Provided is a method of inhibiting degradation of an extractant by an anhydrous environment avoiding and metal stripping, the method including the steps of: (a) stopping the addition of soda ash (Na.sub.2CO.sub.3) to an extracting reaction tank; (b) starting solution recirculation and stopping solvent recirculation of a settler; (c) supplying a solvent from a loaded organic tank to a scrubbing reaction tank, in which the scrubbing reaction tank, stripping reaction tank and extracting reaction tank are connected for circulation and operating stirrers of the scrubbing reaction tank, stripping reaction tank and extracting reaction tank; (d) supplying a sulfuric acid solution having a controlled concentration with a diluting solution to the stripping reaction tank; (e) transferring the solvents of the settler, the loaded organic tank and all the pipes to the scrubbing reaction tank; and (f) stopping the step (e) and initiating solvent recirculation.

A manganese-lithium separation process and a pre-extraction solution preparation process in comprehensive recovery of ternary battery wastes, and a method for comprehensive recovery of cobalt, nickel, manganese and lithium elements from the ternary battery wastes, relates to a method for recycling battery wastes. According to the present disclosure, cobalt and nickel ions are separated from an impurity-removed solution by a hydrolysis method; manganese, lithium and other ions in the impurity-removed solution are free from an extraction procedure, so that most manganese ions are separated and removed by a wet method before extraction, to prevent the manganese ions from entering the extraction system; nickel ions are free from an extraction procedure of full extraction and full back-extraction; and nickel hydroxide is directly precipitated after related impurities are removed by extraction.

A method of manufacturing a cobalt-nickel-containing solution including: preparing a crude nickel hydroxide and/or a crude cobalt hydroxide as a starting material, the crude nickel or cobalt hydroxide containing cobalt and nickel and elements except the cobalt and nickel as impurities, the crude nickel hydroxide containing the nickel more than the cobalt, and the crude cobalt hydroxide containing the cobalt more than the nickel; a water-washing process for obtaining a post-water-washing crude hydroxide from the starting material; a leaching process for obtaining a post-leaching solution from the post-water-washing crude hydroxide; a neutralization process of subjecting the post-leaching solution to neutralization and solid-liquid-separation to remove the impurities as a post-neutralization residue containing one or more of iron, silicon, aluminum, and chromium, thereby obtaining a post-neutralization solution; and an extraction process of subjecting the post-neutralization solution to solvent extraction to obtain a post-extraction solution containing cobalt and nickel with the impurities reduced.

The present invention describes systems and methods of a novel hydrometallurgical process to perform reductive-acid leaching and separation of constituent compounds from solid material generated from the electrodes of lithium-ion batteries, or other source material containing target high-value materials. The process method involves the initial reductive-acid leaching with sulfur dioxide and sulfuric acid of the source material which may be performed in a single or a multi-step embodiment. In a single-step embodiment, the reductive-acid leaching results in two outlet streams, a leachate solution and a bulk solid, such as graphite. In a two-step embodiment, a dilute reductive-acid leaching results in a lithium brine that may be bled as a product stream. The resulting liquor, or leachate, can be subjected to precipitation and oxidation steps to remove other compounds except, for example lithium, cobalt, and nickel. Electrowinning may then be used to separate and recover cobalt and nickel alloys among other high value compounds from a lithium brine.

A method for recovering at least cobalt of valuable metals, cobalt and nickel, from an acidic solution obtained by subjecting waste containing positive electrode materials for lithium ion secondary batteries to a wet process, the acidic solution comprising cobalt ions, nickel ions and impurities, the method including: a first extraction step for Co recovery, the first extraction step being for extracting cobalt ions by solvent extraction from the acidic solution and stripping the cobalt ions; and a second extraction step for Co recovery, the second extraction step being for extracting cobalt ions by solvent extraction from a stripped solution obtained in the first extraction step for Co recovery and stripping the cobalt ions, wherein the first extraction step for Co recovery includes: a solvent extraction process for extracting cobalt ions in the acidic solution into a solvent; a scrubbing process for scrubbing the solvent that has extracted the cobalt ions; and a stripping process for stripping the cobalt ions in the solvent after the scrubbing into a solution.

Cathode material from exhausted lithium ion batteries are dissolved in a solution for extracting the useful elements Co (cobalt), Ni (nickel), Al (Aluminum) and Mn (manganese) to produce active cathode materials for new batteries. The solution includes compounds of desirable materials such as cobalt, nickel, aluminum and manganese dissolved as compounds from the exhausted cathode material of spent cells. Depending on a desired proportion, or ratio, of the desired materials, raw materials are added to the solution to achieve the desired ratio of the commingled compounds for the recycled cathode material for new cells. The desired materials precipitate out of solution without extensive heating or separation of the desired materials into individual compounds or elements. The resulting active cathode material has the predetermined ratio for use in new cells, and avoids high heat typically required to separate the useful elements because the desired materials remain commingled in solution.

Provided is a method for separating copper from nickel and cobalt, which can efficiently and selectively separate copper from nickel and cobalt in a substance containing copper, nickel, and cobalt in a waste lithium ion battery, etc. In this method, a substance containing copper, nickel, and cobalt is sulfurated to obtain a sulfide, the obtained sulfide that contains copper, nickel, and cobalt is brought into contact with an acid solution to obtain a solid containing copper and a leachate containing nickel and cobalt. The sulfide preferably contains copper sulfide as a main component, and contains nickel metal and cobalt metal. In-addition, when bringing the sulfide into contact with the acid solution, the added amounts of the sulfide and the acid solution are preferably adjusted such that the oxidation-reduction potential of the obtained leachate is maintained at 150 mV or less where a silver/silver chloride electrode is a reference electrode.

A process for recovering a nickel cobalt manganese hydroxide from recycled lithium-ion battery (LIB) material such as black mass, black powder, filter cake, or the like. The recycled LIB material is mixed with water and either sulfuric acid or hydrochloric acid at a pH less than 2. Cobalt, nickel, and manganese oxides from the recycled lithium-ion battery material dissolve into the acidic water with the reductive assistance of gaseous sulfur dioxide. Anode carbon is filtered from the acidic water, leaving the dissolved cobalt, nickel, and manganese oxides in a filtrate. The filtrate is mixed with aqueous sodium hydroxide at a pH greater than 8. Nickel cobalt manganese hydroxide precipitates from the filtrate. The nickel cobalt manganese hydroxide is filtered from the filtrate and dried. The filtrate may be treated ammonium fluoride or ammonium bifluoride to precipitate lithium fluoride from the filtrate. The composition ratio of nickel to cobalt to manganese in the acid filtrate may be adjusted to a desired ratio. The anode carbon is recovered and purified for reuse.

Disclosed is a method for purifying a nickel-cobalt-manganese leaching solution. The method may include: heating a nickel-cobalt-manganese leaching solution, adding a manganese powder thereto, adjusting the pH, reacting same, and filtering same to obtain iron-aluminum slag and a liquid with iron and aluminum removed therefrom; heating the liquid with iron and aluminum removed therefrom, adding a manganese powder thereto, adjusting the pH, reacting same, and filtering same to obtain copper slag and a solution with copper removed therefrom; heating the solution with copper removed therefrom, adding an alkaline solution thereto, adjusting the pH, reacting same, and filtering same to obtain a nickel-cobalt-precipitated solution and nickel-cobalt-manganese hydroxide; and adding water into nickel-cobalt-manganese hydroxide for slurrying, heating same, adding an acidic solution for dissolution, adjusting the pH, reacting same, heating same, adding a manganese powder thereto, adjusting the pH, and filtering same to obtain iron-aluminum slag and a nickel-cobalt-manganese sulfate solution.

A method of recovering cobalt and nickel includes the steps of: adding alkaline to an acidic solution containing aluminum together with cobalt and nickel, adjusting pH of the acidic solution to 5 to 7, and converting the cobalt, the nickel and the aluminum into hydroxides thereof; recovering the hydroxides by solid-liquid separation, mixing the recovered hydroxides with an alkaline solution, and leaching aluminum contained in the hydroxides under a liquid condition of pH 8 or more; and recovering a cobalt hydroxide and a nickel hydroxide that aluminum is separated therefrom by solid-separation on a leachate.