Positive electrode active material including particle comprising crystal structure changing from a layered structure to a spinel structure, method of manufacturing the positive electrode active material, and non-aqueous electrolyte secondary battery using the positive electrode active material
View Patent ↗A positive electrode active material having a lithium-excess lithium-transition metal composite oxide particle represented by the chemical formula Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 . The lithium-excess lithium-transition metal composite oxide particle has an inner portion (1) having a layered structure and a surface adjacent portion (2) having a crystal structure gradually changing from a layered structure to a spinel structure from the inner portion (1) toward the outermost surface portion (3). The layered structure and the spinel structure have an identical ratio of the amount of Mn and the total amount of Ni and Co.
1. A positive electrode active material comprising:
a lithium-excess lithium-transition metal composite oxide particle represented by the chemical formula Li 1+x−s Mn 1−x−y M y O 2−t , where 0<x<0.33, 0<y<0.66, 0<s<0.3, 0<t<0.15, and M is at least one transition metal other than manganese; and
the lithium-excess lithium-transition metal composite oxide particle comprising an inner portion having a layered structure and a surface adjacent portion having a crystal structure changing from a layered structure to a spinel structure from an inner part thereof toward a surface part thereof, and the layered structure and the spinel structure having an identical ratio of the Mn and the M in the chemical formula.
2. The positive electrode active material according to claim 1 , wherein the lithium-excess lithium-transition metal composite oxide particle is represented by the chemical formula Li 1+x−s Mn 1−x−p−q Ni p Co q A r O 2−t , where 0<x<0.33, 0<p<0.5, 0<q<0.33, 0≦r<0.05, 0<s<0.3, 0<t<0.15, and A is Mg, Zr, or Nb.
3. The positive electrode active material according to claim 1 , wherein the lithium-excess lithium-transition metal composite oxide particle has a Raman intensity ratio [I(635)/I(605)] in the range 0.6<I(635)/I(605)<1.5.
4. The positive electrode active material according to claim 1 , wherein the inner portion having a layered structure contains at least a structure belonging to the space group C2/m or C2/c.
5. The positive electrode active material according to claim 1 , further comprising a protective layer formed on the surface of the lithium-excess lithium-transition metal composite oxide particle.
6. A non-aqueous electrolyte secondary battery comprising a negative electrode, a non-aqueous electrolyte, and a positive electrode containing a positive electrode active material according to claim 1 .