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.

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.

The present disclosure refers to a method of obtaining metal ions from a battery, the method comprising adding a crushed battery to a leaching solution comprising fruit and organic acid, thereby obtaining a leachate comprising metal ions, wherein the method is performed at a temperature above 80° C.

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.

The present invention relates to a process for recovering one or more metal ions selected from the group consisting of Cobalt, Nickel, Manganese and a mixture thereof from metal-containing residues comprising: A) leaching the residue with a leaching solution comprising lactic acid to obtain a filtrate 1 and a solid cake 1; B) separating the filtrate 1; C) precipitating the Cobalt lactate, Nickel lactate or Manganese lactate from the filtrate 1 to obtain a filtrate 2 and a precipitate 1; and D) separating the precipitate 1; or alternatively, A) leaching the residue with the leaching solution to obtain a filtrate 1 and a solid cake 1; E) precipitating the Cobalt lactate, Nickel lactate or Manganese lactate from the filtrate 1 to obtain a filtrate 3 and a solid cake 2; and F) separating the solid cake 2; and G) separating the Cobalt lactate, Nickel lactate or Manganese lactate from the solid cake 2.

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.

The present disclosure discloses a recycling method for a mixed waste material of lithium nickel manganese cobalt oxide (LNMCO) and lithium iron phosphate (LFP), including: conducting acid-leaching to obtain an acid-leaching liquor with nickel, cobalt, manganese, phosphorus, iron, and lithium; conducting adsorption separation with a resin, washing the resin with sulfuric acid to obtain a mixed solution of nickel sulfate, cobalt sulfate, and manganese sulfate, and subjecting the mixed solution to precipitation to obtain an LNMCO cathode material precursor; and subjecting an obtained solution with phosphorus, iron, and lithium to lithium precipitation to obtain a lithium salt precipitate, and subjecting a post-precipitation solution to concentration and electrospinning to obtain a ferric phosphate/carbon material. The process of the present disclosure can achieve comprehensive recycling of a mixed waste material of LNMCO and LFP and the directed circulation of waste LNMCO and LFP materials.

A method for extracting secondary metal values from a sulfuric acid leachate is provided. The method includes providing a leachate which contains a primary metal and a plurality of secondary metals, wherein the primary metal is selected from the group consisting of Cu, Li and Ni and is derived from sulfuric acid leaching of an ore; passing the leachate through a first ion exchange resin which is selective to, and releasably binds, the plurality of secondary metals; stripping the plurality of secondary metals from the second or third ion exchange resins, thereby obtaining a first extract; and recovering the secondary metals from the first extract.

A process is disclosed for the recovery of valuable metals from oxidic ores, in particular from polymetallic nodules. The process is suitable for the recovery of Cu, Co, Ni, Fe, and Mn, which are the main metals of interest in such polymetallic nodules. The present process is, among others, characterized by the handling of Fe, which is dissolved and kept in solution until the step of crystallization rather than removed at an earlier stage. A mixed Mn—Fe residue is obtained, which, after thermal treatment, provides a Mn—Fe oxide that is suitable for the steel or for the manganese industry. Excellent Cu, Co and Ni yields are obtained, while Fe is leached and valorized together with Mn.

The present disclosure concerns a process for the recovery of valuable metals from polymetallic nodules. A two-stage process using SO.sub.2 in an acidic aqueous media is disclosed. In a first step, performed in mildly acidic conditions, Mn, Ni, and Co are dissolved; in a second, more acidic step, Cu is dissolved. Under these conditions, the leachate of the first step contains most of the Mn, Ni, and Co, while being nearly Cu-free. The Ni and Co are precipitated as sulfides; the Mn can be recovered as sulfate by crystallization. Cu, which is leached in the second step, is secretively precipitated, also as sulfide.