroxide precursors can be done carefully at well-defined conditions such as temperature, gas atmosphere and timewhich are conditions that can interact, for example a higher drying temperature requires less time to obtain the desired product, especially for mass production scale. On the one hand, NMC precursor drying at low temperature under vacuum or protective gas may not be efficient to remove hydrogen, but on the other hand NMC precursor drying at elevated temperature under oxidizing atmosphere will certainly cause phase separation into multiple Ni-, Mn- and Co-oxides or -oxyhydroxides. Phase separation goes against the incentive to obtain a well-mixed precursor at atomic level by the co-precipitation process. Phase separation in the precursor induces the necessity of a lithiation at a higher temperature and for a longer time afterwards, to get a perfect Li-M-O.sub.2 layered structure. Phase separation will most probably also create local strain at the interface of the different phases and hence the precipitated crystal structure may collapse. This again causes the need for a longer time and higher temperature lithiation process.

(13) All in all, controlling the precursor drying temperature, atmosphere and drying time may be crucial to get precursors with the smallest amount of hydrogen possible, and without creating phase separation.

(14) Description of Test Conditions in the Examples: X-Ray Diffraction Test

(15) In this invention XRD is applied to characterize the dried precursor compound. The NMC precursor compounds with unique XRD features according to the invention have been found to guarantee the resulting NMC cathode materials having a low irreversible capacity Qirr and a high discharge capacity DQ. X-ray diffraction is carried out using a Rigaku D/MAX 2200 PC diffractometer equipped with a Cu (K-Alpha) target X-ray tube and a diffracted beam monochromator at room temperature in the 15 to 85 2-Theta () degree range. The lattice parameters of the different phases are calculated from the X-ray diffraction patterns using full pattern matching and Rietveld refinement methods. It is known that the structural model of NMC hydroxide precursor (w=2 in F1) is the II-Ni(OH).sub.2 structure (space group P-3m1, no. 164) the structural model of NMC oxyhydroxide precursor (w=1 in F1) is the III-NiOOH structure (space group R-3m, no. 166) the structure of spinel Me.sub.3O.sub.4 belongs to space group Fd-3mZ, no. 227
Description of Cathode Material Preparation

(16) In this invention, in order to evaluate the electrochemical behavior in a coin cell, cathode materials are prepared from the precursor compounds according to the invention, by using conventional high temperature sintering at representative MP (mass production) scale. Li.sub.2CO.sub.3 (Chemetall) or LiOH (SQM) is dry mixed with the precursor compound in a certain Li:M molar ratio using a blender for 30 mins. The mixture is reacted at a high temperature (>900 C.) for 10 hr under air, using mass production scale equipment. The Li:M molar blending ratio and sintering temperature are standard, but they differ for precursors with different Ni contents, which will be specified in each individual example. After firing, the sintered cake is crushed, classified and sieved so as to obtain a non-agglomerated powder with a mean particle size D50 similar to that of the precursor.

(17) Description of Test Conditions: Peak Intensity Ratio

(18) The current invention observes that the discharge capacity of the final NMC product is optimized when the NMC precursors have an XRD pattern with twin peaks at 2 around 38, and preferably also at around 33 and 52, with an intensity ratio between the twin peaks at 38 within a specific range, and the XRD pattern being free of peaks belonging to either one or both of a spinel and an oxyhydroxide compound. The reason of the twin peak formation is discussed in the Explanatory Examples below. For precursors being dried under different conditions, the intensity ratio of the twin peaks at those 2 positions changes. Therefore, in the current invention, the peak intensity ratio is calculated and applied as a parameter to characterize the dried NMC precursors. For example, with peak splitting, the XRD pattern from 35.5 to 43 is cut out for peak fitting and peak intensity ratio calculation. The numerical peak fitting is done by using the method of least squares using two sets of Gaussian and Lorentzian functions with the same G/L ratio and with the same full width at half maximum (FWHM). The intensity (the area under the fitted peak) is used to calculate the peak intensity ratio:

(19) $R=\frac{\mathrm{Area}\mathrm{of}\mathrm{right}\mathrm{peak}}{\mathrm{Area}\mathrm{of}\mathrm{left}\mathrm{peak}}.$
Description of Test Conditions: Preparation of Coin Cells

(20) Electrodes are prepared as follows: about 27.27 wt. % of active cathode material, 1.52 wt. % polyvinylidene fluoride polymer (KF polymer L #9305, Kureha America Inc.), 1.52 wt. % conductive carbon black (Super P, Erachem Comilog Inc.) and 69.70 wt. % N-methyl-2-pyrrolidone (NMP) (from Sigma-Aldrich) are intimately mixed by means of high speed homogenizers. The slurry is then spread in a thin layer (typically 100 micrometer thick) on an aluminum foil by a tape-casting method. After evaporating the NMP solvent at 120 C. for 3 hr, the cast film is processed through two constantly spinning rolls with a 40 micrometer gap. Electrodes are punched from the film using a circular die cutter measuring 14 mm in diameter. The electrodes are then dried overnight at 90 C. The electrodes are subsequently weighed to determine the active material loading. Typically, the electrodes contain 90 wt. % active materials with an active materials loading weight of about 17 mg (11 mg/cm.sup.2). The electrodes are then put in an argon-filled glove box and assembled within a 2325-type coin cell body. The anode is a lithium foil having a thickness of 500 micrometers (origin: Hosen); the separator is a Tonen 20MMS microporous polyethylene film. The coin cell is filled with a 1M solution of LiPF.sub.6 dissolved in a mixture of ethylene carbonate and dimethyl carbonate in a 1:2 volume ratio (origin: Techno Semichem Co.). Each cell is cycled at 25 C. using Toscat-3100 computer-controlled galvanostatic cycling stations (from Toyo) at different rates in the 4.33.0V/Li metal window range. The initial charge capacity CQ1 and discharge capacity DQ1 are measured in constant current mode (CC) at 0.1 C rate. The irreversible capacity Qirr is expressed in % as

(21) $Q_{\mathrm{Irr}.}=\frac{\left(\mathrm{CQ}1-\mathrm{DQ}1\right)}{\mathrm{CQ}1}100\left(\%\right)$
Description of Test Conditions: Preparation of Full Cells

(22) A slurry is prepared by mixing 1000 g of Li-Me-O.sub.2 with NMP, 32.61 g of super P (conductive carbon black of Timcal), 10.87 g graphite and 434.78 g of 10 wt. % PVDF based binder in a NMP (N-methyl-2-pyrrolidone) solution. The mixture is mixed for 2.5 hr in a planetary mixer. During mixing additional NMP is added. The mixture is transferred to a Disper mixer and mixed for 1.5 hr under further NMP addition. A typical total amount of NMP used is 585.28 g. The final solid content in the slurry is about 65 wt %. The slurry is transferred to a coating line, where it is coated on both sides of a current collector resulting in an electrode having a smooth surface and a loading of 13.4 mg/cm.sup.2. The electrodes are compacted by a roll press to achieve an electrode density of about 3.25 g/cm.sup.3. In addition, the slurry viscosity is measured by Brookfield viscometer. The typical slurry viscosity is about 2000 to 4000 cps. Low slurry viscosity is always preferred to guarantee slurry coating quality.

(23) To prepare pouch cell type full cells, the positive electrode (cathode) is assembled with a negative electrode (anode) which is typically a graphite type carbon, and a porous electrically insulating membrane (separator). The full cell is prepared by the following major steps: (1) electrode slitting, (2) tab attaching, (3) electrode drying, (4) jellyroll winding, and (5) packaging:

(24) (1) electrode slitting: after coating the electrode active material on the electrode, it can be slit by a slitting machine. The width and length of the electrode are determined according to the battery application;

(25) (2) tab attaching: there are two kinds of tabs. Aluminum tabs are attached to the positive electrode (cathode), and copper tabs are attached to the negative electrode (anode);

(26) (3) electrode drying: the prepared cathode and anode are dried at 85 C. to 120 C. for 8 hr in a vacuum oven;

(27) (4) jellyroll winding: after drying the electrode a jellyroll is made using a winding machine. A jellyroll consists of at least a negative electrode (anode) a porous electrically insulating membrane (separator) and a positive electrode (cathode);

(28) (5) packaging: the prepared jellyroll is incorporated in a 360 mAh cell with an aluminum laminate film package, resulting in a pouch cell. The jellyroll is subsequently impregnated with the electrolyte. The quantity of electrolyte is calculated in accordance with the porosity and dimensions of the positive and negative electrodes and the porous separator. Finally, the packaged full cell is sealed by a sealing machine. The packaged full cell includes a gas room aside, which is to collect gas during precharging.
(6) precharge and degassing: the prepared cells are pre-charged at 0.25 C rate with constant current (CC) mode to 15% of the expected cell capacity. 1 C rate corresponds to the current which discharges a charged cell within 1 hr. (it follows that e.g. 3 C is 3 times faster discharged, 0.25 C is 4 times slower). The cells are aged for 48 hours and then the cell gas room part is removed;
(7) formation: the cell is then charged at 0.25 C rate with constant current-constant voltage (CCCV) mode to 4.2V (cut-off current 1/120C). After resting for 10 mins, it is discharged at 0.5 C rate with CC mode to 2.7V. After resting for 10 mins, it is charged at 0.5 C rate with CCCV mode to 4.2V (cut-off current 1/20C). The cell discharge capacity during this formation cycle is recorded and used for full-cell specific capacity calculations;
(8) aging and final charge: the cell after formation is aged at 25 C. for 7 days for an Open Circuit Voltage (OCV) check. The cell is then discharged first at 0.5 C rate with CC mode for recovery capacity check. After resting for 10 mins, it is charged at 1 C rate with CCCV mode to 4.2V (cut-off current 1/20C). After resting for 10 mins, it is discharged at 0.2 C rate with CC mode to 2.7V. After resting for 10 mins, it is finally charged at 1 C rate with CCCV mode to 50% of the cell capacity. The cell is ready for all kinds of full-cell testing.
Description of Test Conditions: Full Cell Temperature Test at 20 C.

(29) The cell after final charge (8) is used for a temperature test. Prior to the test, the cell is discharged and charged between 2.7V and 4.2V for two cycles. Discharging is done at 0.5 C rate with CC mode to 2.7V low cut-off voltage, while charging is done at 1 C rate with CCCV mode to 4.2V upper cut-off voltage (cut-off current 1/20C). The cell at charged state is put into a chamber at 20 C. for 2 hours, followed by a discharge at 0.5 C rate with CC mode to 2.7V. The discharge capacity is recorded as cell retention capacity at 20 C..

(30) Description of Test Conditions: Full Cell Hot Box Test

(31) The cell after final charge (8) is used for a hot box test. The cell is first discharged at 0.5 C rate with CC mode to 2.7V and then fully charged at 1 C rate with CCCV mode to 4.2V. The fully charged cell is put into a hot box chamber, which is heated up at about 0.5 C./min to 180 C. Both the temperature of the chamber and the voltage of the cell are monitored simultaneously. When the cell fails, its voltage drops immediately. The hot box chamber temperature at failure is recorded.

(32) Description of Test Conditions: Full-Cell Cycling Test

(33) The cell after the formation cycle (7) is used for a full-cell cycling test. For each cycle, discharging is conducted at 1 C rate with CC mode to 2.7V, while charging is conducted at 1 C rate with CCCV mode to 4.2V (cut-off current 1/20C). To avoid the influence of self-heating of the cell on the cell temperature during charge and discharge, a 10 mins relaxation time is applied after each charge and discharge step. The retention capacity of each cycle is recorded. For every one hundred cycles, the discharge direct current resistance (DCR) is checked. The cell is charged at 1 C rate with CCCV mode to 4.2V, where a 10 second discharge at 3 C rate is applied. The difference in voltage during pulse discharge and the current of 3 C rate are used to calculate the discharge DCR at 100% state of charge (SOC).

(34) The following examples illustrate the present invention in more detail.

Explanatory Examples

(35) EEX1EEX6

(36) A wet cake of a nickel-manganese-cobalt-hydroxide precursor with molar ratio 60:20:20 (NMC622) is collected from a mass production precipitation. By wet cake we refer to precipitated precursor after washing and filtering but without drying. The wet cake is split into pyroflam trays of about 10 kg per batch and dried in the lab under different defined conditions, which include drying atmosphere, cooling atmosphere, drying temperature and drying time as shown in Table 1A. The purpose is to get precursors with different XRD characteristics.

(37) As shown in Table 1B, EEX1, dried at 150 C. and cooled under N.sub.2, has an ideal II-Me(OH).sub.2 hydroxide crystal structure with space group P-3m1. The length of the a-axis is 3.1596 as determined by XRD refinement. According to the Inorganic Crystal Structure Database (ICSD), the length of the a-axis for Ni(OH).sub.2 (ICSD-13684), Mn(OH).sub.2 (ICSD-13410) and Co(OH).sub.2 (ICSD-58655) with P-3m1 structure is 3.130 , 3.322 and 3.186 , respectively. Calculated by using these values, the weighted average length of a NMC622 precursor is 3.180 , very close to what we have in EEX1. EEX4, dried at 150 C. under vacuum and cooled under dry air (i.e. with an absolute moisture content <1 g/m.sup.3), also shows an XRD pattern belonging to a typical II-Me(OH).sub.2 hydroxide crystal structure. However, all the XRD peaks move to a higher 2 angle compared to those of EEX1, as shown in FIG. 1. The length of the a-axis is 3.0823 , much shorter than that of EEX1. We call it an oxidized II-Me(OH).sub.2, oxidized corresponding to hydrogen deficient or hydrogen depleted. The XRD pattern of EEX2, dried at 135 C. and cooled under vacuum, shows twin or split peaks at 2 of about 33, 38 and 52. The positions of the split peaks fit very well with those characteristic peaks of EEX1 and EEX4, respectively, clearly indicating that EEX2 contains both ideal II-Me(OH).sub.2 and oxidized II-Me(OH).sub.2 structures. On the XRD pattern, the co-existence of both structures is best reflected by these twin peaks at 2 of about 33, 38 and 52, the left peaks corresponding to the ideal (II)-Me(OH).sub.2 structure, while the right ones corresponding to the oxidized (II)-Me(OH).sub.2 structure. The length of the a-axis for both structures is obtained by Rietveld refinement.

(38) EEX3, similar with EEX2, also contains both the ideal II-Me(OH).sub.2 and oxidized II-Me(OH).sub.2 structures, but with different weight percentages. EEX5, dried at 150 C. in air and cooled in air has a majority of oxidized II-Me(OH).sub.2 structure and a minor III-MeOOH defect. The latter has characteristic peaks at 38 and 48. EEX6, dried at a higher T in air than EEX5, shows an even more pronounced III-MeOOH defect and a less pronounced II-Me(OH).sub.2 structure. In FIG. 1, the arrows in EEX5 and EEX6 indicate the formation of (III)-MeOOH defects, which are better illustrated in FIG. 8 where the same XRD patterns are plotted in Ln(CPS) scale. To summarize, some main characteristic structures are captured during precursor drying in the Explanatory Examples EEX16.

(39) EEX712

(40) A similar set of experiments is repeated on a nickel-manganese-cobalt-hydroxide precursor with molar ratio 50:30:20 (NMC532) in EEX7, EEX8, EEX9 and EEX10, as shown in Table 1A&B. In general, NMC532 precursors show exactly the same characteristic structures at different drying temperatures compared to their NMC622 counterparts, being dried under the same conditions. All the details are shown in Table 1A&B.

(41) In addition, two nickel-manganese-cobalt-hydroxide precursors with molar ratio 34:33:33 (NMC333) are dried and cooled under vacuum with EEX11 at 150 C. and EEX12 at 200 C. The XRD patterns show that a spinel Me.sub.3O.sub.4 defect tends to be formed when NMC333 precursor is dried under vacuum between 150 C. and 200 C. In FIGS. 1 and 8, the arrows in EEx12 point the XRD peaks for the spinel Me.sub.3O.sub.4.

(42) For all the explanatory examples, the average length of a-axis is calculated from the weighted mean of the a-axes of both ideal II-Me(OH).sub.2 and oxidized II-Me(OH).sub.2 structures, but not from minor defects such as Me.sub.3O.sub.4, and III-MeOOH.

EXAMPLES

(43) EX1EX17

(44) A series of NMC532 precursors are co-precipitated at a mass production (MP) site for NMC532 cathode production. The NMC532 precursors are continuously removed from the reactor tank, and then washed and filtered, and a wet cake is obtained. Afterwards, they are dried batch by batch at a scale of several tons in a big tumble dryer under vacuum for 10 hrs. and afterwards cooled under vacuum as well. The shell of the tumble dryer is heated by water steam with a target drying temperature of 135 C. All precursors are scanned by XRD at a 2 range from 15 to 85. The XRD pattern is Rietveld refined by commercial software Topas. FIG. 2 shows that the majority of the precursors contains twin peak at 2 around 33, 38 and 52, but with different peak intensity ratios. It has been determined that the lot-to-lot difference is due to the difference in quantity of hydrogen removed by the thermal decomposition of the already dried cake. The mass production tumble drying equipment efficiency can be fine-tuned by setting the target drying temperature as a function of the quantity of material to be dried, the tumble drying time and the water content of the precipitated wet cake. For Ex 1 to Ex 6, the quantity of mole H per mole pure hydroxide precursor that was removed was less than 0.15 mole/mole, for Ex 17, Ex 18 and Ex 21 it was more than 0.30 mole/mole.

(45) Ex1Ex16 are all with the combination of ideal (II)-Me(OH).sub.2 and oxidized (II)-Me(OH).sub.2 structure (see Table 2A). Both structures belong to the same space group with slightly different lattice parameters, i.e. the length of a, c-axes. As shown in Table 2A, there is a tendency for the length of the a-axes for ideal (II)-Me(OH).sub.2 structure to decrease with its decreasing weight fraction, while that for the oxidized (II)-Me(OH).sub.2 structure decreases with its increasing weight fraction. This continuous change of a-axes indicates an intergrowth process of oxidized (II)-Me(OH).sub.2 within the ideal (II)-Me(OH).sub.2 during the drying of the NMC532 precursor. Ex17 mainly contains the oxidized (II)-Me(OH).sub.2 structure, no peaks for ideal (II)-Me(OH).sub.2 structure. Instead, a small amount of (III)-MeOOH is identified, indicating a formation of an oxyhydroxide phase, corresponding to the phase in EEX5 and EEX6.

(46) It is to be noted that the intergrowth of oxidized (II)-Me(OH).sub.2 structure inside the ideal (II)-Me(OH).sub.2 is in principle coherent because both belong to the same space group, and thus it cannot be harmful for the crystal structure. However, the formation of the cubic oxyhydroxide (III)-MeOOH phase, due to its different lattice array, creates a lattice misfit to the oxidized (II)-Me(OH).sub.2 structure, and hence a high local strain. At the applied drying temperature, the presence of this strain makes it very difficult to maintain the crystallite size during the gradual phase transformation from hexagonal to cubic phase. This could be proved by the reducing peak intensity of all characteristic peaks in EEX5 and EEX6. The bad crystallinity of these precursors could lead to a less perfect lattice arrangement after lithiation, which obviously is not preferred.

(47) EX1EX16 all contains twin splitting of the 100 peak)(233, 101 peak) (238), 102 peak (252), the peaks at 38 having the highest intensity and clearest splitting. At each of those positions, the peaks with the slightly higher 2 angle (right peaks) belong to the oxidized (II)-Me(OH).sub.2 while the peaks with slightly lower angles (left peaks) belong to the ideal (II)-Me(OH).sub.2. In the current invention, the XRD pattern from 35.5 to 43 is extracted for peak intensity ratio calculations using the method described before. The peak at slightly lower 2 angle is considered as left peak and the peak at slightly higher 2 angle as right peak. The calculated peak intensity ratio (R) is listed in Table 2B. For EX17, its peak intensity ratio is considered close to infinity due to the absence of ideal (II)-Me(OH).sub.2 structure. In FIG. 2, arrows indicate the formation of (III)-MeOOH defects in EX17 precursor, which are better illustrated in FIG. 8 where the same XRD patterns are plotted in Ln(CPS) scale. EX1EX16 are actually arranged with (R) from small to big.

(48) All the NMC532 precursors are lithiated by using a conventional high temperature sintering process. Li.sub.2CO.sub.3 (Chemetall) is dry mixed with the precursor compound in a Li:M molar ratio around 1.02 by using a blender for 30 mins. The mixture is reacted at 925 C. in trays for 10 hrs under air using mass production scale equipment. After firing, the sintered cake is crushed, classified and sieved so as to obtain a non-agglomerated powder with a mean particle size D50 similar to that of the precursor, i.e. about 11 m. For all NMC532 made from EX1EX16, the 1.sup.st cycle 0.1 C coin cell discharge capacity increases with peak intensity ratio first and then becomes more or less stabilized, as shown in Table 2B and FIG. 3.

(49) Since the charge capacities are the same from EX1EX16, the difference in DQ mainly comes from the difference in Qirr during the first cycle. In addition, the 3 C rate performance also increases with peak intensity ratio and then becomes more or less stabilized, as seen in FIG. 4. The 3 C rate percentage is equal to the discharge capacity at 3 C rate normalized over the discharge capacity at 0.1 C. The biggest difference in discharge capacity at 3 C is as high as 8 mAh/g in the current study. For EX17 having only single peaks in the XRD pattern, it has a much higher loss of capacity during the first cycle, lower DQ and lower 3 C rate performance, which is not supported by its high peak intensity ratio (near infinity). It rather indicates that the formation of the (III)-MeOOH causes a less perfect crystal structure after lithiation, and this deteriorates the cathode performance. Therefore, it is believed that precursor structure and defect configuration are really critical for the reaction kinetics, such as the time needed to achieve a gas equilibrium, the time needed to get a perfect crystal structure and so on. To conclude, NMC532 precursors with the characteristic twin peak structure at around 38 and with a peak intensity ratio R>0.7 (but absent being peaks corresponding to either one or both of a spinel and an oxyhydroxide compound) according to the invention are preferred.

(50) EX18EX19

(51) By using the same production line as NMC532 precursors, NMC111 precursors are co-precipitated at MP scale for NMC111 cathode production. After being washed and filtered, the NMC111 precursor is also dried batch by batch at a scale of several tons in a big tumble dryer under vacuum for 10 hrs., and afterwards cooled under vacuum. The shell of the tumble dryer is heated by water steam with a target drying temperature of 135 C. The precursors are scanned by XRD at a 2 range from 15 to 85, the results are shown in Table 2A. Ex18 shows both the ideal (II)-Me(OH).sub.2 structure and the oxidized (II)-Me(OH).sub.2 structure. However it contains spinel Me.sub.3O.sub.4 impurities, as shown in FIGS. 5 & 8, where the arrows highlight the spinel impurity. Ex19 contains a big fraction of the oxidized (II)-Me(OH).sub.2 structure and a small fraction of the ideal (II)-Me(OH).sub.2, but without any impurities. The calculated peak intensity ratio is about 3. This variation between two NMC111 precursors is believed to be due to the same reasons as for the NMC532 precursors.

(52) Both NMC111 precursors are lithiated in a conventional high temperature sintering process. Li.sub.2CO.sub.3 (Chemetall) is dry mixed with the precursor compound in a Li:M molar ratio around 1.11 by using a blender for 30 mins. The mixture is reacted at 980 C. for 10 hr under air, using a mass production scale equipment. After firing, the sintered cake is crushed, classified and sieved so as to obtain a non-agglomerated powder with a mean particle size D50 similar to that of the precursor, i.e. about 10 m. As shown in Table 2B, the NMC111 cathode from Ex19 has a higher 1st cycle DQ, higher rate performance and lower Qirr compared to that from Ex18. It is partially attributed to its higher peak intensity ratio. Besides, the spinel impurity is also believed to be a reason for the low capacity and rate performance of EX18. To conclude, an NMC111 precursor with characteristic twin peak structure and with peak intensity ratio R>0.7 is preferred, i.e. the same conclusion as for the NMC532 precursors.

(53) EX20EX21

(54) Ex20 is an NMC622 precursor co-precipitated, filtered, washed and dried under the same conditions as the NMC111 and NMC532 precursors. It contains both ideal and oxidized (II)-Me(OH).sub.2 structures with peak intensity of 1.61, as shown in FIG. 5. Ex21 is a commercial NMC622 precursor bought from an external supplier. It has very similar physicochemical properties as Ex20, except that it has mainly an oxidized (II)-Me(OH).sub.2 structure (only single peaks in the XRD pattern) and a small fraction of (III)-MeOOH defect, comparable to EX19 in NMC532 (see Table 2A). In FIGS. 5 & 8, the arrows in Ex21 indicate the (III)-MeOOH defect. All the NMC622 precursors are lithiated by using conventional high temperature sintering process. LiOH (Chemetall) is dry mixed with the precursor compound in a Li:M molar ratio around 1.02 by using a blender for 30 mins. The mixture is reacted at 880 C. for 10 hr under air, using a mass production scale equipment. After firing, the sintered cake is crushed, classified and sieved so as to obtain a non-agglomerated powder with a mean particle size D50 similar to that of the precursor, i.e. about 12 m. As shown in Table 2B, the NMC622 cathode made from Ex20 has an excellent coin cell 1st cycle DQ and good rate performance, while the one made from Ex21 has a 2.7 mAh/g lower DQ and a 4% lower rate performance at 3 C rate. This amounts to more than 9 mAh/g loss in discharge capacity at 3 C rate, which is huge. To conclude, an NMC622 precursor with the characteristic twin peak structure and with a peak intensity ratio R>0.7 is preferred, as already concluded for the NMC111 and NMC532 precursors.

(55) EX2-I, EX10-I, EX2-II, EX10-II

(56) The precursors of EX2 and EX10 have peak intensity ratios of 0.43 and 1.72 respectively. To demonstrate the impact of the precursor on the cathode performance, from these two precursors, four more cathodes are prepared in a mass production line using the same lithiation conditions as described above in EX1EX17, except that: EX2-I and EX10-I are lithiated in a tray with a blend loading of 3 kg; EX2-II and EX10-II are lithiated in a tray with a blend loading of 7 kg. At a blend loading of 3 kg, EX10-I, compared to EX2-I, has a higher coin cell 0.1 C DQ with a similar CQ, lower Qirr, and higher 3 C rate performance, as listed in Table 3A.

(57) The cathode active materials are also incorporated in full cells as described before. Table 3B shows the slurry viscosity, at a half hour after the full cell slurry preparation. The cathode made from EX10-I clearly has a lower slurry viscosity, which makes it easier for cathode coating onto the Al foil current collector. Besides, the full cell specific capacity and 3 C rate performance is consistent with the coin cell data. When tested at 20 C., the full cell made from EX10-I also shows a slightly higher capacity retention, compared to that made from EX2-I. As for the hot box testing, the voltage of EX10-I is maintained up to a temperature higher than that of EX2-I, which indicates better safety.

(58) FIG. 6 shows the full cell cycle life tested at 25 C., where EX10-I and EX2-I basically have the same capacity fading during cycling. However, the former clearly has less DCR increase compared to the latter. FIG. 7 shows the full cell cycle life data tested at 45 C. Consistently, EX10-I has less DCR increase compared to EX2-I, despite the fact that their cycling stability at 45 C. are the same.

(59) For the blend loading of 7 kg, coin cell testing data and full cell testing data confirm that cathodes made from EX10-II have a benefit over those made from EX2-II, as shown in Table 3A&B and FIGS. 6 & 7. For cathode mass production, a high temperature firing using trays, and a low blend load factor typically ensure a complete solid state reaction and a better cathode crystal structure and hence better cathode performance. So it is normal that EX2-II fired at 7 kg blend loading has worse performance compared to EX2-I at 3 kg blend loading, as is also the case for EX10-II against EX10-I. However, if we compare the performance degradation in EX2-II versus EX2-I to the performance degradation of EX10-II versus EX10-I (the latter being smaller than the former), it is shown that this performance degradation occurring at a high blend loading can be reduced if a precursor compound with high(er) peak intensity ratio is applied (R being smaller for EX2 than for EX10).

(60) TABLE-US-00001 TABLE 1A Explanatory examples on 10~12 m precursor being dried under defined conditions Precursor Drying Cooling Drying Drying No Ni/Mn/Co atmosphere atmosphere T ( C.) time (hrs.) EEX1 60/20/20 N.sub.2 N.sub.2 150 24 EEX2 60/20/20 Vacuum Vacuum 135 24 EEX3 60/20/20 Vacuum Vacuum 150 24 EEX4 60/20/20 Vacuum Dry air 150 24 EEX5 60/20/20 Dry air Dry air 150 24 EEX6 60/20/20 Dry air Dry air 200 24 EEX7 50/30/20 N.sub.2 N.sub.2 150 24 EEX8 50/30/20 Vacuum Vacuum 150 24 EEX9 50/30/20 Vacuum Dry air 150 24 EEX10 50/30/20 Dry air Dry air 150 24 EEX11 34/33/33 Vacuum Vacuum 150 24 EEX12 34/33/33 Vacuum Vacuum 200 24

(61) TABLE-US-00002 TABLE 1B Explanatory examples on 10~12 m precursor being dried under defined conditions -ctd. Ideal (II)-Me(OH).sub.2 Oxidized (II)-Me(OH).sub.2 (III)-MeOOH Me.sub.3O.sub.4 Average a- Peak intensity N Wt % a() c() Wt % a() c() Yes or no? Yes or no? axis () ratio R EEX1 100 3.1596 4.6533 No No 3.160 0.00 EEX2 46.6 3.1624 4.6561 53.4 3.1117 4.5960 No No 3.135 0.80 EEX3 9.1 3.1583 4.6241 90.9 3.0991 4.5878 No No 3.104 8.91 EEX4 100 3.0823 4.5832 No No 3.082 / EEX5 100 3.0145 4.5677 Yes No 3.015 / EEX6 100 2.9823 4.5744 Yes No 2.982 / EEX7 100 3.1846 4.6666 No No 3.185 0.00 EEX8 73.5 3.1845 4.6632 26.5 3.1520 4.6607 No No 3.176 0.31 EEX9 47.9 3.1737 4.6742 52.1 3.0633 4.6103 No No 3.116 1.10 EEX10 100 3.0000 4.5571 Yes No 3.000 / EEX11 65.0 3.1954 4.6775 35.0 3.1232 4.6265 No No 3.170 EEX12 18.9 3.1642 4.6682 65.4 3.1069 4.6019 No Yes 3.120 /

(62) TABLE-US-00003 TABLE 2A Example NMC precursors for Li-Me-O.sub.2 cathode mass production Precursor Ideal (II)-Me(OH).sub.2 Oxidized (II)-Me(OH).sub.2 No Ni/Mn/Co Wt % a () c() Wt % a() c() EX1 50/30/20 62.6 3.1759 4.6725 37.4 3.1041 4.6405 EX2 50/30/20 56.9 3.1723 4.6701 43.1 3.1049 4.6341 EX3 50/30/20 55.3 3.1676 4.6691 44.7 3.1100 4.6332 EX4 50/30/20 50.4 3.1737 4.6729 49.6 3.1030 4.6341 EX5 50/30/20 48.4 3.1716 4.6729 51.6 3.1066 4.6292 EX6 50/30/20 48.2 3.1676 4.6648 51.8 3.1054 4.6351 EX7 50/30/20 41.8 3.1700 4.6733 58.2 3.1020 4.6279 EX8 50/30/20 37.7 3.1712 4.6790 62.3 3.1042 4.6253 EX9 50/30/20 36.4 3.1661 4.6786 63.6 3.0983 4.6231 EX10 50/30/20 31.5 3.1678 4.6836 68.5 3.1020 4.6220 EX11 50/30/20 35.4 3.1652 4.6763 64.6 3.0964 4.6268 EX12 50/30/20 35.5 3.1642 4.6788 64.5 3.0968 4.6269 EX13 50/30/20 35.9 3.1670 4.6783 64.1 3.0940 4.6285 EX14 50/30/20 35.5 3.1613 4.6882 64.5 3.0886 4.6238 EX15 50/30/20 17.6 3.1590 4.6940 82.4 3.0949 4.6133 EX16 50/30/20 16.2 3.1570 4.6039 83.8 3.0857 4.6185 EX17 50/30/20 0.0 100.0 3.0354 4.6069 EX18 34/33/33 59.2 3.1892 4.6751 40.8 3.1195 4.6349 EX19 34/33/33 18.4 3.1844 4.6841 81.6 3.1027 4.6073 EX20 60/20/20 42.1 3.1410 4.6649 57.9 3.1080 4.6146 EX21 60/20/20 0.0 100 3.0267 4.5705

(63) TABLE-US-00004 TABLE 2B Example NMC precursors for Li-Me-O.sub.2 cathode mass production -ctd. (III)- Avg. Coin cell performance MeOOH Me.sub.3O.sub.4 a-axis D50 CQ DQ Qirr 3 C rate N Yes/no? Yes/no? () R (m) (mAh/g) (mAh/g) (%) (%) EX1 No No 3.149 0.32 11.2 190.4 164.5 13.6 83.0 EX2 No No 3.143 0.43 11.0 190.6 165.6 13.1 84.1 EX3 No No 3.142 0.43 11.6 190.9 166.6 12.7 84.3 EX4 No No 3.139 0.51 11.2 190.8 165.8 13.1 85.0 EX5 No No 3.138 0.59 11.8 189.7 166.8 12.1 85.5 EX6 No No 3.135 0.42 11.3 191.5 167.1 12.8 85.4 EX7 No No 3.130 0.78 10.6 190.9 168.7 11.6 85.7 EX8 No No 3.129 1.03 11.0 190.8 168.0 11.9 85.8 EX9 No No 3.123 1.43 10.7 190.6 168.7 11.5 86.0 EX10 No No 3.123 1.72 11.7 191.1 169.4 11.3 85.8 EX11 No No 3.121 1.05 10.5 190.6 169.0 11.3 86.2 EX12 No No 3.121 1.33 10.8 190.8 169.1 11.4 85.7 EX13 No No 3.120 1.20 10.2 191.6 170.5 11.0 86.2 EX14 No No 3.114 2.04 EX15 No No 3.106 3.33 10.8 191.5 169.4 11.6 85.6 EX16 No No 3.097 4.17 10.8 191.4 170.0 11.2 85.6 EX17 Yes No 3.035 / 11.5 190.1 165.3 13.0 84.0 EX18 No Yes 3.161 / 10.3 177.2 154.7 12.7 86.0 EX19 No No 3.118 3.03 10.2 177.8 157.1 11.7 86.8 EX20 No No 3.122 1.61 13.0 199.6 178.9 10.4 85.9 EX21 Yes No 3.027 / 12.8 200.3 176.2 12.0 81.9

(64) TABLE-US-00005 TABLE 3A Example NMC precursors for Li-Me-O.sub.2 cathode mass production Precursor Peak intensity Lithiation Coin cell performance N Ni/Mn/Co ratio (R) condition CQ (mAh/g) DQ (mAh/g) Qirr (W) 3 C rate EX2-I 50/30/20 0.43 3 kg in tray 190.7 168.7 11.5 85.2 EX10-I 50/30/20 1.72 3 kg in tray 191.1 169.4 11.3 85.5 EX2-II 50/30/20 0.43 7 kg in tray 190.3 163.0 14.4 83.0 EX10-II 50/30/20 1.72 7 kg in tray 190.9 166.7 12.7 84.5

(65) TABLE-US-00006 TABLE 3B Example NMC precursors for LiMeO.sub.2 cathode mass production -ctd. Full cell performance Slurry Specific Discharge viscosity capacity capacity at Hot box T after 0.5 at 0.2 C 20 C. 3 C rate at failure No hrs. (cps) (mAh/g) (%) (%) ( C.) EX2-I 2978 161.4 70.4 87.2 165.2 EX10-I 2132 162.0 71.1 90.1 169.0 EX2-II 3535 157.6 66.7 87.7 165.5 EX10-II 2957 159.1 68.9 88.3 170.1