Lithium-containing complex oxide, non-aqueous secondary battery using the lithium-containing complex oxide, and method for producing the lithium-containing complex oxide
View Patent ↗Because of the composition represented by General Formula: Li 1+x+α Ni (1−x−y+δ)/2 Mn (1−x−y−δ)/2 M y O 2 (where 0≦x≦0.05, −0.05≦x+α≦0.05, 0≦y≦0.4; −0.1≦δ≦0.1 (when 0≦y≦0.2) or −0.24≦δ≦0.24 (when 0.2<y≦0.4); and M is at least one element selected from the group consisting of Ti, Cr, Fe, Co, Cu, Zn, Al, Ge and Sn), a high-density lithium-containing complex oxide with high stability of a layered crystal structure and excellent reversibility of charging/discharging can be provided, and a high-capacity non-aqueous secondary battery excellent in durability is realized by using such an oxide for a positive electrode.
1. A method for producing a lithium-containing complex oxide, comprising:
coprecipitating a complex compound containing at least Ni and Mn as constituent elements in an inactive atmosphere;
mixing the complex compound and a compound of Li at a predetermined ratio; and
sintering the mixture at a sintering temperature of about 700° C. to 1100° C. in an atmosphere containing oxygen, thereby forming a complex oxide with a layered crystal structure,
wherein the lithium-containing complex oxide further contains a substituent element M,
wherein the substituent element M contains Co, and assuming that a total quantity of Ni, Mn, and the substituent element M is 1-x, and a quantity ratio of the substituent element M is y, x satisfies 0≦x≦0.05, y satisfies 0.1<y≦0.4, and a quantity ratio of Co is 0.1 or more,
wherein a composition of the complex compound containing at least Ni and Mn as constituent elements is adjusted so that a difference δ in a quantity ratio between Ni and Mn constituting the lithium-containing complex oxide satisfies −0.1≦δ≦0.1, and
wherein an average valence of Mn constituting the lithium-containing complex oxide is set to be about 3.3 to 4.
2. The method for producing a lithium-containing complex oxide according to claim 1 , wherein, for mixing the complex compound containing at least Ni and Mn as constituent elements and the compound of Li at a predetermined ratio, the complex compound and the compound of Li are dispersed in a solvent to form a slurry.
3. A method for producing a lithium-containing complex oxide according to claim 1 , wherein an average valence of Mn is about 4.
4. The method for producing a lithium-containing complex oxide according to claim 1 , wherein an average valence of Mn is about 4 and an average valence of Ni is about 2.
5. The method for producing a lithium-containing complex oxide according to claim 1 , wherein the complex compound is one selected from an oxide and a hydroxide.
6. The method for producing a lithium-containing complex oxide according to claim 1 , wherein the lithium-containing complex oxide has a composition represented by General Formula Li 1+x+α Ni (1−x−y+δ)/2 Mn (1−x−y−δ)/2 M y O 2 where 0≦x≦0.05, −0.05≦x+α≦0.05, 0<y≦0.2, −0.1≦δ≦0.1; M is at least one element containing Co, and a quantity ratio of Co is 0.1 or more.
7. The method for producing a lithium-containing complex oxide according to claim 1 , wherein pre-heating is conducted at a temperature lower than the sintering temperature before the sintering.
8. The method for producing a lithium-containing complex oxide according to claim 7 , wherein a temperature during the pre-heating is about 250° C. to 850° C.
9. The method for producing a lithium-containing complex oxide according to claim 1 , wherein a quantity ratio among Ni, Mn, and the substituent element M in the lithium-containing complex oxide is 1:1:1.
10. The method for producing a lithium-containing complex oxide according to claim 1 , wherein y=⅓.
11. The method for producing a lithium-containing complex oxide according to claim 1 , wherein, in an x-ray diffraction measurement of the lithium-containing complex oxide using a CuKα-ray, two diffraction peaks are present at a diffraction angle 2θ in a range of 63° to 66°.
12. The method for producing a lithium-containing complex oxide according to claim 6 , wherein the substituent element M in the General Formula is at least one element containing at least Co, selected from the group consisting of Ti, Cr, Fe, Co, Cu, Zn, Al, Ge, and Sn.
13. A method for producing a lithium-containing complex oxide, comprising:
coprecipitating a complex compound containing at least Ni and Mn as constituent elements in an inactive atmosphere;
mixing the complex compound and a compound of Li at a predetermined ratio; and
sintering the mixture at a sintering temperature of about 700° C. to 1100° C. in an atmosphere containing oxygen, thereby forming a complex oxide with a layered crystal structure,
wherein the lithium-containing complex oxide further contains a substituent element M,
wherein the substituent element M contains Co, and assuming that a total quantity of Ni, Mn, and the substituent element M is 1-x and a quantity ratio of the substituent element M is y, x satisfies 0≦x≦0.05, and y satisfies 0.2<y≦0.4,
wherein a composition of the complex compound containing at least Ni and Mn as constituent elements is adjusted so that a difference δ in a quantity ratio between Ni and Mn constituting the lithium-containing complex oxide satisfies −0.24≦δ≦0.24, and
wherein an average valence of Mn constituting the lithium-containing complex oxide is set to be about 3.3 to 4.
14. The method for producing a lithium-containing complex oxide according to claim 13 , wherein the lithium-containing complex oxide has a composition represented by General Formula Li 1+x+α Ni (1−x−y+δ)/2 Mn (1−x−y−δ)/2 M y O 2 where 0≦x≦0.05, −0.05≦x+α≦0.05, 0.2<y≦0.4, −0.24≦δ≦0.24; M is at least one element containing Co.
15. The method for producing a lithium-containing complex oxide according to claim 14 , wherein the substituent element M in the General Formula is at least one element containing at least Co selected from the group consisting of Ti, Cr, Fe, Co, Cu, Zn, Al, Ge, and Sn.
16. The method for producing a lithium-containing complex oxide according to claim 13 , wherein an average valence of Mn is about 4.
17. The method for producing a lithium-containing complex oxide according to claim 13 , wherein an average valence of Mn is about 4 and an average valence of Ni is about 2.
18. The method for producing a lithium-containing complex oxide according to claim 13 , wherein y=⅓.
19. The method for producing a lithium-containing complex oxide according to claim 13 , wherein, in an x-ray diffraction measurement of the lithium-containing complex oxide using a CuKα-ray, two diffraction peaks are present at a diffraction angle 2θ in a range of 63° to 66°.