Low-temperature preparation of cathode active material

Patent metadata

Field	Value
Publication number	US-12062775-B2
Application number	US-201816769216-A
Country	US
Kind code	B2
Filing date	Dec 10, 2018
Priority date	Dec 8, 2017
Publication date	Aug 13, 2024
Grant date	Aug 13, 2024

Abstract

The invention discloses a method of preparing a current collector surface enriched with cathode active material. The method comprises preparing a precursor solution by dissolving at least two metal salts and one or more organic acids in a first solvent, adding one or more basic compounds and one or more non-metallic salts to the precursor solution, diluting the precursor solution by adding a second solvent, preparing a surface-treated current collector by disposing at least part of the diluted precursor solution on a current collector surface material, and heating the surface-treated current collector at a temperature of 500° C. or less under an oxidative or inert atmosphere, thereby decomposing the diluted precursor solution.

First claim

The invention claimed is:

1. A method of preparing a current collector surface enriched with cathode active material comprising the following steps:
a) preparing a precursor solution by dissolving at least two metal salts and one or more organic acids in a first solvent, said metal salts comprising lithium, and one or more selected from the group consisting of aluminium, cobalt, manganese and nickel;
b) adding one or more basic compounds and one or more non-metallic salts to the precursor solution;
c) diluting the precursor solution obtained in step b) by adding a second solvent;
d) preparing a surface-treated current collector by disposing at least part of the diluted precursor solution on a current collector surface material;
e) heating the surface-treated current collector at a temperature of 500° C. or less under an oxidative or inert atmosphere, thereby decomposing the diluted precursor solution.

2. The method of claim 1 , wherein the metal salts comprise a lithium cation, and additionally one or more cations selected from the group of manganese, cobalt, aluminium and nickel, and one or more anions selected from the group consisting of acetate, acetylacetates, alkoxide, chloride, citrate, glycolate, hydroxide, nitrate, and oxalate.

3. The method of claim 1 , wherein the molar ratio of metals present in the precursor solution, precursor solution obtained in step b), and diluted precursor solution is represented by one of the following chemical formulae in which oxygen has been omitted,
Li y Co z wherein 0.1<y<2.0, and 0.1<z<2.0,
Li y Mn z wherein 0.1<y<2.0 and 0.1<z<2.0,
Li x Ni y Mn z wherein 0.1<x<2.0, 0.1<y<2.0 and 0.1<z<2.0,
Li w Ni x Co y Al z wherein 0.1<w<2.0, 0.1<x<2.0, 0.1<y<1.0 and 0<z<1.0, or
Li w Ni x Mn y Co z wherein 0.1<w<2.0, 0.1<x<2.0, 0<y<1.0 and 0<z<1.0.

4. The method of claim 3 , wherein the molar ratio of metals present in the precursor solution, precursor solution obtained in step b), and diluted precursor solution is represented by the following chemical formula in which oxygen has been omitted,
Li y Co z , wherein
0.1<y<1.5, and 0.5<z<1.5, or 0.1<z<1.0.

5. The method of claim 3 , wherein the molar ratio of metals present in the precursor solution, precursor solution obtained in step b), and diluted precursor solution is represented by the following chemical formula in which oxygen has been omitted,
Li y Mn z , wherein
0.1<y<1.5, and
0.5<z<1.5.

6. The method of claim 3 , wherein the molar ratio of metals present in the precursor solution, precursor solution obtained in step b), and diluted precursor solution is represented by the following chemical formula in which oxygen has been omitted,
Li x Ni y Mn z , wherein
0.5<x<1.5, or 0.1<x<1.0,
0.2<y<1.2, or 0.1<y<1.0, and
0.8<z<1.2, or 0.1<z<1.0.

7. The method of claim 3 , wherein the molar ratio of metals present in the precursor solution, precursor solution obtained in step b), and diluted precursor solution is represented by the following chemical formula in which oxygen has been omitted,
Li w Ni x Co y Al z , wherein
0.5<w<1.5, or 0.1<w<1.0,
0.2<x<1.2, or 0.1<x<1.0,
0.1<y<0.5, and
0<z<0.5.

8. The method of claim 3 , wherein the molar ratio of metals present in the precursor solution, precursor solution obtained in step b), and diluted precursor solution is represented by the following chemical formula in which oxygen has been omitted,
Li w Ni x Mn y Co z , wherein
0.5<w<1.5,
0.1<x<1.2,
0<y<0.5, or 0.1<y<1.0, and
0<z<0.5, or z=1−x−y.

9. The method of claim 1 , wherein the molar ratio of metals present in the precursor solution, precursor solution obtained in step b), and diluted precursor solution is represented by one of the following chemical formulas in which oxygen has been omitted: LiCo, LiMn, LiMn 2 , Li 2 Mn, LiNiMn, LiNi 0.8 Co 0.15 Al 0.05 , LiNi 0.8 Mn 0.1 Co 0.1 , LiNi 1/3 Mn 1/3 Co 1/3 and Li[Li 0.2 Mn 0.54 Ni 0.13 Co 0.13 ].

10. The method of claim 1 , wherein the first solvent comprises one or more selected from the group consisting of ammonia, t-butanol, n-butanol, n-propanol, iso-propanol, nitromethane, ethanol, methanol, 2-methoxyethanol, acetic acid, formic acid, and water.

11. The method of claim 1 , wherein the second solvent comprises one or more selected from the group consisting of ammonia, t-butanol, n-butanol, n-propanol, iso-propanol, nitromethane, ethanol, methanol, 2-methoxyethanol, acetic acid, formic acid, and water.

12. The method of claim 1 , wherein the organic acid comprises one or more selected from the group consisting of citric acid, aconitic acid, tricarballylic acid, trimesic acid, propionic acid, glycolic acid, lactic acid, malic acid, and mandelic acid.

13. The method of claim 1 , wherein the organic acid is selected from the group consisting of glycolic acid, propionic acid, lactic acid, malic acid, tartaric acid, and mandelic acid.

14. The method of claim 1 , wherein the organic acid is glycolic acid.

15. The method of claim 1 , wherein the one or more organic acids are added to the metal salts in step a) in a molar ratio between organic acid and metal salts of 5:1 to 1:3.

16. The method of claim 1 , wherein the basic compound comprises one or more selected from the group consisting of ammonia, aluminium hydroxide, lithium hydroxide, nickel hydroxide, or pyridine.

17. The method of claim 1 , wherein the basic compound comprises ammonia.

18. The method of claim 1 , wherein the one or more basic compounds are added in step b) in an amount sufficient to obtain a precursor solution in a pH range of 5 to 9.

19. The method of claim 1 , wherein the one or more non-metallic salts comprise one or more selected from the group of ammonium nitrate, ammonium perchlorate, ammonium permanganate or ammonium sulphate.

20. The method of claim 1 , wherein the one or more non-metallic salts are added in step b) in a molar ratio between anion of the non-metallic salt and organic acid of the precursor solution in the range of 8:1 to 1:8.

21. The method of claim 1 , wherein the second solvent is added to the precursor solution in step c) in a volumetric ratio of 1:1 or less.

22. The method of claim 1 , wherein the diluted precursor solution of step d) is disposed on the surface of a current collector material selected from the group consisting of platinum, nickel, titanium nitride, gold, copper, tantalum, aluminium, tantalum nitride, indium tin oxide, antimony tin oxide, fluorine doped tin oxide, and aluminium doped zinc oxide.

23. A current collector surface enriched with cathode active material obtainable by the method of claim 1 .

24. A coating comprising the current collector surface of claim 23 , wherein said coating has less than 0.5% of binder material, based on total weight of the coating.

Assignees

• TNO

Inventors

• Van Den Ham Evert Jonathan

Classifications

• H01M2004/028

  Positive electrodes · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M4/131

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title