Processes for making dense, spherical active materials for lithium-ion cells

• US 8,062,792 B2
• Filed: 04/25/2006
• Issued: 11/22/2011
• Est. Priority Date: 04/26/2005
• Status: Active Grant

• Current Assignee: U Chicago Argonne, LLC
• Original Assignee: UChicago Argonne LLC (University of Chicago)
• Inventors: Kang, Sun-Ho, Amine, Khalil
• Primary Examiner(s): APICELLA, KARIE O
• Application Number:
  US11/410,757
• Publication Number:
  US 20060239883A1
• Time in Patent Office: 2,037 Days
• Field of Search: 429/231.1, 429/231.95, 423/304
• US Class Current: 429/231.1
• CPC Class Codes: C01B 13/185 Preparing mixtures of oxides
• CPC Class Codes: C01B 25/265 General methods for obtaining phosphates
• CPC Class Codes: C01B 25/30 Alkali metal phosphates
• CPC Class Codes: C01B 25/45 containing plural metal, or metal and ammonium
• CPC Class Codes: C01B 32/60 Preparation of carbonates or bicarbonates in general of percarbonates C01B15/10; of specific carbonates or bicarbonates according to the cation C01B-C01G
• CPC Class Codes: C01D 15/02 Oxides; Hydroxides
• CPC Class Codes: C01G 31/00 Compounds of vanadium
• CPC Class Codes: C01G 45/006 Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen manganates, manganites or permanganates C01G45/12
• CPC Class Codes: C01G 51/006 Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen cobaltates C01G51/40
• CPC Class Codes: C01G 51/42 containing alkali metals, e.g. LiCoO2
• CPC Class Codes: C01G 51/50 of the type [MnO2]n- , e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
• CPC Class Codes: C01G 53/006 Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen nickelates C01G53/40
• CPC Class Codes: C01G 53/42 containing alkali metals, e.g. LiNiO2
• CPC Class Codes: C01G 53/50 of the type [MnO2]n- , e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
• CPC Class Codes: C01P 2002/52 containing elements as dopants
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/32 Spheres
• CPC Class Codes: C01P 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C01P 2006/40 Electric properties
• 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 2004/021 : Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 4/02 : Electrodes composed of, or comprising, active material
• CPC Class Codes: H01M 4/0497 : Chemical precipitation
• 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 4/1315 : containing halogen atoms, e.g. LiCoOxFy
• CPC Class Codes: H01M 4/364 : as mixtures
• CPC Class Codes: H01M 4/48 : of inorganic oxides or hydroxides
• 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 4/582 : Halogenides
• CPC Class Codes: H01M 4/5825 : Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries

Abstract

Processes are provided for making dense, spherical mixed-metal carbonate or phosphate precursors that are particularly well suited for the production of active materials for electrochemical devices such as lithium ion secondary batteries. Exemplified methods include precipitating dense, spherical particles of metal carbonates or metal phosphates from a combined aqueous solution using a precipitating agent such as ammonium hydrogen carbonate, sodium hydrogen carbonate, or a mixture that includes sodium hydrogen carbonate. Other exemplified methods include precipitating dense, spherical particles of metal phosphates using a precipitating agent such as ammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, or a mixture of any two or more thereof. Further provided are compositions of and methods of making dense, spherical metal oxides and metal phosphates using the dense, spherical metal precursors. Still further provided are electrodes and batteries using the same.

Claims

1. A method comprising:

precipitating spherical particles comprising one or more metal carbonates or one or more metal phosphates from a combined aqueous solution comprising a precipitating agent, wherein;

the precipitating agent is selected from ammonium hydrogen carbonate, sodium hydrogen carbonate, or a mixture comprising sodium hydrogen carbonate when the spherical particles are the one or more metal carbonates and the metal carbonates are selected from the group consisting of (Ni_α

Co_β

Mn_γ

Me′

_δ

)CO₃, wherein Me′

is selected from the group consisting of Fe, Ag, Cu, Zn, or Mg;

0<

α

≦

1, 0<

β

≦

1, 0<

γ

≦

1, and 0≦

δ

≦

1; and

the sum of α

, β

, γ

, and δ

is 1;

or

the precipitating agent is ammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, or a mixture comprising any two or more thereof when the spherical particles are the one or more metal phosphates wherein the metal phosphates are selected from the group consisting of (Ni<sub>α

′</sub>

Co<sub>β

′</sub>

Mn<sub>γ

′</sub>

Fe_δ

)(PO₄);

wherein 0≦

α

′

≦

1, 0≦

β

′

≦

1, 0≦

γ

′

≦

1, and 0≦

δ

≦

1; and

where the sum of α

′

, β

′

, γ

′

, and δ

is 1.

2. The method of claim 1, wherein the spherical particles are calcined from about 100°

C. to about 1000°

C.

3. The method of claim 1, wherein the spherical particles have a diameter of from about 0.1 μ

m to about 100 μ

m and a tap density from about 1.5 g/cm³ to about 3 g/cm³.

4. The method of claim 1, further comprising:

forming the combined aqueous solution by adding an aqueous solution of one or more metal salts to an aqueous solution comprising the precipitating agent.

5. The method of claim 4, wherein the one or more metal salts are selected from metal sulfates, metal acetates, metal nitrates, metal chlorides, or a mixture of any two or more thereof.

6. The method of claim 4, wherein when the spherical particles are the metal phosphates, the method further comprises purging the combined solution with nitrogen, argon, carbon dioxide, or oxygen gas during the precipitating step.

7. The method of claim 4, wherein a concentration of metal ions in the aqueous solution of one or more metal salts is from about 0.01 M to about 5 M.

8. The method of claim 4, wherein a pH of the aqueous solution of one or more metal salts is from about 4 to about 8.

9. The method of claim 4, wherein a concentration of precipitating agent is from 0.1 M to 5 M.

10. The method of claim 1, wherein the mixture comprising sodium hydrogen carbonate, further comprises ammonium carbonate, sodium carbonate, or both ammonium carbonate and sodium carbonate.

11. The method of claim 1, wherein the precipitating step is carried out in the presence of a chelating agent.

12. The method of claim 11, wherein the chelating agent is selected from the group consisting of ammonium sulfate, ammonium hydroxide, ammonium chloride, ammonium acetate, ammonium nitrate, urea, or a mixture of any two or more thereof.

13. The method of claim 11, wherein a total concentration of chelating agent is from about 0.005 M to about 2 M.

14. The method of claim 1, further comprising calcining a mixture comprising the spherical particles and a lithium salt to provide spherical lithium particles selected from spherical lithium metal oxides and spherical lithium metal phosphates.

15. The method of claim 14, wherein the lithium salt is selected from lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate, or a mixture of any two or more thereof.

16. The method of claim 14, wherein the mixture further comprises a metal cation dopant selected from the group consisting of Mg, Zn, Al, Ga, B, Zr, Si, Ti, Nb, and W.

17. The method of claim 14, wherein the mixture further comprises an anion dopant selected from the group consisting of F, S, Cl, Br, and I.

18. The method of claim 14, wherein the mixture is calcined in an inert atmosphere or in the presence of oxygen and the calcining is performed from about 450°

C. to about 1100°

C.

19. The method of claim 14, wherein the spherical lithium metal oxide comprises Li_1+xNi_α

Co_β

Mn_γ

Me_yO_2-zX_z wherein Me is selected from the group consisting of Mg, Zn, Al, Ga, B, Zr, Si, Ti, Nb, and W;

X selected from the group consisting of F, S, Cl, and I;

0≦

x≦

0.33;

0<

α

≦

1, 0<

β

≦

1, 0<

γ

≦

1, 0≦

y≦

0.2, and 0≦

z≦

0.3; and

where the sum of x, α

, β

, γ

, and y is equal to 1.

20. The method of claim 14, wherein the spherical lithium metal oxide comprises Li_1+xNi_aCo_bMn_cMe_yO_4-zX_z wherein Me is selected from the group consisting of Mg, Zn, Al, Ga, B, Zr, Si, Ti, Nb, and W;

X selected from the group consisting of F, S, Cl, and I;

0≦

x≦

0.33;

0<

a≦

2, 0<

b≦

2, 0<

c≦

2, 0≦

y≦

0.2, and 0≦

z≦

0.3; and

where the sum of x, a, b, c, and y is equal to 2.

21. The method of claim 14, wherein the spherical lithium metal phosphate comprises Li_1+x′

(Ni<sub>α

′</sub>

Co<sub>β

′</sub>

Mn<sub>γ

′</sub>

Fe_δ

)_1-y′

Me″

_y′

PO₄ wherein Me″

is selected from the group consisting of Al, Zr, Si, Ti, Nb, Mo and W;

0≦

x′

≦

0.1;

0≦

α

′

≦

1, 0≦

β

′

≦

1, 0≦

γ

′

≦

1, and 0≦

y′

≦

0.1.

22. A composition prepared by the method of claim 14.