Production process for composite oxide, positive-electrode active material for lithium-ion secondary battery and lithium-ion secondary battery
A composite oxide is produced via the following: a raw-material mixture preparation step of preparing a raw-material mixture by mixing a metallic-compound raw material and a molten-salt raw material with each other, the metallic-compound raw material at least including one or more kinds of Mn-containing metallic compounds being selected from the group consisting of oxides, hydroxides and metallic salts that include one or more kinds of metallic elements in which Mn is essential, the molten-salt raw material including lithium hydroxide and lithium nitrate, and exhibiting a proportion of the lithium hydroxide with respect to the lithium nitrate (i.e., (Lithium Hydroxide)/(Lithium Nitrate)) that falls in a range of from 0.05 or more to less than 1 by molar ratio; a molten reaction step of reacting said raw-material mixture at from 300° C. or more to 550° C. or less by melting it: and a recovery step of recovering said composite oxide being generated from said raw-material mixture that has undergone the reaction.
1. A production process for composite oxide being characterized in that:
it is a production process for composite oxide comprising a dual crystal structure of layered rock-salt structure and spinel structure, and the composite oxide at least including lithium (Li) element and manganese (Mn) element;
said composite oxide is obtained via the following:
a raw-material mixture preparation step of preparing a raw-material mixture by mixing a metallic-compound raw material and a molten-salt raw material with each other,
the metallic-compound raw material at least including one or more kinds of Mn-containing metallic compounds being selected from the group consisting of oxides, hydroxides and metallic salts that include one or more kinds of metallic elements in which Mn is essential,
the molten-salt raw material including lithium hydroxide and lithium nitrate, and exhibiting a proportion of the lithium hydroxide with respect to the lithium nitrate (i.e., (Lithium Hydroxide)/(Lithium Nitrate)) that falls in a range of from 0.05 or more to less than 1 by molar ratio;
a molten reaction step of reacting said raw-material mixture at from 300° C. or more to 550° C. or less by melting it: and
a recovery step of recovering said composite oxide being generated from said raw-material mixture that has undergone the reaction.
2. The production process for composite oxide as set forth in claim 1 further including a heat-calcination treatment step, in which said composite oxide being recovered is heated, after said recovery step.
3. The production process for composite oxide as set forth in claim 2 , wherein said heat-calcination treatment step is a step of heating said composite oxide in an oxygen-containing atmosphere.
4. The production process for composite oxide as set forth in claim 1 , wherein said metallic-compound raw material further includes one or more kinds of second metallic compounds being selected from the group consisting of oxides, hydroxides and metallic salts that include one or more kinds of metallic elements other than Mn.
5. The production process for composite oxide as set forth in claim 4 , wherein said second metallic compounds include one or more kinds of transition metal elements other than Mn.
6. The production process for composite oxide, wherein a precursor synthesis step, in which an aqueous solution including at least two kinds of metallic elements is alkalified in order to obtain precipitates, is further carried out before the raw-material mixture preparation step in the production process for composite oxide as set forth in claim 1 , and then said metallic-compound raw material including the precipitates is employed at the mixture preparation step.
7. The production process for composite oxide as set forth in claim 1 , wherein said molten-salt raw material exhibits a proportion of lithium hydroxide with respect to lithium nitrate (i.e., (Lithium Hydroxide)/(Lithium Nitrate)), the proportion falling in a range of from 0.2 or more to 0.7 or less by molar ratio.
8. The production process for composite oxide as set forth in claim 1 , wherein said raw-material mixture exhibits a proportion of metal being included in said metallic-compound raw material with respect to lithium metal being included in said molten-salt raw material (i.e., (Metal in Metallic-compound Raw Material)/(Lithium Metal in Molten-salt Raw Material)), the proportion falling in a range of from 0.01 or more to 0.2 or less by molar ratio.
9. The production process for composite oxide as set forth in claim 1 , wherein said molten reaction step is carried out in an oxygen-containing atmosphere.
10. The production process for composite oxide as set forth in claim 1 , wherein said molten-salt raw material does not include any lithium peroxide.
11. The production process for composite oxide as set forth in claim 1 , wherein the molten reaction step of reacting said raw-material mixture is conducted at from 330° C. or more to 550° C. or less.