Material consisting of composite oxide particles, method for preparing same, and use thereof as electrode active material

Patent metadata

Field	Value
Publication number	US-9431675-B2
Application number	US-201013394665-A
Country	US
Kind code	B2
Filing date	Sep 15, 2010
Priority date	Sep 15, 2009
Publication date	Aug 30, 2016
Grant date	Aug 30, 2016

Abstract

A positive electrode material, having particles having a complex oxide OC1 core, an at least partial complex oxide OC2 coating, and an adhesive carbon surface deposit. The material is characterized in that the complex oxide OC1 is an oxide having a high energy density and in that the oxide OC2 is an oxide of a metal having a catalytic effect on the reaction of the carbon deposit, the oxide having good electronic conductivity. The presence of the OC2 layer facilitates the deposit of a carbon adhesive layer at the surface of the oxide particles, and improves the conductivity of the material when the latter is used as an electrode material. The electrode material can particularly be used in the manufacture of a lithium battery.

First claim

The invention claimed is:

1. A positive electrode material composed of particles having a core of a complex oxide CO1, an at least partial coating of a complex oxide CO2 and an adherent surface deposit of carbon, wherein:
the complex oxide CO1 has a potential of greater than 2.5 V and comprises a first alkali metal and at least one metal selected from the group consisting of Mn, Co, Ge, Au, Ag and Cu, and
the oxide CO2 comprises a second alkali metal and at least one metal selected from the group consisting of Fe, Mo, Ni, Pt and Pd; and
wherein the core of oxide CO1 has a mean size from 20 nm to 100 μm, the coating of oxide CO2 has a thickness from 1 nm to 6 μm and the carbon deposit has a thickness from 0.1 nm to 100 nm.

2. The material as claimed in claim 1 , wherein the first alkali metal is chosen from Li, Na and K.

3. The material as claimed in claim 2 , wherein the first and second alkali metals are the same.

4. The material as claimed in claim 1 , wherein the oxide CO1 is an oxide A z M 1 (1-a) M 2 a XO 4 in which M 1 represents at least one metal selected from the group consisting of Mn, Co, Cu and Ge, M 2 represents a transition metal other than Mn and Co, 0≦a≦0.5, 0≦z≦2 and X represents an element selected from the group consisting of P, Si, V and Ti.

5. The material as claimed in claim 4 , wherein the oxide CO1 is LiMnPO 4 in which Mn can be partially replaced by Co and/or Ni.

6. The material as claimed in claim 1 , wherein the oxide CO2 is:
LiFeBO 3 ; or
oxides A z M 3 (1-b) M 4 b X′O 4 and oxides A x [M 3 (1-c) M 4 c ) 2 (X″O 4 ) 3 ] in which M 3 represents at least one metal selected from the group consisting of Fe, Mo, Pt and Pd, M 4 represents a transition metal other than M 3 , 0≦b≦0.5, 0≦c≦0.5, 0≦x≦3, 0≦z≦2, and X′ or X″ represents at least one element selected from the group consisting of P, Si, S, V, Ti and Ge.

7. The material as claimed in claim 6 , wherein the oxide CO2 is selected from the group consisting of LiFePO 4 , LiFeVO 4 , Li 2 FeSiO 4 , LiFeTiO 4 and Li 2 FeGeO 4 .

8. A process for the preparation of a material as claimed in claim 1 , wherein it comprises the following stages:
a) preparation of particles of oxide CO from its precursors;
b) introducing the particles of oxide CO1 into a solution of precursors of the oxide CO2 and carrying out a heat treatment in order to bring about the reaction of the precursors of the oxide CO2;
c) bringing the particles of oxide CO1 carrying a coating of oxide CO2 into contact with an organic precursor of carbon and carrying out a heat treatment so as to reduce the organic precursor to carbon.

9. The process as claimed in claim 8 , wherein the preparation of the CO1 particles in stage a) is carried out by a process consisting in at least partially dissolving the precursors in a carrier liquid, in applying a heat treatment in order to bring about the reaction of the precursors and to give rise to the precipitation of the oxide CO1, in allowing the reaction medium to cool, in recovering the particles, in washing them and in drying them.

10. The process as claimed in claim 9 , wherein the heat treatment is carried out at a temperature of between 120° C. and 250° C.

11. The process as claimed in claim 8 , wherein the heat treatment of stage b) is carried out at a temperature of between 120° C. and 250° C.

12. The process as claimed in claim 8 , wherein stage c) is carried out according to one of the following methods:
pyrolysis of an organic precursor chosen from hydrocarbons and their derivatives, polyhydric compounds and polymers;
bringing the complex particles resulting from stage b) into contact with a compound which has one or more carbon-halogen bonds and reducing said compound at low or moderate temperatures below 400° C.;
bringing the complex particles resulting from stage b) into contact with a compound which has one or more —CH—CY— bonds and eliminating the hydrogenated compound HY by a low-temperature reaction, according to the reaction scheme —CH—CY—+B=>—C═C—+BHY, in which Y denotes a halogen or a pseudohalogen and B denotes a base.

13. An electrode composed of a composite material deposited on a current collector, wherein said composite material comprises a material as claimed in claim 1 as active material.

14. The electrode as claimed in claim 13 , wherein the current collector is a metal stable toward oxidation chosen from aluminum, titanium and stainless steel.

15. The electrode as claimed in claim 13 , wherein the composite material comprises at least 60% by weight of active material, a binder and/or an additive which confers electronic conduction.

16. A battery comprising a positive electrode, a negative electrode and an electrolyte, in which the negative electrode is a sheet of lithium or of intermetallic lithium alloy, or a material capable of reversibly inserting lithium ions, and the electrolyte comprises at least one lithium salt in solution in a solvent which can be chosen from polar aprotic liquid solvents optionally gelled by addition of a polymer, and solvating polymers optionally plasticized by an aprotic liquid solvent, wherein the positive electrode is an electrode as claimed in claim 13 .

17. The process as claimed in claim 8 , wherein the oxide CO1 is an oxide of the formula A z M 1 (1-a) M 2 a XO 4 in which M 1 represents at least one element selected from Mn, Co, Cu and Ge, M 2 represents a transition metal other than Mn and Co, 0≦a≦0.5, 0≦z≦2 and X represents 15 an element chosen from P, Si, V and Ti.

18. The process as claimed in claim 8 , wherein the oxide CO1 is LiMnPO 4 in which Mn can be partially replaced by Co and/or Ni.

19. The process as claimed in claim 8 , wherein the oxide CO2 is selected from:
LiFeBO 3 ;
the oxides A z M 3 (1-b) M 4 b X′O 4 and the oxides A x [M 3 (1-c) M 4 c ) 2 (X″O 4 ) 3 ] in which M 3 represents at least one element chosen from Fe, Mo, Pt and Pd, M 4 represents a transition metal other than M 3 , 0≦b≦0.5, 0≦c≦0.5, 0≦x≦3, 0≦z≦2, and X′ or X″ represents at least one element selected from P, Si, S, V, Ti and Ge.

20. The process as claimed in claim 8 , wherein the oxide CO2 is selected from LiFePO 4 , LiFeVO 4 , Li 2 FeSiO 4 , LiFeTiO 4 and Li 2 FeGeO 4 .

Assignees

• Guerfi Abdelbast
• Labrecque Jean-François
• Dontigny Martin
• Charest Patrick
• Zaghib Karim
• Hydro Quebec

Inventors

• Guerfi Abdelbast
• Labrecque Jean-François
• Dontigny Martin
• Charest Patrick
• Zaghib Karim

Classifications

• H01M4/54

  of silver · CPC title

• H01M4/52 Primary

  of nickel, cobalt or iron · CPC title

• H01M4/1315

  containing halogen atoms, e.g. LiCoOxFy · CPC title

• H01M4/667

  in the form of layers, e.g. coatings · CPC title

• H01M4/366

  as layered products · CPC title