Method for the synthesis of a positive electrode active material for sodium-ion batteries

Abstract

The present disclosure concerns a method of synthesizing a Sodium Layered Oxide Cathode Material, comprising: providing a transition metal hydroxide precursor material comprising Ni and Mn; blending the transition metal hydroxide precursor material with sodium hydroxide, a zinc source and a titanium source to obtain a first mixture; heating the first mixture up to a temperature T1, 600°C≤T1≤900°C in an oxidizing atmosphere, holding the first mixture at T1 for a duration D1, 3 ≤ D1 ≤ 9h, cooling down to a temperature T2, 20°C≤T2≤300°C, to obtain a second mixture; optionally grinding the second mixture; heating the, optionally ground, second mixture up to a temperature T3, 900°C≤T3≤1100°C, with T3≥T1+100°C, in an oxidizing atmosphere, holding the first mixture at T3 for a duration D2, 3h ≤ D2 ≤ 20h, cooling down to a temperature T4, 20° C≤T4≤300°C, to obtain a third mixture; and optionally sieving; to obtain a Sodium Layered Oxide Cathode Material.

Description

DescriptionTitleMETHOD FOR THE SYNTHESIS OF A POSITIVE ELECTRODE ACTIVE MATERIAL FOR SODIUM-ION BATTERIES Technical Field

[0001] The present disclosure concerns a method for the synthesis of a positive electrode active material, a Sodium Layered Oxide Cathode Material, for sodium-ion batteries. The present disclosure further concerns a positive electrode active material for sodium-ion batteries obtained by the present method and a sodium ion battery comprising said positive electrode active material.Description of Related Art

[0002] Sodium-ion secondary batteries are rechargeable batteries that use sodium ions (Na+) as charge carriers, similar to lithium-ion batteries but with sodium as the intercalating ion. These batteries are gaining attention due to the abundance of sodium, lower cost, and environmental benefits compared to lithium-ion batteries. Sodium-ion batteries still need improvement in their performance in comparison to lithium-ion batteries.Summary

[0003] The present disclosure concerns a method of synthesizing a Sodium Layered Oxide Cathode Material, comprising:a. providing a transition metal hydroxide precursor material comprising Ni and Mn;

[0004] blending the transition metal hydroxide precursor material with sodium hydroxide, a zinc source and a titanium source to obtain a first mixture;a. heating the first mixture up to a temperature T1, 600°C< T1<900°C in an oxidizing atmosphere, holding the first mixture at T1 for a duration D1, 3 < D1 < 9h, cooling down to a temperature T2, 20°C< T2<300°C, to obtain a second mixture;b. optionally grinding the second mixture;c. heating the, optionally ground, second mixture up to a temperature T3, 900°C< T3<1100°C, with T3> T1+100°C, in an oxidizing atmosphere, holdingthe first mixture at T3 for a duration D2, 3h < D2 < 20h, cooling down to a temperature T4, 20°C< T4<300°C, to obtain a third mixture; and d. optionally sieving to obtain the Sodium Layered Oxide Cathode Material.

[0005] The method of the present disclosure comprises thus a sequence of two separate heating steps, a first heating step at a lower temperature, followed, after a cool-down period, by a second heating step at a higher temperature. The inventors have found that the Sodium Layered Oxide Cathode Material obtained by the method of the present disclosure, provides high levels of discharge capacity after more than 10, more than 30, and even more than 40 charge-discharge cycles. Furthermore, high levels of 03, thus a high level of purity, can be obtained.Brief Description of the Drawings

[0006] Figure 1 shows an SEM image of cathode active material not according to embodiments of the present disclosure.

[0007] Figure 2 shows SEM images of cathode active material according to embodiments of the present disclosure.Detailed Description

[0008] In an embodiment of the present disclosure, the transition metal hydroxide precursor material is a blend of a first transition metal hydroxide precursor P1 and a second transition metal hydroxide precursor P2, P1 having a particle size distribution value D50i ranging from 8.0 pm to 12.0 pm and P2 having a particle size distribution value D502 ranging from 3.0 pm to 6.0 pm.

[0009] In an embodiment of the present disclosure, P1 comprises Ni and Mn in a molar ratio R1 of Ni to Mn ranging from 0.25 to 4.

[0010] In an embodiment of the present disclosure, P2 comprises Ni and Mn in a molar ratio R2 of Ni to Mn ranging from 0.25 to 4.

[0011] In an embodiment of the present disclosure, heating the first mixture up to a temperature T1 is performed at a rate of 0.5°C / min to 5°C / min, in particular of about 1 °C / min to about 4°C / min, in particular of about 2°C / min to about 4°C / min.

[0012] In an embodiment of the present disclosure, heating the, optionally ground, second mixture up to a temperature T3 is performed at rate of 0.5°C / min to 5°C / min, inparticular of about 1°C / min to about 4°C / min, in particular of about 2°C / min to about 4°C / min

[0013] In an embodiment of the present disclosure, cooling from T1 to T2 is performed at a cooling rate of 0.5°C / min to 5°C / min, in particular of about 0.5°C / min to about 4°C / min, in particular of about 1 °C / min to about 3°C / min.

[0014] In an embodiment of the present disclosure, cooling from T3 to T4 is performed at a cooling rate of 0.5°C / min to 5°C / min, in particular of about 0.5°C / min to about 4°C / min, in particular of about 1 °C / min to about 3°C / min.

[0015] In an embodiment of the present disclosure, P2’s particle size distribution value D50i is at least 8.0pm, at least 8.5pm, at least 9.0 pm, or at least 9.5 pm.

[0016] In an embodiment of the present disclosure, D50i is at most 12.0 pm, at most 11.5 pm, at most 11.0 pm or at most 10.5 pm.

[0017] In an embodiment of the present disclosure, D50i is about 10.0pm.

[0018] In an embodiment of the present disclosure, P2’s particle size distribution value D502 is at least 3.0pm, at least 3.5pm, or at least 4.0 pm.

[0019] In an embodiment of the present disclosure, D502 is at most 6.0 pm, at most 5.5 pm, or at most 5.0 pm.

[0020] In an embodiment of the present disclosure, D502 is about 4.5 pm.

[0021] In an embodiment of the method present disclosure, the sodium Layered Oxide Cathode Material comprises Na, M and O, wherein M comprises:a. Ni in an atomic content a wherein 0.10s£as=0.40 relative to M;b. Mn in an atomic content c, wherein 0.10s£cs=0.60 relative to M;c. Zn in an atomic content q, wherein 0.0q 0.10 relative to M;d. Ti in an atomic content f, wherein 0.0f 0.20 relative to M;e. D‘ in an atomic content d, wherein 0d 0.20 relative to M, and wherein D‘ is at least one element selected from the group of Li, Mg, Al, B, Si, K, Ca, Co, Cu, Sr, Zr, Nb, Mo, Sn, and W;wherein a, c, q, f, and d are measured by ICP-OES, and a+c+d+q+f+d=1,

[0022] In an embodiment of the present disclosure the sodium Layered Oxide Cathode Material comprises secondary particles consisting of a plurality of primary particles. It was found that such secondary particles may show higher resistance to the stress and strain from volume changes during battery cycling than monolithic particles. The morphology of the sodium Layered Oxide Cathode Material may be confirmed by scanning electron microscopy (SEM) measurements.

[0023] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the Ni atomic content a is at least 0.10 relative to M, at least 0.20, or at least 0.30.

[0024] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the Ni atomic content a may be at most 0.40 relative to M, or at most 0.39.

[0025] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the Ni atomic content a is about 0.39 relative to M.

[0026] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the Ni atomic content a is between 0.20 and 0.40 relative to M.

[0027] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the Mn atomic content c is at least 0.10 relative to M, at least 0.20, or at least 0.30.

[0028] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the Mn atomic content c is at most 0.60 relative to M, or at most 0.45.

[0029] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the Mn atomic content c is about 0.47 relative to M.

[0030] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the Mn atomic content c is between 0.35 and 0.55 relative to M.

[0031] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the Zn atomic content q is at least 0.01 relative to M, at least 0.03, or at least 0.05.

[0032] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the Zn atomic content q may be at most 0.10 relative to M.

[0033] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the Zn atomic content q is about 0.10 relative to M.

[0034] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the Zn atomic content q is between 0.03 and 0.10 relative to M.

[0035] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the Ti atomic content f is at least 0.01 relative to M, at least 0.03, or at least 0.05.

[0036] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the Ti atomic content f may be at most 0.15 relative to M.

[0037] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the Ti atomic content f is about 0.05 relative to M.

[0038] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the Ti atomic content f is between 0.01 and 0.10 relative to M.

[0039] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, D‘ is Al, and the Al atomic content d is at least 0.00001 relative to M, at least 0.00005, or at least 0.0001.

[0040] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, D‘ is Al, and the Al atomic content d may be at most 0.01 relative to M.

[0041] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, D‘ is Al, and the Al atomic content d is about 0.01 relative to M.

[0042] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, D‘ is Al, and the Al atomic content d is between 0.00001 and 0.01 relative to M.

[0043] In an embodiment of the present disclosure, in the sodium Layered Oxide Cathode Material, the atomic ratio Na / M ranges from 0.8 to 1.5.

[0044] In an embodiment of the present disclosure, the sodium Layered Oxide Cathode Material is according to a general formula (I): NaxNiaiMnciZnqiTifiD’diO2 (I).

[0045] In an embodiment of the present disclosure, the sodium Layered Oxide Cathode Material is according to formula (I), wherein 0.8s£xs=1.50; 0.20 s=a1 s=0.40; 0.35s=c1 s=0.55; 0.03s=q1 ^0.10; 0.01 s=f1 ^0.10; 0.00001 s=d1 ^0.01; wherein D’ is Al, and wherein a1+c1+d1+q1+f1+d1 = 1.

[0046] The present disclosure further concerns a sodium Layered Oxide Cathode Material obtained using the method of the present disclosure in any embodiment or combination of embodiments.

[0047] The present disclosure further concerns a sodium battery comprising a sodium Layered Oxide Cathode Material obtained using the method of the present disclosure in any embodiment or combination of embodiments.

[0048] The present disclosure further concerns the use of a battery comprising a sodium Layered Oxide Cathode Material obtained using the method of to the present disclosure in any embodiment or combination of embodiments, 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.

[0049] BET - Gas adsorption was conducted using the Brunauer-Emmett-Teller (BET) theory to determine the specific surface area (SSA) of the material. Samples were first pre-treated by weighing 1 g into a suitable sized gas adsorption sample vial. The sample is then heated to 150°C under nitrogen flow for 1 hour using a Micromeritics VacPrep 061 to move any adsorbed species. BET SSA is then measured using a Micromeritics TriStar 3020.

[0050] Inductively coupled plasma (ICP-OES) - The composition of the positive electrode active material powder was measured by the inductively coupled plasma (ICP) method using an Agilent 720 ICP-OES. 1 gram of powder sample is dissolved into 50 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 was covered by a watch glass and heated on a hot plate at 380 °C until the powder is completely dissolved. After being cooled to room temperature, the solution from the Erlenmeyer flask was poured into a first 250 mL volumetric flask. Afterwards, the first volumetric flask was filled with deionized water up to the 250 mL mark, followed by a complete homogenization process (1st dilution). An appropriate amount of the solution from the first volumetric flask was taken out by a pipette and transferred into a second 250 mL volumetric flaskfor the 2nd dilution, where the second volumetric flask was filled with an internal standard element and 10 % hydrochloric acid up to the 250 mL mark and then homogenized. Finally, this solution was used for ICP measurement.

[0051] Scanning Electron Microscopy (SEM) - The morphology of positive electrode active materials is analyzed by a Scanning Electron Microscopy (SEM) technique. The measurement is performed using a ZEISS SIGMA 300 under a high vacuum environment of 8x1 O’6Pa at 25 °C. The particles in the image should be well distributed therefore avoiding overlap 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 dry air to remove the excess powder.

[0052] Particle size - The particle size distribution (PSD) of the positive electrode active material powders is measured using a Malvern Mastersizer 3000 equipped with an Aero S dry dispersion accessory. The powders are introduced into the instrument through a dry feeder system, where they are dispersed in a stream of compressed air. To ensure effective dispersion and prevent agglomeration, the air pressure is set at 2 bar. The D50 values - D50i, D502, D50i2 - are defined as the particle size at which 50% of the cumulative volume is smaller and 50% is larger. The PSD Span refers to the width of a particle size distribution. It is calculated using the formula: Span = (D90 - D10 / D50, where: D90 is the particle size below which 90% of the sample's volume is contained, D10 is the particle size below which 10% of the sample's volume is contained, and D50 is the median particle size, meaning 50% of the sample's volume is low this size. This formula gives an indication of how far apart the 10% and 90% points are normalized with the midpoint.

[0053] Coin cell preparation - The method comprises forming a slurry comprising a positive electrode active material powder, a conductive material (Li-435, Denka), and a binder (KF#9700, Kureha) in a weight ratio of 92:4.0:4.0, respectively, in a solvent (NMP, N-Methyl-2-pyrrolidone, Sigma-Aldrich). The slurry is homogenized using a centrifugal Thinky mixer. The homogenized slurry is then uniformly applied to one side of an aluminum foil substrate using a doctor's blade coater with a gap of 280 pm. The coated foil is subsequently dried in an oven at a temperature of 120 °C. Following the drying step, the coated foil is pressed using a calendaring tool, achieving a density of 2.5g / cm3. The coin cell is assembled within an argon-filled glovebox to prevent contamination. A separator (glass microfiber filter) is placed between the positiveelectrode and a piece of sodium foil, which serves as the negative electrode. An electrolyte solution comprising 0.6M NaPFe in a mixture of propylene carbonate (PC) and fluoroethylene carbonate (FEC, 2% by weight of FEC in PC) is added between the separator and the electrodes. The coin cell is then sealed to prevent electrolyte leakage, completing the assembly process.

[0054] Coin cell testing - The tests for discharge capacity (DQ) and irreversible capacity (Qirr) are performed using coin cells with electrodes consisting of 92 wt% of the cathode active material described in this invention. The electrode loading is approximately 11 mg / cm2The discharge capacity for the first cycle (DQ1) is measured within the voltage range of 2.2-4.2 V at a rate of 0.1 C (expressed in mA / g) at a temperature of 25°C. The cell testing procedure uses a 1 C current definition of 180 mA / g.

[0055] Table 1 below summarizes the conditions used for the cycle test of the examples and comparative examples of the present disclosure. Charging is performed at the indicated charging current in CC mode (constant current) up to 4.2V. Discharge is performed at the indicated discharge current in CC mode down to 2.2V. Rest times between charge and discharge were 10 minutes.

[0056] Table 1 - Cycle testCycle Charge End End Discharge End number current Current voltage (V) current voltage (V) 1 to 3 C / 10 C / 10 4.2 C / 10 2.2 4 C / 4 C / 10 4.2 C / 10 2.2 5 C / 4 C / 10 4.2 C / 5 2.2 6 C / 4 C / 10 4.2 C / 2 2.2 7 C / 4 C / 10 4.2 1C 2.2 8 and 9 C / 10 C / 10 4.2 C / 10 2.2 10 C / 4 C / 10 4.2 C / 10 2.2 11 C / 3 C / 10 4.2 C / 3 2.2 12 C / 4 C / 10 4.2 1C 2.2 13 to 37 C / 2 C / 10 4.2 1C 2.2 38 and 39 C / 10 C / 10 4.2 C / 10 2.240 C / 4 C / 10 4.2 C / 10 2.241 C / 3 C / 10 4.2 C / 3 2.2 42 C / 4 C / 10 4.2 1C 2.2

[0057] Examples and comparative examples

[0058] CE1 - A transition metal hydroxide precursor material is provided. The precursor material is a blend of a first transition metal hydroxide precursor having a having a particle size distribution value D50i of about 4pm and second transition metal hydroxide precursor having a having a particle size distribution value D502 of about 10pm. A blend of the precursor material, NaOH, ZnO and TiO2 is prepared using a high intensity mixer, mixing for 2 minutes at 400rpm in a dry room. The blended powder is calcined in a furnace under dry air. The blended powder is heated up to 950°C at a rate of 3°C / min, held at 950°C for 12h, and then cooled down to about 80°C at a rate of about 1°C / min. A sodium Layered Oxide Cathode Material CE1 is obtained having the composition indicated in Table 1 herein below. In CE1, the proportions of precursor material, NaOH, ZnO and TiO2 are adapted so as to obtain an atomic ratio of sodium to the sum of Ni, Mn, Ti and Zn of 0.936 and a molar ratio Ni: Mn: Ti: Zn of 38.5:46.7:9.9:4.9.

[0059] CE2 is prepared in the same manner as CE1 except that the proportions of precursor material, NaOH, ZnO and TiO2 are modified so as to obtain an atomic ratio of sodium to the sum of Ni, Mn, Ti and Zn of 0.885.

[0060] E1 - A transition metal hydroxide precursor material is provided. The precursor material is a blend of a first transition metal hydroxide precursor having a having a particle size distribution value D50i of about 4pm and second transition metal hydroxide precursor having a having a particle size distribution value D502 of about 10pm. A blend of the precursor material, NaOH, ZnO and TiO2 is prepared using a high intensity mixer, mixing for 2 minutes at 400 rpm in a dry room. The blended powder is heated in a first furnace under dry air. The blended powder is heated up to 800°C at a rate of 3°C / min, held at 800°C for 6 h, and then cooled down to about 200°C at a rate of about 1°C / min. The heated blended powder is ground. The grounded powder is calcined in a furnace under dry air. The grounded powder is heated up to 950°C at a rate of 3°C / min, held at 950°C for 6 h, and then cooled down to about 200°C at a rate of about 1 °C / min. A sodium Layered Oxide Cathode Material E1 is obtained having the composition indicated in Table 1 herein below. In E1, theproportions of precursor material, NaOH, ZnO and TiO2 are adapted so as to obtain an atomic ratio of sodium to the sum of Ni, Mn, Ti, Zn and Al of 0.877 and a molar ratio Ni: Mn: Ti: Zn: AI of 38.5:46.7:9.9:4.9:0.10.

[0061] E2 is prepared in the same manner as E1 except that the proportions of precursor material, NaOH, ZnO and TiO2 are modified so as to obtain an atomic ratio of sodium to the sum of Ni, Mn, Ti and Zn of 0.929.

[0062] E3 - A transition metal hydroxide precursor material is provided. The precursor material is a blend of a first transition metal hydroxide precursor having a having a particle size distribution value D50i of about 4pm and second transition metal hydroxide precursor having a having a particle size distribution value D502 of about 10pm. A blend of the precursor material, NaOH, ZnO and TiO2 is prepared using a high intensity mixer, mixing for2minutes at 400rpm in a dry room. The blended powder is heated in a first furnace under dry air. The blended powder is heated up to 800°C at a rate of 3°C / min, held at 950°C for 6h, and then cooled down to about 200°C at a rate of about 1°C / min. The heated blended powder is ground. The grounded powder is calcined in a furnace under dry air. The grounded powder is heated up to 950°C at a rate of 3°C / min, held at 950°C for 12h, and then cooled down to about 200°C at a rate of about 1°C / min. A sodium Layered Oxide Cathode Material E3 is obtained having the composition indicated in Table 1 herein below. In E1, the proportions of precursor material, NaOH, ZnO and TiO2 are adapted so as to obtain an atomic ratio of sodium to the sum of Ni, Mn, Ti, Zn and Al of 0.878 and a molar ratio Ni: Mn: Ti: Zn: AI of 38.5:46.7:9.9:4.9:0.01.

[0063] E4 is prepared in the same manner as E1 except that the proportions of precursor material, NaOH, ZnO and TiO2 are modified so as to obtain an atomic ratio of sodium to the sum of Ni, Mn, Ti and Zn of 0.931.

[0064] Table 2 - CompositionNi Mn Zn Ti AlNa / metal 03 P2 NiO content content content content contentratio (wt %) (wt%) (wt.%) a c q f dE1 0.877 0.385 0.467 0.099 0.049 0.001 97.82 1.19 0.99 E2 0.929 0.385 0.467 0.098 0.049 0.001 97.90 1.76 0.34 E3 0.878 0.389 0.474 0.097 0.039 0.0001 96.46 2.74 0.80 E4 0.931 0.388 0.474 0.099 0.039 0.0001 93.10 6.57 0.33CE1 0.885 0.385 0.467 0.099 0.049 - 97.51 1.31 1.18 CE2 0.936 0.385 0.467 0.099 0.049 - 99.01 0.52 0.47

[0065] Table 3 – BET and PSD dataBET (m2 / g) D10 (pm) D50 (pm) D90 (pm) Span E1 0.482 3.59 7.38 17.6 1.9 E2 0.526 3.63 7.24 15.9 1.7 E3 0.646 4.16 9.72 33.2 3.0 E4 0.466 4.75 12.0 36.2 2.6 CE1 0.556 2.87 5.89 13.8 1.9 CE2 0.538 2.89 5.96 14.4 1.9

[0066] As can be seen in Table 3 on E1, E2, E3, and E4, higher D50 values can be achieved using the method of the present disclosure, and a range of D50 values can be achieved using different calcination durations in the second heating step. E1 and E2 achieve particularly high 03 wt% levels as can be seen in Table 2. The aluminum in E1-E4 stems from crucible corrosion during repeated heating cycles.

[0067] Table 4 – Electrochemical performanceCQ1 DQ1 Qirr DQ4 DQ12 DQ40 DQ42 E1 163.27 157.48 3.55 159.35 143.52 150.98 132.09 E2 172.13 159.03 7.61 161.99 150.44 154.57 141.18 E3 165.63 156.42 5.56 155.07 141.52 143.46 125.15 E4CE1 165.3 157.7 4.60 156.81 140.45 145.11 128.45 CE2 174.5 159.35 8.68 160.14 144.39 148.83 131.65

[0068] As can be seen in Table 4, in particular for longer calcination durations used for E1 and E2, discharge capacities after repeated cycling is higher than for CE1 and CE2 and also for E3 and E4.

Claims

Claims

1. Method of Synthesizing a Sodium Layered Oxide Cathode Material, comprising:a. providing a transition metal hydroxide precursor material comprising Ni and Mn;[0069] blending the transition metal hydroxide precursor material with sodium hydroxide, a zinc source and a titanium source to obtain a first mixture;b. heating the first mixture up to a temperature T1, 600°C< T1<900°C in an oxidizing atmosphere, holding the first mixture at T1 for a duration D1, 3 < D1 < 9h, cooling down to a temperature T2, 20°C< T2<300°C, to obtain a second mixture;c. optionally grinding the second mixture;d. heating the, optionally ground, second mixture up to a temperature T3, 900°C< T3<1100°C, with T3> T1+100°C, in an oxidizing atmosphere, holding the first mixture at T3 for a duration D2, 3h < D2 < 20h, cooling down to a temperature T4, 20°C< T4<300°C, to obtain a third mixture; and e. optionally sieving to obtain the Sodium Layered Oxide Cathode Material.

2. Method according to claim 1, wherein the transition metal hydroxide precursor material is a blend of a first transition metal hydroxide precursor P and a second transition metal hydroxide precursor P2, P1 having a particle size distribution value D501ranging from 8.0 µm to 2.0 µm and P2 having a particle size distribution value D502ranging from 3.0 µm to 6.0 µm.

3. Method according to claim 2, wherein P1 comprises Ni and Mn in a molar ratio R1 of Ni to Mn ranging from 0.25 to 4.

4. Method according to claim 2 or claim 3, wherein P2 comprises Ni and Mn in a molar ratio R2 of Ni to Mn ranging from 0.25 to 4.

5. Method according to any one preceding claim, wherein D501is at least 8.0µm, at least 8.5µm, at least 9.0 µm, or at least 9.5 µm and / or wherein D501is at most 12.0 µm, at most 11.5 µm, at most 11.0 µm or at most 10.5 µm.

6. Method according to any one preceding claim, wherein D502is at least 3.0µm, at least 3.5µm, or at least 4.0 µm and / or wherein D502is at most 6.0 µm, at most 5.5 µm, or at most 5.0 µm.

7. Method according to any one preceding claim, wherein, the sodium Layered Oxide Cathode Material comprises Na, M and O, wherein M comprises a. Ni in an atomic content a wherein 0.10s£as=0.40 relative to M;b. Mn in an atomic content c, wherein 0.10s£cs=0.60 relative to M;c. Zn in an atomic q, wherein 0.0q 0.10 relative to M;d. Ti in an atomic content f, wherein 0.0f 0.20 relative to M;e. D‘ in an atomic content d, wherein 0d 0.20 relative to M, and wherein D‘ is at least one element selected from the group of Li, Mg, Al, B, Si, K, Ca, Co, Cu, Sr, Zr, Nb, Mo, Sn, and W;wherein a, c, q, f, and d are measured by ICP-OES, and a+c+d+q+f+d=1.

8. Method according to claim 7, wherein the sodium Layered Oxide Cathode Material comprises secondary particles consisting of a plurality of primary particles.

9. Method according to claim 7 or claim 8, wherein a is at least 0.10, at least 0.20, or at least 0.30 and / or wherein a is at most 0.40 or at most 0.35.

10. Method according to any one of claims 7 to 9 wherein c is between 0.35 and 0.55 relative to M.

11. Method according to any one of claims 7 to 10 wherein the atomic ratio Na / M ranges from 0.8 to 1.5.

12. Method according to any one of claims 7 to 11 the sodium Layered Oxide Cathode Material is according to according to a general formula (I): NaxNiaiMnciZnqiTifiD’diO2 (I), wherein 0.8s£xs=1.50; 0.20s=a1 s=0.40; 0.35s=c1 0.55; 0.03 q1 0.10; 0.01 ^f1 ^0.10; 0.00001 s=d1 0.01; wherein D’ is Al, and wherein a1+c1+d1+q1+f1+d1 = 1.

13. Sodium Layered Oxide Cathode Material obtained by the method according any one of claims 1 to 12.

14. A battery comprising a Sodium Layered Oxide Cathode Material according to claim 13.

15. 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 twowheeler transportation system, a rail vehicle, a marine vessel, an aircraft, an aerospace system, a defense system, and a medical device.

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