The present invention relates to a method of preparing a precursor material of a positive electrode active material from a waste lithium secondary battery, to a method of preparing a lithium secondary battery positive electrode active material including a precursor material prepared by the same precursor preparation method, and to a lithium secondary battery positive electrode active material prepared by the same positive electrode active material preparation method.

In a method for recovering an active metal of a lithium secondary battery, a cathode active material mixture is prepared from a cathode of a lithium secondary battery. A first reductive process using a first reductive reaction gas and a second reductive process using a second reductive reaction gas that has a higher reaction source concentration than that of the first reductive reaction gas are performed sequentially and continuously to convert the cathode active material mixture into a preliminary precursor mixture. A lithium precursor is recovered from the preliminary precursor mixture. A lithium recovery ratio may be increased by a stepwise reduction while preventing an increase of heating value.

A green chemistry hydrometallurgical process for recovering one or more metals from a metal-containing material includes leaching the metal-containing material with formic acid, obtaining a leachate comprising the one or more metals as one or more metal formates, and precipitating at least one of the one or more metal formates. The metal-containing material may be a lithium-ion battery cathode material, resulting in Li formate remaining in solution and precipitation of salts including one or more of Ni, Co, and Mn formates. Steps may include filtration of the leachate, sulphurization of retained metal formate salts to produce metal sulphate salts, purification of filtered leachate by adding lithium carbonate and filtering, dewatering of the purified leachate, and thermal decomposition of resulting lithium salts to produce battery grade lithium carbonate. Carbon dioxide, water, and formic acid may be recovered and reused, without liquid or solid waste produced.

A method, a system, and an apparatus for preparing manganese sulfate are provided. The method comprises introducing materials comprising a first stream, a second stream, and a reductant to a reactor to form a mixture. The first stream comprises a sulfate-containing acid, and the second stream comprises a manganese oxide compound. At least a portion of the mixture is reacted to provide a reactor outlet stream comprising an aqueous portion and an undissolved portion. The method comprises separating at least a portion of the aqueous portion from the undissolved portion in the reactor outlet stream to produce an aqueous stream comprising manganese sulfate and an undissolved stream.

A method, a system, and an apparatus for preparing manganese sulfate are provided. The method comprises introducing materials comprising a first stream, a second stream, and a reductant to a reactor to form a mixture. The first stream comprises a sulfate-containing acid, and the second stream comprises a manganese oxide compound. At least a portion of the mixture is reacted to provide a reactor outlet stream comprising an aqueous portion and an undissolved portion. The method comprises separating at least a portion of the aqueous portion from the undissolved portion in the reactor outlet stream to produce an aqueous stream comprising manganese sulfate and an undissolved stream.

A variety of systems, methods and compositions are disclosed, including, in one method for recycling a spent alkaline battery comprising: dissolving insoluble metal ions in aqueous solution thereby producing pregnant leach solution; extracting zinc sulfate from aqueous solution thereby producing zinc sulfate product and raffinate solution comprising manganese sulfate and potassium sulfate; separating manganese hydroxide from raffinate solution thereby producing manganese sulfate product and aqueous potassium sulfate solution; crystallizing aqueous potassium sulfate solution to produce solid potassium sulfate product. A system for recycling spent alkaline battery comprising: first liquid-solid extraction unit capable of dissolving insoluble metal ions in aqueous solution thereby producing pregnant leach solution; liquid-liquid extraction unit capable of extracting zinc from pregnant leach solution; second liquid-solid extraction unit capable of precipitating manganese hydroxide from raffinate produced by liquid-liquid extraction unit; and third liquid-solid extraction unit capable of crystallizing aqueous potassium sulfate solution produced by second liquid-solid extraction unit.

A variety of systems, methods and compositions are disclosed, including, in one method for recycling a spent alkaline battery comprising: dissolving insoluble metal ions in aqueous solution thereby producing pregnant leach solution; extracting zinc sulfate from aqueous solution thereby producing zinc sulfate product and raffinate solution comprising manganese sulfate and potassium sulfate; separating manganese hydroxide from raffinate solution thereby producing manganese sulfate product and aqueous potassium sulfate solution; crystallizing aqueous potassium sulfate solution to produce solid potassium sulfate product. A system for recycling spent alkaline battery comprising: first liquid-solid extraction unit capable of dissolving insoluble metal ions in aqueous solution thereby producing pregnant leach solution; liquid-liquid extraction unit capable of extracting zinc from pregnant leach solution; second liquid-solid extraction unit capable of precipitating manganese hydroxide from raffinate produced by liquid-liquid extraction unit; and third liquid-solid extraction unit capable of crystallizing aqueous potassium sulfate solution produced by second liquid-solid extraction unit.

Provided is a method for inhibiting extractant degradation in the DSX process through the manganese extraction control, the method comprising: (a) stirring DSX solvent and DSX feed solution, which is a solution containing a valuable metal from which iron has been removed in an agitator, in which soda ash (Na.sub.2CO.sub.3) is further added to maintain a constant pH; and (b) scrubbing the manganese from the DSX solvent, extracted in step (a).

Provided is a method for inhibiting extractant degradation in the DSX process through the manganese extraction control, the method comprising: (a) stirring DSX solvent and DSX feed solution, which is a solution containing a valuable metal from which iron has been removed in an agitator, in which soda ash (Na.sub.2CO.sub.3) is further added to maintain a constant pH; and (b) scrubbing the manganese from the DSX solvent, extracted in step (a).

In a method for recovering an active metal of a lithium secondary battery, a sulfuric acid solution is added to a lithium metal composite oxide so as to prepare a sulfated active material solution. A transition metal is extracted from the sulfated active material solution. A lithium precursor is recovered by adding a lithium extracting agent to the solution remaining after the transition metal has been extracted from the sulfated active material solution. In the method, the amount of impurities is reduced, and sulfuric acid and the neutralizing agent can be recycled so that a high-yield lithium precursor recovery is enabled.