WO2017013520A1

WO2017013520A1 - Cathode material for rechargeable solid state lithium ion battery

Info

Publication number: WO2017013520A1
Application number: PCT/IB2016/054062
Authority: WO
Inventors: Jens Paulsen; Xin XIA; Song-Yi Han; Jing Zhang
Original assignee: Umicore NV SA; Umicore Korea Ltd
Current assignee: Umicore NV SA; Umicore Korea Ltd
Priority date: 2015-07-22
Filing date: 2016-07-07
Publication date: 2017-01-26
Anticipated expiration: 2018-01-22
Also published as: JP2018523892A; KR102018470B1; JP6694054B2; TWI623136B; EP3326226A1; US20180226631A1; TW201712928A; CN108028371A; US10333135B2; CN108028371B; PL3326226T3; EP3326226B1; EP3326226A4; KR20180029254A

Abstract

A lithium transition metal oxide powder for a positive electrode material in a solid-state lithium ion battery, the powder consisting of particles having a core and a surface layer consisting of an inner and an outer layer, wherein the powder has a D50 between 35 and 60µm, wherein the core has the general formula Li_xCoO₂ with 0.99<x<1.04 and wherein the inner surface layer comprises Li_yNi_1-a-bMn_aCo_bO₂, with 0<y<1, 0.3<a<0.8 and 0<b<0.3; and wherein the outer surface layer consists of discrete monolithic sub-micron sized particles having the general formula Li_1+z(Ni_1-m-nMn_mCo_n)_1-zO₂, with 0≤z≤0.05, 0<m≤0.50 and 0<n≤0.70, preferably 0<n≤0.30.10

Description

Cathode material for rechargeable solid state lithium ion battery

Technical field and Background

This invention relates to surface-modified UC0O2 powders, applicable as positive electrode for a rechargeable solid state lithium ion battery. The cathode material improves the battery performance, such as the rate capability.

Secondary lithium ion batteries are currently the technology of choice, especially for portable applications like mobile devices and notebooks, due to their advantage of high voltage, high volumetric and gravimetric energy density, and long cycle life. However, the high cell voltage of a Li ion battery poses the problem of electrolyte instability since, at high voltages, an aqueous electrolyte will decompose. The alternative organic solvents containing supporting salts are flammable and cause safety issues in the Li ion battery. Especially, with the gradually increasing demand of large-size Li ion batteries, large amounts of combustible electrolyte are required and applied in the devices. This leads to a serious safety issue, such as high potentiality of leaking, overheating and burning. Thus, a solid state electrolyte is expected to be a solution to this problem, due to its non-flammability. Starting from the middle of the 20^th century, the demand for higher safety has boosted the development of solid state lithium ion batteries. The use of a solid electrolyte cannot only solve the safety concerns by its non-flammability, but also provide the possibility to achieve a higher energy density and excellent cyclability. Solid electrolyte has the property of "single-ion" conduction. Typical liquid electrolytes are binary conductors having anodic and cathodic ionic conductivity which causes unwanted effects, for example electrolyte salt depletion. Thus single ion electrolytes in principle can show a superior sustainable power. Additionally a solid/solid interface can be less reactive compared to a liquid electrolyte/cathode interface. This reduces side reactions happening between liquid electrolyte and electrode materials, further preventing the decomposition of electrolyte and finally improving battery life. The advantage of less side reactions also allows the application of solid state lithium ion batteries at high voltage. In "Journal of the Electrochemical Society, 149 (11), A1442-A1447, 2002", the use of Lithium phosphorous oxy-nitride "U PON" electrolytes (with the composition Li_xPO_yNz, where x=2y+3z-5) assists cathode material of UC0O2 (further referred to as LCO) to achieve a high capacity of 170mAh/g at 4.4V. In "Electrochemical and Solid-State Letters, 11 (6), A97-A100, 2008", a high capacity at elevated voltage is achieved with the assistance of 0.01Li3PO4-0.63Li2S-0.36SiS2 sulfide glass electrolytes. The combination of high voltage cathode material and solid electrolyte is expected to be useful in applications requiring a high energy density. Besides, the use of solid electrolytes can simplify the battery structure and reduce the number of safeguards in the battery design, which lower the energy density when using liquid electrolyte.

Despite its promising characteristics there are still big limitations to a practical application, the biggest disadvantage of solid-state lithium ion batteries being the low power density. This is considered to be caused by the low ionic conductivity of solid electrolytes, as well as a large charge transfer resistance between solid electrolytes and cathode materials. Currently, many published studies have attempted to improve the bulk conductive properties of various solid electrolytes, like glass electrolyte and polymer electrolyte. Polymer electrolytes are flexible and easy for making close contact between electrolyte and electrodes, but their ionic conductivity and transport number of lithium ions are not satisfying. Glass electrolytes have a relatively high ionic conductivity. U2S-P2S5 glass ceramic was proposed as one of the most promising solid electrolyte systems in "Advanced Material, 17, 918, 2015". This literature indicated 70Li₂S-30P₂S5 showing a good stability against both electrodes at high voltage, and having a high conductivity of 3.2x 10 ³ S/cm, which is greater by three orders of magnitude than the conventional Upon thin film solid electrolyte. However, a drawback has still remained hidden, which is that the power densities of solid-state lithium batteries are not comparable with that of organic-solvent liquid electrolytes, in spite of the high ionic

conductivities. To further solve this issue, the charge-transfer resistance at the electrode/electrolyte interface has to be considered, especially for the

cathode/electrolyte interface. This parameter is essential to fabricate high power density batteries, because the rate of charge transfer at the electrode/electrolyte interface directly relates to the battery performance. A few investigations have focused on this topic.

Most of the prior art tried to reduce the charge-transfer resistance at the positive electrode/solid electrolyte interface by providing a buffer or contacting layer on top of the positive electrode. In WO2015-050031 Al, a layer of Li ion conductive oxide is coated on the cathode, particularly LiNb03, U BO2, etc. In WO2015-045921 Al, an active substance layer is applied on the surface of the positive electrode, which comprises positive active material, solid electrolyte and a conduction auxiliary agent. US7993782 B2 disclosed a layer comprising Li ion conductive titanium oxide interposed between cathode material and sulfide electrolyte, to avoid the formation of a high resistance layer at a potential of 4V or more. The above prior art presents the advantage of reducing the interfacial charge transfer resistance, which may lead to improved power performance in solid state batteries, but this has not been proved in their publications.

The charge-transfer resistance at the cathode/electrolyte interface can be decreased not only by adding a conductive surface layer, but also by increasing the contacting area between cathode and electrolyte, which can be understood as requiring a high specific surface area for the cathode particles and a close contact between cathode particle and electrolyte. Normally, a high specific surface area is achieved by providing small particles or porous big particles. But in the case of solid state lithium ion batteries, a small particle size of cathode material would result in a low packing density, which further cuts down the energy density; combined with the consumption of large amounts of electrolyte, which may raise the cost. The use of big porous particles makes it difficult to avoid inner pores, which may result in a poor contact with the electrolyte. Thus, it is necessary to provide a new model of particle morphology of cathode material to increase the specific surface area and finally satisfy the power demand of solid state lithium ion batteries. This is also the target of this invention.

More specifically, this invention aims to develop a cathode material having a large bulk particle size and high BET, which provides excellent power performance when applied in solid state lithium ion batteries. Summary

Viewed from a first aspect, the invention can provide the following product embodiments:

Embodiment 1 : A lithium transition metal oxide powder for a positive electrode material in a solid-state lithium ion battery, the powder consisting of particles having a core and a surface layer consisting of an inner and an outer layer, wherein the powder has a D50 between 35 and δθμιτι, wherein the core has the general formula Li_xCo02 with 0.99<x< 1.04, and wherein the inner surface layer comprises LiyNii a-bMnaCOb02, with 0<y< l, 0.3<a<0.8 and 0<b<0.3; and wherein the outer surface layer consists of discrete monolithic sub-micron sized particles having the general formula Lii+z(Nii m-nMnmCon) i-z02, with 0<z≤0.05, 0<m <0.50 and

0<n<0.70. Here it may also be that 0<n<0.30, since Co is a costly metal.

Embodiment 2 : The lithium transition metal oxide powder, wherein 0.20<y<0.60, 0.45<a<0.60 and 0.05<b≤0.15.

Embodiment 3 : The lithium transition metal oxide powder, wherein 0<z<0.03, 0.25≤m<0.35 and 0.15≤n<0.25.

Embodiment 4: The lithium transition metal oxide powder may have a BET value that is at least twice the BET value of the core material before the application of the surface layer.

Embodiment 5 : The lithium transition metal oxide powder of embodiment 4, having a BET value of at least 0.20m²/g.

Embodiment 6 : The lithium transition metal oxide powder, wherein the core may further comprise up to 5 mole% of a dopant A, with A being either one or more elements of the group consisting of Al, Mg, Ti, Cr, V, Fe and Ga.

Embodiment 7 : The lithium transition metal oxide powder, wherein the surface layer may further comprise up to 5 mole% of a dopant A', with A' being either one or more elements of the group consisting of A, F, S, N, Ca, Sr, Y, La, Ce and Zr, with A being either one or more elements of the group consisting of Al, Mg, Ti, Cr, V, Fe and Ga.

Embodiment 8 : The lithium transition metal oxide powder, wherein the inner surface layer may consist of a multitude of islands densely sintered to the core material, the islands being Mn and Ni rich islands have a thickness of at least lOOnm and covering less than 70% of the surface of the core. Preferably the Mn and Ni rich islands bearing core comprises at least 10 mole% of both Ni and Mn. Each of the individual product embodiments described hereabove can be combined with one or more of the product embodiments described before it.

Viewed from a second aspect, the invention can provide the following method embodiments:

Embodiment 9 : A method for preparing the lithium transition metal oxide powder according to the invention, comprising the steps of: - providing a first mixture of lithium carbonate and C03O4, with a molar ratio of Li : Co between 1.07 : 1 and 1.12: 1,

- firing the first mixture at a temperature between 950 and 1050°C, for 8 to 24 hours under air, thereby obtaining a core material having a D50 value between 35 and 60μιη,

- providing a second mixture of the core material and either a first Li-Ni-Mn-Co- oxide, or a set of a Ni-Mn-Co precursor powder and a Li-precursor compound,

- sintering the second mixture at a temperature of at least 900°C for 1 to 48hrs,

- providing a second lithium nickel-manganese-cobalt oxide powder having the general formula Lii+z(Nii-_m-nM nmCon)i-z02, with 0≤z<0.05, 0<m <0.40 and

0<n<0.30,

- reducing the D50 value of the second lithium nickel-manganese-cobalt oxide powder below Ιμιη, and

- mixing the second lithium nickel-manganese-cobalt oxide powder with the sintered second mixture, and heating the obtained (third) mixture at a temperature between 750 and 850°C for 3 to 10 hours. When the first mixture is fired at temperatures of 1000°C or more, a loss of Li of 2-4% is to be expected. The PSD of the particles that constitute the outer surface layer can be influenced by the process conditions, where the desired increase of the BET value is the essential feature. The method could also be applied to core materials having the general formula Lii+z'(Nii_-m'-n'M nm'Con')i-zO2, with 0≤z'<0.05, 0<m'<0.50 and 0<n'<0.70, preferably 0<n'<0.30.

Embodiment 10: The method wherein the sintered first mixture consists of Mn and Ni bearing UC0O2 particles, said particles having Mn and Ni enriched islands on their surface, said islands comprising at least 5 mole% of Mn.

Embodiment 11 : The method wherein the D50 value of the second lithium nickel- manganese-cobalt oxide powder is reduced to a value between 100 and 200nm. Embodiment 12: The method according wherein the quantity of second lithium nickel-manganese-cobalt oxide powder is between 3 and 10wt% of the sintered second mixture.

Viewed from a third aspect, the invention can provide a rechargeable solid-state lithium ion battery comprising the lithium transition metal oxide powder of the invention. The solid-state battery may comprise lithium phosphorous oxy-nitride electrolytes, or sulfide glass system electrolyte with the general formula

a"Li3P04-b"Li₂S-c"SiS2, with a"+b"+c"=l, or LisS-PzSs glass ceramics.

Brief description of the drawings

Figure 1 : SEM images of Cexl ((a) and (b)) and Exl ((c) and (d))

Figure 2 : SEM image of NMC powder

Figure 3 : SEM images of PVDF-modified Cexl (a) and Exl(b)

Figure 4 : Cyclability of Exl and Cexl Detailed description

This invention discloses a cathode powder for solid state batteries. The bulk of the cathode particles is dense and has a high ionic conductivity, thus the bulk of the cathode contributes to the transport of Li across the electrode. There is less requirement for the electrolyte itself to transport lithium and a higher power can be achieved. The larger the particles, the more transport will be facilitated by the cathode. Large dense particles naturally have a small surface area, and the charge transfer of Li ions between electrolyte and cathode will occur across this surface. However, in solid state batteries the charge transfer reaction often is slow and rate- limited. The charge-transfer resistance will be less if the surface area is increased. There are many different morphologies which create an increased surface area.

Most desired is a morphology which increases the surface area but still allows for a relatively straight conduction path of lithium into the inner of the particle. Desired are "structured" morphologies resembling that of tire profiles, studs, mountain- valleys, mushrooms etc. Less desired are porous shells and spikes because the Li diffusion paths into the interior of the particle are too long, or because there is poor or only partial contact between the electrolyte and the cathode surface.

In the following LCO stands for LixCoCh and N MC stands for Lii_+z(NirMnrCot)i-z02, with r+s+t=l . This invention provides nickel-manganese-cobalt-coated lithium cobalt oxide powders having a large bulk particle size and a high BET (Brunauer- Emmett-Teller) value, which is induced by the surface modification through the coating with small NMC particles. The large bulk particle size is believed to provide close contact with the solid state electrolyte, without consuming too much of the electrolyte when the powder is applied as cathode material in the rechargeable solid-state lithium ion battery. The good ionic conductivity of bulk particles and high specific surface area provide an excellent power property that is required and desired in solid state batteries. Therefore, this cathode material is promising for the application of rechargeable solid-state lithium ion battery.

This invention discloses NMC-coated L1C0O2 powders consisting of a core and a (double) surface layer, where the core has the general formula of Li*Co02,

0.99<x< 1.04; where the surface layer consists of an inner and an outer layer, the inner layer having the formula Li_yNii-a-bMn_aC0b02, with 0<y< l, 0.3<a<0.8 and 0<b<0.3, provided by coating the core with NMC-precursors, followed by firing, and where the outer layer comprises monolithic - massive, solid and uniform - sub- micron sized lithium nickel-manganese-cobalt oxide powder (having a D50 <1μπι), forming the outer surface layer and being dispersed on top of the inner surface layer. The powder according to the invention is thus a monolithic N MC-coated and surface-modified LCO. The outer surface layer is believed to play an important role to increase the specific surface area of the powders of the invention, which is reflected in the high BET value. In an embodiment, the outer layer is a coating with 5wt% of monolithic Lii.o2(Nio.5oM no.3oCoo.2o)o.9e02 powder, which has a particle size expressed by the D50 value close to 200nm (between 150 and 250nm) or even close to lOOnm (for example between 75 and 125nm). The BET value of the obtained powder is twice the value of an LCO sample without such coating. The increased BET can reduce the charge transfer resistance and further result in an improved power performance. In an embodiment, coin cells based on cathode materials with higher BET value show a much greater remaining capacity at high current rate. Thus, the outer layer coating with sub-micron sized NMC is beneficial to improve the rate capability.

The authors believe that a large particle size of the cathode material is a

prerequisite to solid state cells, which can reduce the consumption of electrolyte and have a good electrical contact with electrolyte particles. However, the large particles of cathode material lead to long diffusion paths for the lithium ions, which may result in poor rate performance. Thus, it is inevitable to make a compromise between size and power, which is highly related to the composition, which includes the Li : Co ratio of the core compound. In the case of LCO powder, the particle size is mainly determined by the sintering temperature and the Li : Co ratio. Higher temperatures and a greater ratio are favorable for larger particle sizes. In an embodiment, the sintering temperature is set as 1000°C and the Li : Co ratio is chosen as 1.09 : 1 to guarantee a mean particle size of around 50pm . A dry coating followed by a heat treatment by NMC-precursors is applied to correct the Li : M (M = metal) ratio close to 1 : 1, thereby optimizing the rate performance. As an example, if the 1^st powder has a composition Lii.osCoC +x and we add 0.05 mole MOx (M=transition metal like Nio.sMno.s) then we obtain a stoichiometric Li : M = l : l compound UC0O2- U MO2. The amount of NMC-precursor is controlled to optimize the power and to avoid too much decomposition of large particles. If too much NMC-precursor is used, too many lithium ions from the LCO core-particles may diffuse to form lithiated nickel-manganese-cobalt oxide particles, so that the LCO structures may be crushed and large monolithic LCO particles may be decomposed. On the other hand, if the Li : Co ratio is too high the rate performance deteriorates.

In an embodiment, for the inner surface layer, 5 mole% of NMC precursor is applied to coat the core obtained from firing particles having the formula U1.09C0O2. During heat treatment Co diffuses into the Li-Me-oxide (Me=Ni-Mn-Co) particles and Ni and Mn can diffuse into the core. As a result the core is still mainly UC0O2 but some doping can happen. Particularly it is possible that a minor doping of the core with Ni and Mn further increases the high ionic conductivity of the core.

As a result of the NMC coating and sintering, a high power cathode material is obtained which consists of a core and provides the inner surface of the final cathode material.

The authors observe that in the coating step of the outer surface layer, the size of monolithic NMC powders and sintering temperature are appropriate parameters to determine the morphology of the final coated product. NMC powders have to be small enough to get them uniformly dispersed on the (outer) surface of the cores.

The temperature of sintering NMC powders on the pristine or coated LCO cores has to be optimized. If the temperature is too high, there would be too much diffusion of NMC particles into the cores; if the temperature is too low, the NMC particles cannot attach to the surface. The following gives detailed description of analysis method.

PSD test

The median particle size (D50) of the precursor compound is preferably obtained by a laser particle size distribution measurement method. In this description, the laser volumetric particle size distribution is measured using a Malvern Mastersizer 2000 with Hydro 2000MU wet dispersion accessory, after dispersing the powder in an aqueous medium . In order to improve the dispersion of the powder in the aqueous medium, sufficient ultrasonic irradiation, typically 1 minute for an ultrasonic displacement of 12, and stirring, are applied and an appropriate surfactant is introduced. The span is (D90-D10)/D50.

SEM test

In this invention, the morphology of powders is analyzed by scanning electron microscopy. This measurement is conducted by JEOL JSM 7100F scanning electron microscope equipment under vacuum of 9.6x10 ⁵ Pa at 25°C. The images of the sample with various magnifications are taken to reveal the sample morphology and microstructure.

BET test

The specific surface area is measured with the Brunauer-Emmett-Teller (BET) method using a Micromeritics Tristar 3000. The material is degassed in vacuum at 300°C for 1 hour prior to the measurement, in order to remove adsorbed species.

Simulated solid state coin cell preparation

In order to simulate the performance of cathode material according to the invention in a solid state battery, a layer of polyvinylidene fluoride (PVDF, KF polymer L #9305, Kureha America Inc.) is coated on the surface of the cathode material followed by a heat treatment. During the heat treatment the PVDF decomposes and forms an inorganic film of LiF. We use this Li F film to model the solid electrolyte (or buffering layer + electrolyte) of the solid-state battery. The following steps describe the coating and electrode making process: 0.3wt% PVDF is blended with cathode material for 5 hours by a dry mixing process and then fired at 375°C for 5 hours under atmosphere. The calcined product is used to prepare a positive electrode in a coin cell. 99wt% of the prepared PVDF coated active materials and lwt%

conductive carbon black (Super P, Erachem Comilog Inc.) are intimately grinded in a mortar for 5mins. 500mg of mixture is then pelletized under 5N for lmin. The obtained pellet serves as positive electrode in the coin cells, that are prepared to measure the electrochemical properties of the cathodes prepared by a standard coating process. These measurements confirm that the cathode material of this invention - despite having very large dense particles - has an excellent rate power performance. The coin cells are prepared to be tested under conditions which are more relevant for solid state battery operation.

The coin cells are prepared as follows: the positive electrode is 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 few drops of a 1M solution of LiPFe dissolved in a mixture of ethylene carbonate and dimethyl carbonate in a 1 : 2 volume ratio (origin : Techno Semichem Co.).

Coin cell test

In this invention, the coin cells are cycled at 25°C using Toscat-3100 computer- controlled galvanostatic cycling stations (from Toyo). The simulated solid state coin cell testing schedule used to evaluate Exl and Cexl (see below) is detailed in Table 1. The schedules use a 1C current definition of 160mA/g and comprise three parts:

(i) Part I is the evaluation of rate performance at 0.1C, 1C, 2C and 3C in the 4.3~3.0V/Li metal window range. With the exception of the 1^st cycle where the initial charge capacity CQ1 and discharge capacity DQ1 are measured in constant current mode (CC), all subsequent cycles feature a constant current-constant voltage during the charge with an end current criterion of 0.05C. A rest time of 30 minutes for the first cycle and 10 minutes for all subsequent cycles is allowed between each charge and discharge. The irreversible capacity Qirr. is expressed in % as:

(CQ1 - DQ1)

Qirr. = _{CQ 1} ^{X 10}° (^%)

The rate performance at 1C, 2C and 3C is expressed as the ratio between the retained discharge capacity DQn, with n=2, 3 and 4 for respectively nC=lC, 2C and 3C as follows:

DQn

nC— rate = x 100 (%)

DQ1

For example, rate

' 3C - (in%) =—DQl x 100 (ii) Part II is the evaluation of cycle life at IC. The charge cutoff voltage is set as 4.5V/U metal. The discharge capacity at 4.5V/U metal is measured at 0.1C at cycle 5 (DQ5) and IC at cycle 6. Capacity fadings at 0.1C and IC are calculated as follows and are exp

Energy fadings at 0.1C and IC are calculated as follows and are expressed in % per 100 cycles. Vn is

(iii) Part III is an accelerated cycle life experiment using IC-rate for the charge and IC rate for the discharge between 4.5 and 3.0V/Li metal. Capacity and energy fading are calculated as follows:

Table 1. Schedule of simulated solid state coin cell test

Cexl is also measured with a normal coin cell testing schedule which is detailed in Table 2. This test aims to evaluate the power performance of non-aqueous liquid electrolyte cells. The rate capability is calculated following the same procedure as described in "Coin cell test-(i) Part I". The normal coin cell is prepared following the description in "Simulated solid state coin cell preparation", but the positive electrode is prepared through a different process: An NMP (% N-methyl-2- pyrrolidone from Sigma-Aldrich) based slurry containing 83.3wt. % of active cathode material, 8.3wt. % polyvinylidene fluoride polymer (KF polymer L #9305, Kureha America Inc.), and 8.3wt% of conductive carbon black (Super P, Erachem Comilog Inc.) (wt%= solid content) is prepared by intimately mixing at high speed the solids into the NMP homogenizers. The slurry is then spread in a thin layer (typically about 100 micrometer thick) on an aluminum foil by a tape-casting method. After evaporating the NMP solvent, the cast film is processed through a roll-press using a 15 micrometer gap. The active material loading is small (about 3.5g/cm²) to limit lithium plating/stripping effects and thus allowing testing at high discharge rates. Electrodes are punched from the film using a circular die cutter measuring 14mm in diameter. The electrodes are then dried overnight at 90°C and ready to be assembled in a coin cell.

Table 2. Schedule of normal coin cell test

The invention is further illustrated in the following examples:

Example 1

This example presents NMC coated LCO powders consisting of large size coated cores of L11.09C0O2 and small size surface particles of NMC 532 according to the invention. The detailed preparation procedure is described below:

(1) Preparing large particle size U 1.09C0O2: Lithium carbonate and cobalt oxide (C03O4) are homogenously blended by a dry powder mixing process, following the molar ratio of Li :Co 1.09 : 1. After blending, the mixtures are fired at 1000°C for 12 hours in a box furnace under air atmosphere. The sintered product is milled in a grinding machine and sieved to a particle size distribution with a D50 of around 50μιτι, and a span of around 1. The sieved powders are named PI .

(2) 1^st dry coating with NMC particles: N MC-precursors with the formula of

Nio.55M no.3oCoo.i500H are mixed with PI in a tubular mixing machine in a dry powder mixing process. The molar ratio of NMC to PI is set at 1 : 20. After mixing, mixtures are sintered at 1000°C for 12 hours under air atmosphere. The sintered product is milled in a coffee machine for 30 seconds to eliminate agglomerates.

(3) Preparing small particle size of NMC 532: A premixed Ni-Mn-Co carbonate with a molar ratio of Ni : Mn :Co as 0.5 :0.3 :0.2 is blended with lithium carbonate in a tubular mixing machine by a dry powder mixing process. The molar ratio of lithium source to metal precursor is 1.02: 1. After mixing, the mixtures are sintered at 850°C for 10 hours under dry air. The fired powders are post-treated in a grinding machine to obtain nanosized powders. This final NMC powder is named P2.

(4) 2^nd dry coating with P2 : 5wt% of P2 from step (3) is homogeneously mixed with powders from step (2) by a dry powder mixing process. After mixing, the mixtures are sintered at 800°C for 5 hours under 10 L/min of dry air flow. The sintered product is then post-treated in a grinding machine to eliminate agglomerates. This final coated sample is named Exl .

Counter Example 1

This example uses LiCoCh-based powder obtained from step (2) in Example 1, and is labelled Cexl.

Discussion of Example 1 and Counter Example 1 :

Table 3 lists D50 and BET of PI from the first preparation step of Example 1 (large particle size U 1.09C0O2), Cexl and Exl. Comparing the D50 of these three samples, there is a small decrease of particle size from PI to CExl, which indicates that the 1^st coating with Nio.55M no.3Coo.i500H succeeds to correct the Li : M ratio without crushing or decomposing the large particle. The same phenomenon is observed in the 2^nd coating with sub-micron sized monolithic NMC powders. This coating step provides the positive effect of creating a structured surface, thus increasing the BET. Table 3 shows that Exl has a BET value that is twice the value of Cexl. SEM images (a) and (b) in Figure 1 show the morphology of Cexl (with different magnification), while (c) and (d) present Exl. Image (b) clearly shows the coating of small particles of NMC from step (2) in the description of Example 1. Compared to image (b), there are more small particles on the surface in image (d) - which are NMC powders from step (3) of Example 1, and the size of these small particles is around 200nm. The SEM image of these NMC powders (P2) is presented in Figure 2. The coating of these nanoparticles leads to the improvement of the BET of Exl. Furthermore, the larger value of BET may result in a better power performance of Exl. Table 3. Physical properties of Exl .

Figure 3 shows the SEM images of the cathode materials obtained by the PVDF coating route described above. Image (a) presents the surface morphology of PVDF coated Cexl and image (b) belongs to PVDF coated Exl . In the pictures, a scalelike coating layer is shown on the surface of bulk materials, which is believed to be the layer of PVDF used for the simulation of the solid-state coin cells. Table 4 summarizes the charge capacity, discharge capacity and irreversible capacity percentage during the first cycle, which is cycled at 3.0 to 4.3V, and the discharge capacity cycled at the range of 3.0 to 4.5V, as well as rate capability at 1C, 2C and 3C, for Exl and Cexl . Compared with Cexl, the retaining capacities at different current rates of Exl are all higher, especially at high rates like 3C, where the improvement is more obvious, which confirms the contribution of the high BET value of Exl. Exl has also good capacity properties. In Table 4, CQl, DQl and DQ5 of Exl are greater than the values of Cexl, while Qirr of Exl is smaller than that of Cexl, which indicates that the coating with sub-micron NMC 532 particles may also contribute to enhance the capacities.

Table 4. Rate capability of Exl and Cexl in simulated solid state coin cell

Table 5 shows the capacity and energy fading of Exl and Cexl during cycling. For all the fading parameters, a coin cell based on Exl shows less fade when compared with Cexl, thus Exl has better cyclability. Figure 4 shows the cycling behaviour of Exl and Cex 1. Table 5. Cyclability of Exl and Cexl

Table 6 lists the rate capability of Cexl which is tested in a normal coin cell following the schedule detailed in Table 2. In Table 6, the capacity retention of Cexl at 1C, 5C, IOC, 15C and 20C is summarized. The discharge capacity at 0.1C is set to 100%. The value at 1C is about 96%. When increasing the capacity rate to 20C, there is no big drop of capacity, even at 20C, the capacity retention is still above 80%. Generally speaking, this rate performance is excellent and quite acceptable for high power application.

Table 6. Rate capability of Cexl in non-aqueous liquid electrolyte coin cell

According to the above discussion, Cexl, which is manufactured with only the 1^st dry coating step, has good power performance, but possesses low BET and poor surface contact with solid electrolyte that is mimicked by a Li F layer in this invention. Thus, Cexl presents non-satisfying power properties in the simulated solid state coin cell test. By coating with the 2^nd layer of monolithic sub-micron sized NMC 532, sample Exl exhibits a higher BET, better rate capability and cyclability, compared with Cexl . The good rate performance of Exl is considered as a promising property for the application in a solid state battery. Thus, Exl can be a candidate cathode material for use in a rechargeable solid-state lithium ion battery.

Claims

1. A lithium transition metal oxide powder for a positive electrode material in a solid-state lithium ion battery, the powder consisting of particles having a core and a surface layer consisting of an inner and an outer layer, wherein the powder has a D50 between 35 and 60μιη, wherein the core has the general formula LixCoCte with 0.99<x<1.04 and wherein the inner surface layer comprises Li_yNii-a-bMn_aC0b02, with 0<y< l, 0.3<a<0.8 and 0<b<0.3; and wherein the outer surface layer consists of discrete monolithic sub-micron sized particles having the general formula

Lii+z(Nii-m-nM n_mCon) i-z02, with 0≤z≤0.05, 0<m<0.50 and 0<n≤0.70.

2. The lithium transition metal oxide powder of claim 1, wherein 0.20<y<0.60, 0.45<a<0.60 and 0.05<b<0.15.

3. The lithium transition metal oxide powder of claim 1, wherein 0<z<0.03, 0.25≤m<0.35 and 0.15≤n<0.25.

4. The lithium transition metal oxide powder of claim 1, having a BET value that is at least twice the BET value of the core material before the application of the surface layer.

5. The lithium transition metal oxide powder of claim 4, having a BET value of at least 0.20m²/g-

6. The lithium transition metal oxide powder of claim 1, wherein the core further comprises up to 5 mole% of a dopant A, with A being either one or more elements of the group consisting of Al, Mg, Ti, Cr, V, Fe and Ga.

7. The lithium transition metal oxide powder of claim 1, wherein the surface layer further comprises up to 5 mole% of a dopant A', with A' being either one or more elements of the group consisting of A, F, S, N, Ca, Sr, Y, La, Ce and Zr.

8. The lithium transition metal oxide powder of claim 1, wherein the inner surface layer consists of a multitude of islands densely sintered to the core material, the islands being Mn and Ni rich islands have a thickness of at least lOOnm and covering less than 70% of the surface of the core.

9. A method for preparing the lithium transition metal oxide powder of claim 1, comprising the steps of:

- providing a first mixture of lithium carbonate and C03O4, with a molar ratio of Li : Co between 1.07 : 1 and 1.12: 1,

- firing the first mixture at a temperature between 950 and 1050°C, for 8 to 24 hours under air atmosphere, thereby obtaining a core material having a D50 value between 35 and 60pm,

- providing a second mixture of the core material and either a first Li-Ni-Mn-Co- oxide, or a set of a Ni-Mn-Co precursor powder and a Li-precursor compound, - sintering the second mixture at a temperature of at least 900°C for 1 to 48hrs,

- providing a second lithium nickel-manganese-cobalt oxide powder having the general formula Lii+_z(Nii _m nM n_mCo_n) i z0₂, with 0≤z<0.05, 0<m <0.40 and

0<n≤0.30,

- reducing the D50 value of the second lithium nickel-manganese-cobalt oxide powder below lpm, and

- mixing the second lithium nickel-manganese-cobalt oxide powder with the sintered second mixture, and heating the obtained mixture at a temperature between 750 and 850°C for 3 to 10 hours.

10. The method according to claim 9, wherein the sintered first mixture consists of Mn and Ni bearing L1 C0O2 particles, said particles having Mn and Ni enriched islands on their surface, said islands comprising at least 5 mole% of Mn.

11. The method according to claim 9, wherein the D50 value of the second lithium nickel-manganese-cobalt oxide powder is reduced to a value between 100 and

200nm.

12. The method according to claim 9, wherein the quantity of second lithium nickel- manganese-cobalt oxide powder is between 3 and 10wt% of the sintered second mixture.

13. A rechargeable solid-state lithium ion battery comprising the lithium transition metal oxide powder of claim 1.