Methods of making metal-doped nickel oxide active materials
View Patent ↗Methods of making high-energy cathode active materials for primary alkaline batteries are described. The primary batteries include a cathode having an alkali-deficient nickel(IV)-containing oxide including one or more metals such as Co, Mg, Al, Ca, Y, Mn, and/or non-metals such as B, Si, Ge or a combination of metal and/or non-metal atoms as dopants partially substituted for Ni and/or Li in the crystal lattice; an anode; a separator between the cathode and the anode; and an alkaline electrolyte solution.
1. A method of making a cathode active material, comprising the steps of:
combining an alkali-containing compound, a nickel-containing compound, one or more metal-containing compounds, and one or more non metal-containing compounds at a stoichiometric ratio of from 1:0.98:0.02:0 to 1:0.86:0.12:0.02 to form a mixture;
heating the mixture at a first temperature above at least about 185° C. in flowing oxygen or an oxygen-enriched atmosphere for a first duration;
cooling the mixture to at least about 40° C. in flowing oxygen or an oxygen-enriched atmosphere;
heating the mixture at a second temperature above at least about 775° C. in flowing oxygen or an oxygen-enriched atmosphere for a second duration to form a ANi 1-y-z-w Co y M a z M b w O 2 precursor; and
treating the ANi 1-y-z-w Co y M a z M b w O 2 precursor with an aqueous acid solution at a temperature below about ten degrees Celsius to form an alkali metal deficient nickel oxide having a formula A x Ni 1-y-z-w Co y M a z M b w O 2 ; wherein A is an alkali metal, M a is a metal dopant, M b is a non-metal dopant, 0≦x≦0.12, w is 0 or 0≦w≦0.02, and 0.02≦y+z≦0.25.
2. The method of claim 1 , wherein the nickel-containing compound is selected from nickel monoxide, nickel sesquioxide, nickel hydroxide, nickel oxyhydroxide, nickel carbonate, nickel nitrate, and any combination thereof.
3. The method of claim 1 , wherein the nickel-containing compound is selected from β-nickel oxyhydroxide, metal-doped β-nickel oxyhydroxide, cobalt oxyhydroxide-coated β-nickel oxyhydroxide, γ-nickel oxyhydroxide, metal-doped γ-nickel oxyhydroxide, cobalt oxyhydroxide-coated γ-nickel oxyhydroxide, a mixture of β-nickel oxyhydroxide and γ-nickel oxyhydroxide, and any combination thereof.
4. The method of claim 1 , wherein the metal-containing compound is selected from the group consisting of aluminum, magnesium, cobalt, and manganese metal powders.
5. The method of claim 1 , wherein the metal-containing compound is selected from the group consisting of cobalt oxide, aluminum oxide, magnesium oxide, calcium oxide, yttrium oxide, manganese oxide, and any combination thereof.
6. The method of claim 1 , wherein the metal-containing compound is selected from the group consisting of cobalt hydroxide, cobalt oxyhydroxide, cobalt carbonate, cobalt nitrate, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, calcium hydroxide, calcium carbonate, yttrium hydroxide, manganese hydroxide, manganese carbonate, manganese nitrate, and any combination thereof.
7. The method of claim 1 , wherein the non-metal-containing compound is selected from the group consisting of boron oxide, silicon powder, silicon dioxide, germanium powder, germanium dioxide, and any combination thereof.
8. The method of claim 1 , wherein the alkali-containing compound is selected from the group consisting of lithium hydroxide hydrate, lithium oxide, lithium carbonate, lithium nitrate, and any combination thereof.
9. The method of claim 1 , wherein the stoichiometric ratio of the nickel-containing compound to the one or more metal-containing compounds is between 0.98:0.02 to 0.80:0.20.
10. The method of claim 1 , wherein the stoichiometric ratio of the nickel-containing compound to one or more metal-containing compounds is between 0.96:0.04 to 0.85:0.15.
11. The method of claim 1 , wherein the first temperature is between 185 and 225° C.
12. The method of claim 1 , wherein the second temperature is between 775 and 850° C.
13. The method of claim 1 , wherein the first duration is between 16 and 20 hours.
14. The method of claim 1 , wherein the second duration is between 24 and 60 hours.
15. The method of claim 1 , wherein x is less than 0.1.
16. The method of claim 1 , wherein 0.02≦y≦0.15.
17. The method of claim 1 , wherein y is 0.
18. The method of claim 1 , wherein 0.02≦z≦0.08.
19. The method of claim 1 , wherein z is 0.
20. The method of claim 1 , wherein w is O.
21. The battery method of claim 1 , wherein 0≦w≦0.02.
22. The method of claim 1 , wherein the alkali metal deficient nickel oxide is selected from the group consisting of Li x Ni 1-y Co y O 2 , Li x Ni 1-z Mg z O 2 , Li x Ni 1-y-z Co y Mg z O 2 , Li x Ni 1-z Al z O 2 , Li x Ni 1-y-z Co y Al z O 2 , Li x Ni 1-z (Mg, Al) z O 2 , Li x Ni 1-y-z Co y (Mg, Al) z O 2 , Li x Ni 1-z Ca z O 2 , Li x Ni 1-y-z Co y Ca z O 2 , Li x Ni 1-z Y z O 2 , Li x Ni 1-y-z Co y Y z O 2 , Li x Ni 1-z Mn z O 2 , and Li x Ni 1-y-z Co y Mn z O 2 .
23. The method of claim 1 , wherein the LiNi 1-y-z-w Co y M a z M b w O 2 precursor is treated with the aqueous acid solution for 20 to 60 hours.
24. The method of claim 1 , wherein the LiNi 1-y-z-w Co y M a z M b w O 2 precursor is treated with the aqueous acid solution for at least 40 hours.
25. The method of claim 1 , wherein the aqueous acid solution is selected from the group consisting of aqueous solutions of sulfuric acid, nitric acid, and hydrochloric acid.
26. The method of claim 1 , wherein the aqueous acid solution has a concentration of between 2 M and 12 M.
27. The method of claim 1 , wherein the LiNi 1-y-z-w Co y M a z M b w O 2 precursor is treated with an aqueous acid solution at a temperature of five degrees Celsius or less.
28. The method of claim 1 , wherein the LiNi 1-y-z-w Co y M a z M b w O 2 precursor is treated with an aqueous acid solution at a temperature of zero degree Celsius or more and five degrees Celsius or less.