Positive Electrode Active Material, Method for Manufacturing Positive Electrode Active Material, and Secondary Battery

Abstract

A positive electrode active material which can improve cycle characteristics of a secondary battery is provided. Two kinds of regions are provided in a superficial portion of a positive electrode active material such as lithium cobaltate which has a layered rock-salt crystal structure. The inner region is a non-stoichiometric compound containing a transition metal such as titanium, and the outer region is a compound of representative elements such as magnesium oxide. The two kinds of regions each have a rock-salt crystal structure. The inner layered rock-salt crystal structure and the two kinds of regions in the superficial portion are topotaxy; thus, a change of the crystal structure of the positive electrode active material generated by charging and discharging can be effectively suppressed. In addition, since the outer coating layer in contact with an electrolyte solution is the compound of representative elements which is chemically stable, the secondary battery having excellent cycle characteristics can be obtained.

1 . A lithium-ion secondary battery comprising:
 an electrolyte solution comprising vinylene carbonate; and   a positive electrode comprising a positive electrode active material particle comprising lithium cobaltate,   wherein the positive electrode active material particle comprises a first region and a second region,   wherein the first region comprises a layered rock-salt crystal structure,   wherein the second region comprises a rock-salt crystal structure,   wherein the second region covers at least a first part of the first region,   wherein the positive electrode active material particle comprises titanium, magnesium, fluorine, and oxygen in the second region, and   wherein a crystal orientation of at least a second part of the first region and a crystal orientation of at least a part of the second region are substantially aligned with each other.   
     
     
         2 . The lithium-ion secondary battery according to  claim 1 ,
 wherein the titanium, the magnesium, the fluorine, and the oxygen are provided in a range from a surface of the positive electrode active material particle to a depth of 5 nm.   
     
     
         3 . The lithium-ion secondary battery according to  claim 1 ,
 wherein the positive electrode further comprises a conductive additive, and   wherein the conductive additive comprises carbon fiber, graphene or multilayer graphene.   
     
     
         4 . The lithium-ion secondary battery according to  claim 1 ,
 wherein, in a line analysis of energy dispersive X-ray spectroscopy (EDX), a maximum peak of the fluorine is present in a region from a surface of the positive electrode active material particle to a depth of 3 nm.   
     
     
         5 . The lithium-ion secondary battery according to  claim 1 ,
 wherein, in a line analysis of energy dispersive X-ray spectroscopy (EDX), a maximum peak of the fluorine is present in a region from a surface of the positive electrode active material particle to a depth of 1 nm.   
     
     
         6 . The lithium-ion secondary battery according to  claim 1 ,
 wherein, in a line analysis of energy dispersive X-ray spectroscopy (EDX), a maximum peak of the fluorine is present in a region from a surface of the positive electrode active material particle to a depth of 0.5 nm.   
     
     
         7 . The lithium-ion secondary battery according to  claim 1 ,
 wherein the electrolyte solution further comprises adiponitrile.   
     
     
         8 . A lithium-ion secondary battery comprising:
 an electrolyte solution comprising vinylene carbonate; and   a positive electrode comprising a positive electrode active material particle comprising lithium cobaltate,   wherein the positive electrode active material particle comprises a first region and a second region,   wherein the first region comprises a layered rock-salt crystal structure,   wherein the second region comprises a rock-salt crystal structure,   wherein the positive electrode active material particle comprises titanium, magnesium, fluorine, and oxygen in the second region, wherein the second region extends from a surface of the positive electrode active material particle to an inside of the positive electrode active material particle where magnesium detected by a line analysis of energy dispersive X-ray spectroscopy (EDX) in a depth direction is ⅕ of a maximum peak of the magnesium in the line analysis, and   wherein a crystal orientation of at least a part of the first region and a crystal orientation of at least a part of the second region are substantially aligned with each other.   
     
     
         9 . The lithium-ion secondary battery according to  claim 8 ,
 wherein the titanium, the magnesium, the fluorine, and the oxygen are provided in a range from the surface of the positive electrode active material particle to a depth of 5 nm.   
     
     
         10 . The lithium-ion secondary battery according to  claim 8 ,
 wherein the positive electrode further comprises a conductive additive, and   wherein the conductive additive comprises carbon fiber, graphene or multilayer graphene.   
     
     
         11 . The lithium-ion secondary battery according to  claim 8 ,
 wherein, in the line analysis of energy dispersive X-ray spectroscopy (EDX), a maximum peak of the fluorine is present in a region from the surface of the positive electrode active material particle to a depth of 3 nm.   
     
     
         12 . The lithium-ion secondary battery according to  claim 8 ,
 wherein, in the line analysis of energy dispersive X-ray spectroscopy (EDX), a maximum peak of the fluorine is present in a region from the surface of the positive electrode active material particle to a depth of 1 nm.   
     
     
         13 . The lithium-ion secondary battery according to  claim 8 ,
 wherein, in the line analysis of energy dispersive X-ray spectroscopy (EDX), a maximum peak of the fluorine is present in a region from the surface of the positive electrode active material particle to a depth of 0.5 nm.   
     
     
         14 . The lithium-ion secondary battery according to  claim 8 ,
 wherein the electrolyte solution further comprises adiponitrile.   
     
     
         15 . A lithium-ion secondary battery comprising:
 an electrolyte solution comprising ethylene carbonate, diethyl carbonate, vinylene carbonate, and lithium hexafluorophosphate; and   a positive electrode comprising a positive electrode active material particle comprising lithium cobaltate,   wherein the positive electrode active material particle comprises a first region and a second region,   wherein the first region comprises a layered rock-salt crystal structure,   wherein the second region comprises a rock-salt crystal structure,   wherein the second region covers at least a first part of the first region,   wherein the positive electrode active material particle comprises titanium, magnesium, fluorine, and oxygen in the second region, and   wherein a crystal orientation of at least a second part of the first region and a crystal orientation of at least a part of the second region are substantially aligned with each other.   
     
     
         16 . The lithium-ion secondary battery according to  claim 15 ,
 wherein the titanium, the magnesium, the fluorine, and the oxygen are provided in a range from a surface of the positive electrode active material particle to a depth of 5 nm.   
     
     
         17 . The lithium-ion secondary battery according to  claim 15 ,
 wherein the positive electrode further comprises a conductive additive, and   wherein the conductive additive comprises carbon fiber, graphene or multilayer graphene.   
     
     
         18 . The lithium-ion secondary battery according to  claim 15 ,
 wherein, in a line analysis of energy dispersive X-ray spectroscopy (EDX), a maximum peak of the fluorine is present in a region from a surface of the positive electrode active material particle to a depth of 3 nm.   
     
     
         19 . The lithium-ion secondary battery according to  claim 15 ,
 wherein, in a line analysis of energy dispersive X-ray spectroscopy (EDX), a maximum peak of the fluorine is present in a region from a surface of the positive electrode active material particle to a depth of 1 nm.   
     
     
         20 . The lithium-ion secondary battery according to  claim 15 ,
 wherein, in a line analysis of energy dispersive X-ray spectroscopy (EDX), a maximum peak of the fluorine is present in a region from a surface of the positive electrode active material particle to a depth of 0.5 nm.   
     
     
         21 . The lithium-ion secondary battery according to  claim 15 ,
 wherein the electrolyte solution further comprises adiponitrile.   
     
     
         22 . A lithium-ion secondary battery comprising:
 an electrolyte solution comprising ethylene carbonate, diethyl carbonate, vinylene carbonate, and lithium hexafluorophosphate; and   a positive electrode comprising a positive electrode active material particle comprising lithium cobaltate,   wherein the positive electrode active material particle comprises a first region and a second region,   wherein the first region comprises a layered rock-salt crystal structure,   wherein the second region comprises a rock-salt crystal structure,   wherein the positive electrode active material particle comprises titanium, magnesium, fluorine, and oxygen in the second region, wherein the second region extends from a surface of the positive electrode active material particle to an inside of the positive electrode active material particle where magnesium detected by a line analysis of energy dispersive X-ray spectroscopy (EDX) in a depth direction is ⅕ of a maximum peak of the magnesium in the line analysis, and   wherein a crystal orientation of at least a part of the first region and a crystal orientation of at least a part of the second region are substantially aligned with each other.   
     
     
         23 . The lithium-ion secondary battery according to  claim 22 ,
 wherein the titanium, the magnesium, the fluorine, and the oxygen are provided in a range from the surface of the positive electrode active material particle to a depth of 5 nm.   
     
     
         24 . The lithium-ion secondary battery according to  claim 22 ,
 wherein the positive electrode further comprises a conductive additive, and   wherein the conductive additive comprises carbon fiber, graphene or multilayer graphene.   
     
     
         25 . The lithium-ion secondary battery according to  claim 22 ,
 wherein, in the line analysis of energy dispersive X-ray spectroscopy (EDX), a maximum peak of the fluorine is present in a region from the surface of the positive electrode active material particle to a depth of 3 nm.   
     
     
         26 . The lithium-ion secondary battery according to  claim 22 ,
 wherein, in the line analysis of energy dispersive X-ray spectroscopy (EDX), a maximum peak of the fluorine is present in a region from the surface of the positive electrode active material particle to a depth of 1 nm.   
     
     
         27 . The lithium-ion secondary battery according to  claim 22 ,
 wherein, in the line analysis of energy dispersive X-ray spectroscopy (EDX), a maximum peak of the fluorine is present in a region from the surface of the positive electrode active material particle to a depth of 0.5 nm.   
     
     
         28 . The lithium-ion secondary battery according to  claim 22 ,
 wherein the electrolyte solution further comprises adiponitrile.