Sacrificial active material of a positive electrode for a lithium-ion electrochemical element

• US 11,563,212 B2
• Filed: 05/22/2018
• Issued: 01/24/2023
• Est. Priority Date: 06/20/2017
• Status: Active Grant

• Current Assignee: Centre National De La Recherche Scientifique, Ensicaen, SAFT SA (Totalenergies Se), Unicaen
• Original Assignee: SAFT SA (Totalenergies Se)
• Inventors: Jordy, Christian, Freire, Melanie, Pralong, Valerie
• Primary Examiner(s): Raymond, Brittany L
• Application Number:
  US16/624,632
• Publication Number:
  US 20200136140A1
• Time in Patent Office: 1,708 Days
• CPC Class Codes: C01G 45/1221 Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
• CPC Class Codes: C01G 45/1278 of the type [Mn2O7]n-, e.g. (Sr2-xNdx)Mn2O7, Tl2Mn2O7
• CPC Class Codes: C01G 45/1285 of the type [Mn2O5]n-
• CPC Class Codes: C01P 2002/60 Compounds characterised by their crystallite size
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/362 Composites
• CPC Class Codes: H01M 4/364 as mixtures
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A sacrificial positive active material for a lithium-ion electrochemical element which is a compound of formula (Li₂O)_x (MnO₂)_y(MnO)_z(MO_a)_t in which: x+y+z+t=1; 1−x−y≥0; 0.97≥x≥0.6; y≤0.45; x −0.17; y≥0; y+z>0; t≥0; 1≤a<3. M is selected from the group consisting of Fe, Co, Ni, B, Al, Ti, Si, V, Mo, Zr and a mixture thereof.

Claims

1. Nanostructured compound of formula (Li₂O)_x (MnO₂)_y (MnO)_z (MO_a)_t

wherein

x+y+z+t=1

1−

x−

y≥

0

0.97≥

x≥

0.6

y≤

0.45·

x−

0.17

y≥

0

y+z>

0

t≥

0

1≤

a<

3

M is selected from the group consisting of Fe, Co, Ni, B, Al, Ti, Si, V, Mo, Zr and a mixture thereof,

wherein the nanostructured compound has an X-ray diffraction pattern in which a width at mid-height of a line at a 2-theta angle between 40° and

45°

is greater than 1°

, a wavelength used being the Kalpha wavelength of copper.

2. Nanostructured compound according to claim 1, wherein x≥

0.7.

3. Nanostructured compound according to claim 1, wherein y=z +/−

0.05.

4. Nanostructured compound according to claim 1, wherein y≤

0.2.

5. Nanostructured compound according to claim 1, wherein z≤

0.4.

6. Nanostructured compound according to claim 1, wherein t=0.

7. Composite material comprising the nanostructured compound according to claim 1 and at least one crystalline phase Li₂O.

8. Composite material comprising the nanostructured compound according to claim 1 and containing from 1 to 10% by mass of carbon.

9. Electrode comprising a first electrochemically active material which is the nanostructured compound according to claim 1 and at least one second electrochemically active material.

10. Electrode according to claim 9, wherein the second electrochemically active material is selected from the group consisting of:

nanostructured compound i) of formula Li_xMn<sub>1−

y−

z</sub>M′

_yM″

_z PO₄ (LMP), where M′ and

M″

are different from each other and are selected from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo, with 0.8≤

x≤

1.2;

0≤

y≤

0.6;

0≤

z≤

0.2;

nanostructured compound ii) of formula Li_xM<sub>2−

x−

y−

z−

w</sub>M′

_yM″

_zM′

″

_wO₂ (LMO2), where M, M′

, M″ and

M′

″

are selected from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo, provided that M or M′

or M″

or M′

″

is selected from Mn, Co, Ni or Fe;

M, M′

, M″ and

M′

″

being different from each other;

with 0.8≤

x≤

1.4;

0≤

y<

0.5;

0≤

z≤

0.5;

0≤

w≤

0.2 and x+y+z+w<

2;

nanostructured compound iii) of formula Li_xMn<sub>2−

y−

z</sub>M′

_yM″

_zO₄ (LMO), where M′ and

M′

are selected from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo;

M′ and

M″

being different from each other, and 1≤

x≤

1.4;

0≤

y≤

0.6;

0≤

z≤

0.2;

nanostructured compound iv) of formula Li_xFe<sub>1−

y−</sub>

M_yPO₄, where M is selected from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo;

and 0.8≤

x≤

1.2;

0≤

y≤

0.6;

nanostructured compound v) of formula xLi₂MnO₃;

(1−

x)LiMO₂ where M is selected from Ni, Co and Mn and x≤

1;

and a mixture of one or more of the nanostructured compounds i) to v).

11. Electrode according to claim 10 comprising the nanostructured compound ii) and

M is Ni;

M′

is Mn;

M″

is Co and

M′

″

is selected from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo;

with 0.8≤

x≤

1.4;

0≤

y≤

0.5;

0≤

z≤

0.5;

0≤

w≤

0.2 and x+y+z+w<

2.

12. Electrode according to claim 10 comprising the nanostructured compound ii) and

M is Ni;

M′

is Co;

M″

is Al; and

1≤

x≤

1.15;

y>

0;

z>

0;

w=0.

13. Electrode according to claim 12 comprising the nanostructured compound ii) and

x=1;

0.6≤

2−

x−

y−

z≤

0.85;

0.10<

y≤

0.25;

0.05≤

z≤

0.15.

14. Electrode according to claim 10 comprising the nanostructured compound ii) of formula LiCoO₂.

15. Electrode according to claim 10 comprising the nanostructured compound iv) of formula Li_xFe₁₋

yM_yPO₄, wherein M is selected from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo; and

0.8≤

x≤

1.2;

0≤

y≤

0.6.

16. An electrode according to claim 15 comprising the nanostructured compound iv) of formula LiFePO₄.

17. Electrode according to claim 10 comprising the nanostructured compound iii) with x=1;

0≤

y≤

0.1;

z=0 and M′

is Al.

18. Electrode according to claim 10 comprising the nanostructured compound iii) of formula LiMn₂O₄.

19. Electrode according to claim 10, wherein the mass percentage of the nanostructured compound is less than or equal to 5% based on the total mass of all electrochemically active materials.

20. Electrochemical cell of lithium-ion type comprising an electrode according to claim 9, said electrode being a positive electrode.

21. Electrochemical cell according to claim 20, comprising:

at least one negative electrode comprising a graphite-based active material.

22. Electrochemical cell according to claim 20 comprising:

at least one negative electrode comprising an active material selected from the group consisting of tin, silicon, carbon and silicon based-compounds, carbon and tin based-compounds, carbon, tin and silicon based-compounds, and lithium titanium oxide compounds.

23. Process for manufacturing the nanostructured compound according to claim 1, comprising the steps of:

a) provision of a mixture of Li₂O, MnO, MnO₂ and optionally MO;

b) grinding the mixture in an inert atmosphere;

c) heating the mixture in an inert atmosphere at a temperature between 800 and 1000°

C.;

d) cooling of the mixture to room temperature;

e) grinding the mixture in an inert atmosphere;

f) optionally adding carbon to the mixture;

g) optionally grinding the mixture in an inert atmosphere.