CATHODE MATERIALS FOR LITHIUM ION BATTERIES

• US 20160260965A1
• Filed: 03/06/2015
• Published: 09/08/2016
• Est. Priority Date: 03/06/2015
• Status: Active Grant

• Current Assignee: UChicago Argonne LLC (University of Chicago)
• Original Assignee: UChicago Argonne LLC (University of Chicago)
• Inventors: Wu, Huiming, Amine, Khalil, Lu, Jun
• Granted Patent: US 10,833,321 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C01G 45/02 Oxides; Hydroxides
• CPC Class Codes: C01G 49/00 Compounds of iron
• CPC Class Codes: C01G 49/02 Oxides; Hydroxides C01G49/0018 takes precedence
• CPC Class Codes: C01G 51/04 Oxides; Hydroxides
• CPC Class Codes: C01G 51/42 containing alkali metals, e.g. LiCoO2
• CPC Class Codes: C01G 53/04 Oxides; Hydroxides
• CPC Class Codes: C01G 53/42 containing alkali metals, e.g. LiNiO2
• 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 4/04 Processes of manufacture in general
• CPC Class Codes: H01M 4/0419 involving spraying
• CPC Class Codes: H01M 4/0471 involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• 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 4/139 Processes of manufacture
• CPC Class Codes: H01M 4/1391 of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• 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 4/62 Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A process of forming a coated cathode active material include preparing a cathode material precursor by co-precipitation; coating the cathode material precursor with an electrochemically inert coating material precursor by precipitation to form a coated cathode material precursor; lithiating the coated cathode material precursor with a lithium source material to tern a lithiated coated cathode material precursor; and sintering the lithiated coated cathode material precursor to form a cathode active material coated with an electrochemically inert material.

Claims

1. A process of forming a coated cathode active material, the process comprising:

preparing a cathode material precursor;

coating the cathode material precursor with an coating material precursor to form a coated cathode material precursor;

lithiating or sodiating the coated cathode material precursor with a lithium or sodium source material to form a lithiated or sodiated coated cathode material precursor; and

sintering the lithiated sodiated coated cathode material precursor to form a cathode active material coated with a coating material.

2. The process of claim 1, wherein the preparing the cathode material precursor comprises co-precipitation or spray-drying.

3. The process of claim 1, wherein the preparing the cathode material precursor comprises:

providing an acidic solution of a metal ion and a basic solution;

combining the basic solution and the acidic solution to effect co-precipitation of the cathode active material precursor as a particle.

4. The process of claim 3, wherein a concentration of the metal ion is maintained at a substantially constant value during formation of the cathode active material precursor particle, such that the cathode active material precursor particle contains a substantially uniform metal concentration of the metal along a radius of the particle.

5. The process of claim 3, wherein a concentration of the metal ion is increased or reduced during formation of the cathode active material precursor particle such that the cathode active material precursor contains an increasing or decreasing metal concentration along a radius of the particle.

6. The process of claim 1, wherein the coating of the cathode material precursor comprises co-precipitation or spray-drying.

7. The process of claim 1, wherein the coating the cathode material precursor with an coating material comprises:

providing an acidic solution of a first coating material precursor and a basic solution; and

combining the basic solution and the acidic solution to effect precipitation of a second coating material precursor;

wherein second coating material precursor precipitates as a layer coating on individual particles of the cathode material precursor to form the coated cathode material precursor.

8. The process of claim 7, wherein a concentration of the first coating material precursor in the acidic solution is maintained at a substantially constant value such that the layer of the second coating material precursor has a substantially uniform composition along a radius of the layer.

9. The process of claim 7, wherein a concentration of the first coating material precursor in the acidic solution increased or reduced during precipitation of the second electrochemically inert material precursor such that the layer of the second coating material precursor has an increasing or decreasing concentration along a radius of the layer.

10. The process of claim 1, wherein the coating material precursor is a precursor for an electrochemically active coating, and the cathode is coated with the electrochemically active coating.

11. The process of claim 1, wherein the coating material precursor is a precursor for an electrochemically inert coating, and the cathode is coated with the electrochemically inert coating.

12. The process of claim 1, wherein the cathode active material precursor comprises a metal hydroxide, a metal carbonate, a metal oxalate, or a metal phosphate.

13. The composition of claim 12, wherein the the cathode active material precursor comprises Co(OH)₂, Ni(OH)₂, CoCO₃, MnCO₃, NiC₂O₄, FePO₄, Co_xNi_yMn₁₋

x−

y(OH)₂, CO_xNi_yMn<sub>1−

x−

y</sub>CO₃, Co_xNi_yMn<sub>1−

x−

y</sub>C₂O₄, etc.

14. The composition of claim 1, wherein the coating material precursor comprises a metal hydroxide, a metal carbonate, a metal oxlate, a metal fluoride, a metal phosphate, or a metal oxyfluoride.

15. The composition of claim 12, wherein the coating material precursor comprises Al(OH)₃, Al₂(CO₃)₃, Al₂(C₂O₄)₃, AlF₃, AlPO₄, Zr(OH)₄, Ti(OH)₄, Mg(OH)₂, Zn(OH)₂, ZnCO₃, or Zr(CO₃)₂.

16. The composition of claim 1, wherein a coating material comprises a metal oxide, a metal fluoride, a metal phosphate, or a metal oxyfluoride.

17. The composition of claim 1, wherein the coating material comprises Al₂O₃, ZrO₂, MgO, ZnO, NiO, MnO₂, TiO₂, MgF₂, CaF₂, AlF₃, AlPO₄, CoPO₄, Li₂MnO₃, LiAlO₂, LiV₃O₈, or Li₅FeO₄.

18. The composition of claim 1, wherein the coating material comprises Al₂O₃.

19. The process of claim 1 comprising the lithiating, wherein a lithium source material comprises lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate, lithium oxalate, lithium benzoate, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium oxide, lithium peroxide, lithium sulfate, lithium alloys, lithium silicate, lithium aluminate, or lithium phosphate.

20. The process of claim 1 comprising the sodiating, wherein a sodium source material comprises sodium carbonate, sodium hydroxide, sodium nitrate, sodium acetate, sodium oxalate, sodium benzoate, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium oxide, sodium peroxide, sodium sulfate, sodium alloys, sodium silicate, sodium aluminate, or sodium phosphate.

21. The coated cathode active material produced by the process of claim 1.

22. A cathode comprising the coated cathode active material of claim 21 and a binder.

23. An electrochemical device comprising the cathode of claim 22 and an anode.