Disclosed is a lithium complex oxide and method of manufacturing the same, more particularly, a lithium complex oxide effective in improving the characteristics of capacity, resistance, and lifetime with reduced residual lithium and with different interplanar distances of crystalline structure between a primary particle locating in an internal part of secondary particle and a primary particle locating on the surface part of the secondary particle, and a method of preparing the same.

A lithium metal oxide powder for a cathode material in a rechargeable battery, consisting of a core and a surface layer, the surface layer being delimited by an outer and an inner interface, the inner interface being in contact with the core, the core having a layered crystal structure comprising the elements Li, M and oxygen, wherein M has the formula M=(Ni.sub.z(Ni.sub.1/2Mn.sub.1/2).sub.yCo.sub.x).sub.1-kA.sub.k, with 0.15x0.30, 0.20z0.55, x+y+z=1 and 0<k0.1, wherein the Li content is stoichiometrically controlled with a molar ratio 0.95Li:M1.10; wherein A is at least one dopant and comprises Al; wherein the core has an Al content of 0.3-3 mol % and a F content of less than 0.05 mol %; and wherein the surface layer has an Al content that increases continuously from the Al content of the core at the inner interface to at least 10 mol % at the outer interface, and a F content that increases continuously from less than 0.05 mol % at the inner interface to at least 3 mol % at the outer interface, the Al and F contents in the surface layer being determined by XPS. The surface layer may also have a Mn content that decreases continuously from the Mn content of the core at the inner interface, to less than 50% of the Mn content of the core at the outer interface.

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.

Materials are presented of the formula:

A.sub.xM.sub.yM.sup.i.sub.ziO.sub.2d, where A is sodium or a mixed alkali metal including sodium as a major constituent; x>0; M is a metal or germanium; y>0; M.sup.i, for i=1, 2, 3 . . . n, is a transition metal or an alkali metal; z.sub.i0 for each i=1, 2, 3 . . . n; 0<d0.5; the values of x, y, z.sub.i and d are such as to maintain charge neutrality; and the values of x, y, z.sub.i and d are such that x+y+z.sub.i>2d.

The formula includes compounds that are oxygen deficient. Further the oxidation states may or may not be integers i.e. they may be whole numbers or fractions or a combination of whole numbers and fractions and may be averaged over different crystallographic sites in the material. Such materials are useful, for example, as electrode materials in rechargeable battery applications. Also presented is a method of preparing a compound having the formula A.sub.xM.sub.yM.sup.i.sub.ziO.sub.2d.

An object is to provide a positive electrode active material which can exhibit sufficient cycle characteristics in a non-aqueous electrolyte secondary battery. The positive electrode active material for a non-aqueous electrolyte secondary battery of the present invention is represented by Composition Formula (2): Li.sub.x[Ni.sub.(1/3-a)[M].sub.aMn.sub.2/3]O.sub.2 (in the formula, M represents at least one element selected from the group consisting of Cu, Zn, Mg, Fe, Al, Co, Sc, Ti, V, Cr, Ga, Ge, Bi, Sn, Ca, B, and Zr, 0a, and x represents the number of Li satisfying the atomic valence). In addition, the positive electrode active material for a non-aqueous electrolyte secondary battery is characterized in that it is obtained by reduction-ion exchange of a precursor of the positive electrode active material that is represented by Composition Formula (1): Na.sub.2/3[Ni.sub.(1/3-a)[M].sub.aMn.sub.2/3]O.sub.2 (in the formula, M and a are as defined in Composition Formula (2)).

The invention relates to electrodes comprising doped nickelate-containing compositions comprising a first component-type comprising one or more components with an 03 structure of the general formula: A.sub.aM.sup.1.sub.VM.sup.2.sub.WM.sup.3.sub.XM.sup.4.sub.yM.sup.5.sub.ZO.sub.2 wherein A comprises one or more alkali metal selected from sodium, lithium and potassium; M.sup.1 is nickel in oxidation state 2+, M.sup.2 comprises one or more metals in oxidation state 4+, M.sup.3 comprises one or more metals in oxidation state 2+, M.sup.4 comprises one or more metals in oxidation state 4+, and M.sup.5 comprises one or more metals in oxidation state 3+ wherein 0.85a1; 0<v<0.5; at least one of w and y is >0; x0; z0; and wherein a, v, w, x, y and z are chosen to maintain electroneutrality; together with one or more component-types selected from a second component-type comprising one or more components with a P2 structure of the general formula: A.sub.a<M.sup.1.sub.VM.sup.2.sub.WM.sup.3.sub.X<M.sup.4.sub.y<M.sup.5.sub.ZO.sub.2 wherein A comprises one or more alkali metal selected from sodium, lithium and potassium; M.sup.1 is nickel in oxidation state 2+, M.sup.2 comprises one or more metals in oxidation state 4+, M.sup.3 comprises one or more metals in oxidation state 2+, M.sup.4 comprises one or more metals in oxidation state 4+, and M.sup.5 comprises one or more metals in oxidation state 3+ wherein 0.4a<1; 0<v<0.5; at least one of w and y is >0; x0, preferably x>0; z>0; and wherein a, v, w, x, y and z are chosen to maintain electroneutrality; and a third component-type comprising one or more components with a P3 structure of the general formula: A.sub.aM.sup.1.sub.vM.sup.2.sub.wM.sup.3.sub.xM.sup.4.sub.yM.sup.5.sub.zO.sub.2 wherein A comprises one or more alkali metals selected from sodium, lithium and potassium; M.sup.1 is nickel in oxidation state 2+, M.sup.2 comprises one or more metals in oxidation state 4+, M.sup.3 comprises one or more metals in oxidation state 2+, M.sup.4 comprises one or more metals in oxidation state 4+, and M.sup.5 comprises one or more metals in oxidation state 3+ wherein 0.4a<1, 0<v<0.5, At least one of w and y is >0; x0; z0; and wherein a, v, w, x, y and z are chosen to maintain electroneutrality.

The invention relates to doped nickelate-containing material with the general formula: A.sub.aM.sub.v.sup.1M.sub.w.sup.2M.sub.x.sup.3M.sub.y.sup.4M.sub.z.sup.5O.sub.2- wherein A comprises one or more alkali metals selected from sodium, lithium and potassium; M.sup.1 is nickel in oxidation state 2+, M.sup.2 comprises one or more metals in oxidation state 4+, M.sup.3 comprises one or more metals in oxidation state 2+, M.sup.4 comprises one or more metals in oxidation state 4+, and M.sup.5 comprises one or more metals in oxidation state 3+ wherein 0.4a<0.9, 0<v<0.5, at least one of w and y is >0, x>0, z0, 00.1, and wherein a, v, w, x, y and z are chosen to maintain electroneutrality.

A positive electrode active material includes a lithium transition metal oxide and a coating element M.sup.3-containing coating layer formed on a surface of the lithium transition metal oxide, wherein M.sup.3 comprises at least one of Al, Ti, Mg, Zr, W, Y, Sr, or Co, wherein the lithium transition metal oxide is doped with a doping element M.sup.2, wherein M.sup.2 includes at least one of Al, Ti, Mg, Zr, W, Y, Sr, Co, F, Si, Na, Cu, Fe, Ca, S, or B, wherein the lithium transition metal oxide has a single particle form, and includes a center portion having a layered structure and a surface portion having a rock-salt structure, and the total amount of the doping element M.sup.2 and the coating element M.sup.3 is in a range of 4,580 ppm to 9,120 ppm based on a total weight of the positive electrode active material.

Materials are presented of the formula: A.sub.x M.sub.y M.sup.i.sub.zi O.sub.2d, where A is sodium or a mixed alkali metal including sodium as a major constituent; x>0; M is a metal or germanium; y>0; M.sup.i, for i=1, 2, 3 . . . n, is a transition metal or an alkali metal; z.sub.i0 for each i=1, 2, 3 . . . n; 0<d0.5; the values of x, y, z.sub.i and d are such as to maintain charge neutrality; and the values of x, y, z.sub.i and d are such that x+y+z.sub.i>2d. The formula includes compounds that are oxygen deficient. Further the oxidation states may or may not be integers i.e. they may be whole numbers or fractions or a combination of whole numbers and fractions and may be averaged over different crystallographic sites in the material. Such materials are useful, for example, as electrode materials in rechargeable battery applications. Also presented is a method of preparing a compound having the formula A.sub.x M.sub.y M.sup.i.sub.zi O.sub.2d.

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.