Process for preparing crystalline electrode materials and materials obtained therefrom

Patent metadata

Field	Value
Publication number	US-9871245-B2
Application number	US-201314399233-A
Country	US
Kind code	B2
Filing date	May 28, 2013
Priority date	May 29, 2012
Publication date	Jan 16, 2018
Grant date	Jan 16, 2018

Abstract

There is provided a process for preparing a crystalline electrode material, the process comprising: providing a liquid bath comprising the electrode material in a melted state; and introducing a precursor of the electrode material into the liquid bath, wherein the electrode material comprises lithium, a metal and phosphate. There is also provided a crystalline electrode material, comprising lithium substituted by less than 0.1 atomic of Na or K; Fe and/or Mn, substituted by less than 0.1 atomic ratio of: (a) Mg, Ca, Al and B, (b) Nb, Zr, Mo, V and Cr, (c) Fe(III), or (d) any combinations thereof; and PO 4 , substituted by less than 20% atomic weight of an oxyanion selected from SO 4 , SiO 4 , BO 4 , P 2 O 7 , and any combinations thereof, the material being in the form of particles having a non-carbon and non-olivine phase on at least a portion of the surface thereof.

First claim

The invention claimed is:

1. A process for preparing a crystalline electrode material, the process comprising:
providing a liquid bath comprising the electrode material in a melted state; and
introducing a precursor of the electrode material into the liquid bath, wherein the electrode material comprises lithium, a metal and phosphate,
the process being performed in a continuous or semi-continuous manner.

2. The process according to claim 1 , further comprising withdrawing a portion of the liquid bath and inducing solidification of the portion so as to obtain a solidified electrode material.

3. The process according to claim 2 , further comprising removing an impurity-containing portion from the solidified electrode material.

4. The process according to claim 2 , wherein said inducing solidification step comprises a cooling step, a casting step or an atomization step.

5. The process according to claim 2 , further comprising a pulverization step of the solidified electrode material so as to obtain particles of said solidified electrode material.

6. The process according to claim 1 , wherein the liquid bath is maintained at a temperature between the melting temperature of the electrode material and about 300° C. above the melting temperature so as to maintain the electrode material in said melted state.

7. The process according to claim 6 , wherein assisted convection is performed while maintaining the liquid bath at said temperature.

8. The process according to claim 5 , further comprising adding an organic source of carbon prior to, concomitant with, or after said pulverization step, and heating to obtain a carbon coating on at least part of the surface of the electrode material particles.

9. The process according to claim 1 , wherein said liquid bath comprises a first liquid and a second liquid, or a gas, or a solid, wherein said first liquid comprises said electrode material in the melted state and said first liquid is in thermodynamic equilibrium with said second liquid, or gas, or solid.

10. The process according to claim 9 , wherein said second liquid comprises Cu—Sn, Sn, or a Sn alloy.

11. The process according to claim 1 , wherein said precursor comprises a natural occurring source compound for the metal.

12. The process according to claim 11 , wherein the metal is iron or manganese and said natural occurring source is an oxide containing magnetite or hematite.

13. The process according to claim 1 , wherein the liquid bath is held in an enclosure, wherein at least a portion of the enclosure is made of graphite or graphite-silicon, alumina or zirconia.

14. The process according to claim 2 , wherein the precursor is introduced into the liquid bath at a rate which matches a rate of liquid withdrawing so as to maintain the liquid in the liquid bath at a generally constant level.

15. A crystalline electrode material prepared by the process of claim 1 , having an olivine structure, the material comprising lithium substituted by less than 0.1 atomic ratio relative to lithium of Na or K; a metal selected from Fe, Mn, and a mixture thereof, substituted by less than 0.1 atomic ratio relative to the metal of an atom selected from the group consisting of: (a) Mg, Ca, Al and B, (b) Nb, Zr, Mo, V and Cr, (c) Fe (III), and (d) any combinations thereof; and PO 4 , substituted by less than 20% atomic weight of a non-metal oxyanion selected from SO 4 , SiO 4 , BO 4 , P 2 O 7 , and any combinations thereof, wherein the material is in the form of particles, the particles having on at least a portion of the surface thereof a non-carbon and non-olivine phase.

16. The crystalline electrode material according to claim 15 , wherein the non-carbon and non-olivine phase is present at less than 15 wt. %, or less than 10 wt. %, or less than 5 wt. %-relative to the weight of the electrode material.

17. The crystalline electrode material according to claim 15 , said non-carbon and non-olivine phase comprising Si, Al, Zr or a combination thereof at a concentration of less than 5 wt. % relative to the weight of the electrode material and more than 500 ppm.

18. The crystalline electrode material according to claim 15 , further comprising a non-powdery adherent carbon coating on at least a portion of the surface of said particles, said coating being present at less than 15 wt. % by weight, or less than 10 wt. %, or less than 5 wt. % relative to the weight of the electrode material.

19. The crystalline electrode material according to claim 15 , wherein the electrode material comprises individual particles and agglomerates thereof, where the size of the individual particles is between about 10 nm and about 3 μm, and the size of agglomerates is between about 100 nm and about 30 μm.

20. The crystalline electrode material according to claim 15 , wherein the material has a nominal formula Li (Fe 1-x Mn x ) PO 4 , wherein 0≦x≦1.

Assignees

• Johnson Matthey Plc
• Univ Montreal
• La Corp De L'Ecole Polytechnique De Montreal
• Univ Montreal

Inventors

• Gauthier Michel
• Macneil Dean
• Wontcheu Joseph
• Chartrand Patrice
• Liang Guoxian

Classifications

• C01B25/45 Primary

  containing plural metal, or metal and ammonium · CPC title

• H01M4/5825 Primary

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title

• H01M4/366

  as layered products · CPC title

• H01M4/136 Primary

  Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title

• C01P2006/40

  Electric properties · CPC title