Provided is a new 5 V-class spinel-type lithium-manganese-containing composite oxide capable of achieving both the expansion of a high potential capacity region and the suppression of gas generation. Proposed is the spinel-type lithium-manganese-containing composite oxide comprising Li, Mn, O and two or more other elements, and having an operating potential of 4.5 V or more at a metal Li reference potential, wherein a peak is present in a range of 14.0 to 16.5 at 2, in an X-ray diffraction pattern measured by a powder X-ray diffractometer (XRD) using CuK1 ray.

An improved process is provided for forming a precursor to a lithium metal oxide. An improved lithium metal oxide formed by calcining the precursor is also provided. The process includes providing lithium bicarbonate in a first aqueous mixture. The lithium bicarbonate is then reacted with metal acetate thereby forming a second aqueous mixture comprising metal carbonate, lithium acetate, acetic acid and water wherein the acetic acid is neutralized with lithium hydroxide thereby forming a first mixture comprising metal carbonate and lithium acetate. The first mixture is separated into a second mixture and a third mixture wherein the second mixture comprises the metal carbonate and a first portion of lithium acetate with metal carbonate and lithium acetate being in a predetermined molar ratio. The third mixture comprises a second portion of lithium acetate. The second mixture is dried thereby forming the precursor comprising metal carbonate and lithium acetate in the predetermined molar ratio.

An improved process is provided for forming a precursor to a lithium metal oxide. An improved lithium metal oxide formed by calcining the precursor is also provided. The process includes providing lithium bicarbonate in a first aqueous mixture. The lithium bicarbonate is then reacted with metal acetate thereby forming a second aqueous mixture comprising metal carbonate, lithium acetate, acetic acid and water wherein the acetic acid is neutralized with lithium hydroxide thereby forming a first mixture comprising metal carbonate and lithium acetate. The first mixture is separated into a second mixture and a third mixture wherein the second mixture comprises the metal carbonate and a first portion of lithium acetate with metal carbonate and lithium acetate being in a predetermined molar ratio. The third mixture comprises a second portion of lithium acetate. The second mixture is dried thereby forming the precursor comprising metal carbonate and lithium acetate in the predetermined molar ratio.

The present invention provides a precursor of positive electrode active substance particles for non-aqueous electrolyte secondary batteries which have a high discharge voltage and a high discharge capacity, hardly suffer from side reactions with an electrolyte solution, and are excellent in cycle characteristics, positive electrode active substance particles for non-aqueous electrolyte secondary batteries, and processes for producing these particles, and a non-aqueous electrolyte secondary battery. The present invention relates to positive electrode active substance particles for non-aqueous electrolyte secondary batteries having a spinel structure with a composition represented by the following chemical formula (1), in which the positive electrode active substance particles satisfy the following characteristic (A) and/or characteristic (B) when indexed with Fd3m in X-ray diffraction thereof: (A) when indexed with Fd3m in X-ray diffraction of the positive electrode active substance particles, a ratio of I(311) to I(111) [I(311)/I(111)] is in the range of 35 to 43%, and/or (B) when indexed with Fd3m in X-ray diffraction of the positive electrode active substance particles, a gradient of a straight line determined by a least square method in a graph prepared by plotting sin in an abscissa thereof and B cos in an ordinate thereof wherein B is a full-width at half maximum with respect to each peak position 2 (10 to 90) is in the range of 3.010.sup.4 to 20.010.sup.4; and
Li.sub.1+xMn.sub.2yzNi.sub.yM.sub.zO.sub.4Chemical Formula (1)
wherein x, y, z fall within the range of 0.05x0.15, 0.4y0.6 and 0z0.20, respectively; and M is at least one element selected from the group consisting of Mg, Al, Si, Ca, Ti, Co, Zn, Sb, Ba, W and Bi.

Disclosed are a manganese-doped cobaltosic tetroxide, and a preparation method and application thereof, belonging to the field of battery materials. The preparation method of the manganese-doped cobaltosic tetroxide of the disclosure dopes a manganese element into cobalt carbonate with a specific process and matched with a composite surfactant, which can obtain manganese-doped cobaltosic tetroxide particle products with uniform particle size, dispersion and fineness through high-temperature sintering, a proportion of low-valence manganese in the doped manganese is high, and a crystal form of the products obtained by sintering is complete. The preparation method is simple in operation and can realize industrial large-scale production. The manganese-doped cobaltosic tetroxide prepared by the preparation method and the application thereof are also disclosed.

The present invention provides a precursor of positive electrode active substance particles for non-aqueous electrolyte secondary batteries which have a high discharge voltage and a high discharge capacity, hardly suffer from side reactions with an electrolyte solution, and are excellent in cycle characteristics, positive electrode active substance particles for non-aqueous electrolyte secondary batteries, and processes for producing these particles, and a non-aqueous electrolyte secondary battery. The present invention relates to positive electrode active substance particles for non-aqueous electrolyte secondary batteries having a spinel structure with a composition represented by the following chemical formula (1), in which the positive electrode active substance particles satisfy the following characteristic (A) and/or characteristic (B) when indexed with Fd-3m in X-ray diffraction thereof: (A) when indexed with Fd-3m in X-ray diffraction of the positive electrode active substance particles, a ratio of I(311) to I(111) [I(311)/I(111)] is in the range of 35 to 43%, and/or (B) when indexed with Fd-3m in X-ray diffraction of the positive electrode active substance particles, a gradient of a straight line determined by a least square method in a graph prepared by plotting sin in an abscissa thereof and B cos in an ordinate thereof wherein B is a full-width at half maximum with respect to each peak position 2 (10 to 90) is in the range of 3.010.sup.4 to 20.010.sup.4; and

Li.sub.1+xMn.sub.2-y-zNi.sub.yM.sub.zO.sub.4Chemical Formula (1)

wherein x, y, z fall within the range of 0.05.Math.x.Math.0.15, 0.4.Math.y.Math.0.6 and 0.Math.z.Math.0.20, respectively; and M is at least one element selected from the group consisting of Mg, Al, Si, Ca, Ti, Co, Zn, Sb, Ba, W and Bi.

Provided is a spinel-type lithium metal composite oxide that makes it possible to achieve excellent high-temperature storage characteristics when used as a positive electrode active material of a lithium battery. The spinel-type (Fd-3m) lithium metal composite oxide is characterized by the oxygen occupancy (OCC) thereof as determined by the Rietveld method being 0.965-1.000, the lattice strain thereof as determined by the Williamson-Hall method being 0.015-0.090, and the ratio (Na/Mn) of the molar content of Na to the molar content of Mn satisfying 0.00<Na/Mn<1.0010.sup.2.

Disclosed are a manganese-doped cobaltosic tetroxide, and a preparation method and application thereof, belonging to the field of battery materials. The preparation method of the manganese-doped cobaltosic tetroxide of the disclosure dopes a manganese element into cobalt carbonate with a specific process and matched with a composite surfactant, which can obtain manganese-doped cobaltosic tetroxide particle products with uniform particle size, dispersion and fineness through high-temperature sintering, a proportion of low-valence manganese in the doped manganese is high, and a crystal form of the products obtained by sintering is complete. The preparation method is simple in operation and can realize industrial large-scale production. The manganese-doped cobaltosic tetroxide prepared by the preparation method and the application thereof are also disclosed.

According to one embodiment, there is provided a positive electrode including a positive electrode active material-including layer including a positive electrode active material, which includes a lithium-manganese oxide LiMn.sub.2-xM.sub.xO.sub.4, and a conductive agent. In the positive electrode active material-including layer, an average particle diameter d.sub.50 is within 2 m to 5 m, a particle diameter d.sub.10 and a particle diameter d.sub.90, where a cumulative frequency from a smaller side is, respectively, 10% and 90%, is within 0.5 m to 3 m and within 4 m to 10 m, respectively, in a particle size distribution. X, represented by X=(d.sub.50d.sub.10) /d.sub.50 is within 0.4 to 0.8. Y, represented by Y=(d.sub.90d.sub.50)/d.sub.90 is within 0.2 to 0.6.

A fused product including lithium-manganese spinel, which is optionally doped, having a spinel structure AB.sub.2O.sub.4, where the site A is occupied by lithium and the site B is occupied by manganese, it being possible for the site B to be doped with an element B and it being possible for the site A to exert a substoichiometry or a superstoichiometry with respect to the site B, so that the product observes the formula Li.sub.(1+x)Mn.sub.(2y)B.sub.yO.sub.4, with 0.20x0.4 and 0y1, the element B being chosen from aluminum, cobalt, nickel, chromium, iron, magnesium, titanium, vanadium, copper, zinc, gallium, calcium, niobium, yttrium, barium, silicon, boron, zirconium and their mixtures.