The present disclosure relates to double layered hydroxide-type compounds comprising both di- and tri-valent nickel ions, and the use of such compounds in electrodes for energy storage device in addition to a previously developed electrode using Fe.sup.2+ and Fe.sup.3+ “green rusts related compounds”.

The present disclosure relates to double layered hydroxide-type compounds comprising both di- and tri-valent nickel ions, and the use of such compounds in electrodes for energy storage device in addition to a previously developed electrode using Fe.sup.2+ and Fe.sup.3+ “green rusts related compounds”.

A carbonate precursor compound for manufacturing a lithium metal (M)-oxide powder usable as an active positive electrode material in lithium-ion batteries, M comprising 20 to 90 mol % Ni, 10 to 70 mol % Mn and 10 to 40 mol % Co, the precursor further comprising a sodium and sulfur impurity, wherein the sodium to sulfur molar ratio (Na/S) is 0.4<Na/S<2. Thes lithium metal (M)-oxide powder has a particle size distribution with 10 μm≤D50≤20 μm, a specific surface with 0.9≤BET≤5, the BET being expressed in g/cm.sup.2, the powder further comprises a sodium and sulfur impurity, wherein the sum (2*Na.sub.wt)+S.sub.wt of the sodium (Na.sub.wt) and sulfur (S.sub.wt) content expressed in wt % is more than 0.4 wt % and less than 1.6 wt %, and wherein the sodium to sulfur molar ratio (Na/S) is 0.4<Na/S<2.

A carbonate precursor compound for manufacturing a lithium metal (M)-oxide powder usable as an active positive electrode material in lithium-ion batteries, M comprising 20 to 90 mol % Ni, 10 to 70 mol % Mn and 10 to 40 mol % Co, the precursor further comprising a sodium and sulfur impurity, wherein the sodium to sulfur molar ratio (Na/S) is 0.4<Na/S<2. Thes lithium metal (M)-oxide powder has a particle size distribution with 10 μm≤D50≤20 μm, a specific surface with 0.9≤BET≤5, the BET being expressed in g/cm.sup.2, the powder further comprises a sodium and sulfur impurity, wherein the sum (2*Na.sub.wt)+S.sub.wt of the sodium (Na.sub.wt) and sulfur (S.sub.wt) content expressed in wt % is more than 0.4 wt % and less than 1.6 wt %, and wherein the sodium to sulfur molar ratio (Na/S) is 0.4<Na/S<2.

A positive electrode active material precursor for a nonaqueous electrolyte secondary battery is provided that includes a nickel-cobalt-manganese carbonate composite represented by general formula Ni.sub.xCo.sub.yMn.sub.zM.sub.tCO.sub.3 (where x+y+z+t=1, 0.05≤x≤0.3, 0.1≤y≤0.4, 0.55≤z≤0.8, 0≤t≤0.1, and M denotes at least one additional element selected from a group consisting of Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo, and W) and a hydrogen-containing functional group. The ratio H/Me of the amount of hydrogen H to the amount of metal components Me included in the positive electrode active material precursor is less than 1.60. The positive electrode active material further includes a secondary particle formed by a plurality of primary particles that have been aggregated.

A positive electrode active material precursor for a nonaqueous electrolyte secondary battery is provided that includes a nickel-cobalt-manganese carbonate composite represented by general formula Ni.sub.xCo.sub.yMn.sub.zM.sub.tCO.sub.3 (where x+y+z+t=1, 0.05≤x≤0.3, 0.1≤y≤0.4, 0.55≤z≤0.8, 0≤t≤0.1, and M denotes at least one additional element selected from a group consisting of Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo, and W) and a hydrogen-containing functional group. The ratio H/Me of the amount of hydrogen H to the amount of metal components Me included in the positive electrode active material precursor is less than 1.60. The positive electrode active material further includes a secondary particle formed by a plurality of primary particles that have been aggregated.

In a method for the precipitation of particles of a metal carbonate material comprising nickel and manganese in an atomic ratio of 0≤Ni:Mn≤1:3, aqueous solutions comprising sulfates or nitrates of nickel and manganese are mixed with aqueous solutions of carbonates or mixtures of carbonates and hydroxides of sodium or potassium in a stirred reactor at pH>7.5 without the use of a chelating agent. Thereby agglomerated particles are formed without any subsequent process steps, in particular no subsequent process at temperatures higher than the precipitation temperature.

In a method for the precipitation of particles of a metal carbonate material comprising nickel and manganese in an atomic ratio of 0≤Ni:Mn≤1:3, aqueous solutions comprising sulfates or nitrates of nickel and manganese are mixed with aqueous solutions of carbonates or mixtures of carbonates and hydroxides of sodium or potassium in a stirred reactor at pH>7.5 without the use of a chelating agent. Thereby agglomerated particles are formed without any subsequent process steps, in particular no subsequent process at temperatures higher than the precipitation temperature.

A positive-electrode active material precursor for a nonaqueous electrolyte secondary battery, contains a nickel-cobalt-manganese carbonate composite represented by a general formula of Ni.sub.xCo.sub.yMn.sub.zM.sub.tCO.sub.3 where x+y+z+t=1, 0.05≤x≤0.3, 0.1≤y≤0.4, 0.55≤z≤0.8, and 0≤t≤0.1 are satisfied; and M represents one or more additive elements selected from among Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo, and W. The positive-electrode active material precursor includes secondary particles having an average particle diameter greater than or equal to 4 μm and less than or equal to 9 μm. The secondary particle includes a sparse central portion and a dense outer shell portion outside of the central portion, formed of primary particles.

A positive-electrode active material precursor for a nonaqueous electrolyte secondary battery, contains a nickel-cobalt-manganese carbonate composite represented by a general formula of Ni.sub.xCo.sub.yMn.sub.zM.sub.tCO.sub.3 where x+y+z+t=1, 0.05≤x≤0.3, 0.1≤y≤0.4, 0.55≤z≤0.8, and 0≤t≤0.1 are satisfied; and M represents one or more additive elements selected from among Mg, Ca, Al, Ti, V, Cr, Zr, Nb, Mo, and W. The positive-electrode active material precursor includes secondary particles having an average particle diameter greater than or equal to 4 μm and less than or equal to 9 μm. The secondary particle includes a sparse central portion and a dense outer shell portion outside of the central portion, formed of primary particles.