Fluorinated oxide based on Li and Mn

1. A process for preparation of particles of a Li-rich crystalline fluorinated layered oxide based on Mn, in which F is incorporated within a crystal of the Li-rich crystalline fluorinated layered oxide, the process consisting of incorporating fluorine into a number of oxygen vacancies of an oxygen-deficient oxide of formula (II):

[Li x Mn IV y Ni IV z Co IV w ]O 2-u   (II)

wherein:

0<x<⅔;

0<y≤⅔;

z≥0;

w≥0;

⅓<y+z+w≤⅔;

0<u<⅔;

to provide the Li-rich crystalline fluorinated layered oxide of formula (I):

[Li x Mn IV y Ni n′ z Co n″ w ]O 2-u F t   (I)

wherein:

0<x<⅔;

0<y≤⅔;

z≥0;

w≥0;

⅓<y+z+w≤⅔;

0<u<⅔;

0<t≤u;

x+4y+n′z+n″w=2(2−u)+t; and

n′ and n″ correspond to an average oxidation state of respectively Ni and Co, n′ ranging from +II to +IV and n″ ranging from +III to +IV, and

wherein the fluorine is provided by a fluorinating agent decomposed so as to generate a fluorinated reactive species.

2. The process according to claim 1 , wherein the process consists of contacting the oxygen-deficient oxide with an atmosphere comprising the fluorinated reactive species generated by thermal decomposition of the fluorinating agent.

3. The process according to claim 2 wherein the oxygen-deficient oxide and the fluorinating agent are placed in a confined vessel, the fluorinated agent being decomposed so as to generate the fluorinated reactive species.

4. The process according to claim 1 , wherein u is less than ½; or wherein ⅓≤y≤⅔; or wherein t=u; or wherein:

w=z=0; or

w=0; or

z=0; or

y=⅔ and w=z=0.

5. The process according to claim 1 , wherein the particles of the Li-rich crystalline fluorinated layered oxide are characterized by a D50 below 100 nm, D50 being the median diameter determined from a distribution (in volume) obtained by laser diffraction.

6. The process according to claim 1 , wherein the fluorinating agent is selected in the group consisting of HF, F 2 , XeF 2 , TbF 4 , CeF 4 , CoF 3 , AgF 2 , MoF 3 , AgF, CuF 2 , FeF 3 , CuF, VF 3 and CrF 3 or wherein the fluorinated agent is a fluorinated organic compound.

7. The process according to claim 1 , wherein the Li-rich crystalline fluorinated layered oxide exhibits an O1-type layered structure.

8. The process according to claim 1 , wherein the Li-rich crystalline fluorinated layered oxide is of formula Li x Mn 2/3 O 2-u F t ;

wherein:

0<x<⅔;

0<u<⅔;

0<t≤u.

9. The Li-rich crystalline fluorinated layered oxide based on Mn of formula (I):

[Li x Mn IV y Ni n′ z Co n″ w ]O 2-u F t   (I)

wherein:

0<x<⅔;

0<y≤⅔;

z≥0;

w≥0;

⅓<y+z+w≤⅔;

0<u<⅔;

0<t≤u;

x+4y+n′z+n″w=2 (2−u)+t;

wherein

n′ and n″ correspond to an average oxidation state of respectively Ni and Co, n′ ranging from +II to +IV and n″ ranging from +III to +IV, and

is obtained by the process according to claim 1 .

10. The Li-rich crystalline fluorinated layered oxide based on Mn of claim 9 , wherein the Li-rich crystalline fluorinated layered oxide is of formula (I):

[Li x Mn IV y Ni n′ z Co n″ w ]O 2-u F t   (I)

wherein:

0<x<⅔;

0<y≤⅔;

z≥0;

w≥0;

⅓<y+z+w≤⅔;

0<u<⅔;

0<t≤u;

x+4y+n′z+n″w=2 (2−u)+t;

and wherein n′ and n″ correspond to an average oxidation state of respectively Ni and Co, n′ ranging from +II to +IV and n″ ranging from +III to +IV, and

is characterized by the following ratio:

0< I LiF /I F ≤0.50,

wherein:

I LIF designates an intensity of a peak of LiF centered at a chemical shift between −200 ppm and −210 ppm;

I F designates an intensity of a peak of fluorine incorporated within the crystal of the Li-rich crystalline fluorinated oxide centered at a chemical shift between −140 ppm and −160 ppm;

wherein both the intensity of the peak of LiF and the intensity of the peak of fluorine are deduced from a spectrum being obtained by 19 F solid-state MAS NMR spectroscopy.

11. A cathode comprising a composite material comprising the Li-rich crystalline fluorinated layered oxide of claim 9 , at least one conductive material and optionally at least one polymer binder.

12. A battery comprising the cathode of claim 11 .