Process for preparing various metal hydroxides and oxides and their derivatives

Abstract

To provide a process that can reduce the manufacturing cost of hydroxides, which serve as raw materials for cathode materials of lithium-ion batteries.SOLUTION: A process for preparing a metal hydroxide comprises reacting a metal sulfate comprising (i) at least one metal chosen from nickel and cobalt and optionally (ii) at least one metal chosen from manganese and aluminum with sodium hydroxide and optionally a chelating agent in order to obtain a solid comprising the metal hydroxide and a liquid comprising sodium sulfate; separating the liquid and the solid from one another to obtain the metal hydroxide; submitting the liquid comprising sodium sulfate to an electromembrane process for converting sodium sulfate into sodium hydroxide; and reusing the sodium hydroxide obtained by the electromembrane process for reacting with the metal sulfate.SELECTED DRAWING: Figure 27

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This disclosure claims priority to U.S. Patent Application No. 62 / 590,260, filed November 22, 2017, and U.S. Patent Application No. 62 / 735,013, filed September 21, 2018, which are incorporated herein by reference in their entireties.

[0002] The present disclosure relates to improvements in the field of processes for preparing metal hydroxides and oxides containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum. For example, such materials may be useful in the production of cathode materials for ion batteries. [Background technology]

[0003] Processes for preparing nickel-cobalt-manganese hydroxide, nickel-cobalt-aluminum hydroxide, lithium-cobalt hydroxide, nickel-cobalt-manganese oxyhydroxide, nickel-cobalt-aluminum oxyhydroxide, lithium-cobalt oxyhydroxide, nickel-cobalt-manganese oxide, nickel-cobalt-aluminum oxide, and lithium-cobalt oxide are known, for example, however, the known processes result in high costs for the production of such hydroxides and oxides and the consumption of various chemicals.

[0004] Therefore, there is a need for at least an alternative preparation process for such hydroxides or oxides. Summary of the Invention

[0005] Thus, according to one aspect of the present disclosure, there is provided a process for preparing a metal hydroxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising: reacting a metal sulfate containing (I) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, with lithium hydroxide and optionally a chelating agent to obtain a solid containing the metal hydroxide and a liquid containing lithium sulfate; separating the liquid and the solid from each other to obtain a metal hydroxide; providing a liquid comprising lithium sulfate to an electromembrane process for converting the lithium sulfate to lithium hydroxide; and recycling the lithium hydroxide obtained by the electromembrane process to react with metal sulfates.

[0006] According to another aspect, there is provided a process for preparing a metal oxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising the steps of: reacting a metal sulfate containing (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, with lithium hydroxide and optionally a chelating agent to obtain a solid containing a metal hydroxide containing (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, and a liquid containing lithium sulfate; separating the liquid and the solid from each other to obtain a metal hydroxide; providing a liquid comprising lithium sulfate to an electromembrane process for converting the lithium sulfate to lithium hydroxide; recycling at least a first portion of the lithium hydroxide obtained by the electromembrane process to react with a metal sulfate; reacting at least a second portion of the lithium hydroxide obtained by the electromembrane process with the obtained metal hydroxides to obtain a mixture of metal hydroxides; roasting the mixture of metal hydroxides to obtain metal oxides.

[0007] According to another aspect of the present disclosure, there is provided a process for preparing a metal hydroxide comprising at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum, comprising: reacting a metal sulfate containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum with a base and optionally a chelating agent to obtain a solid containing a metal hydroxide and a liquid containing lithium sulfate; separating the liquid and the solid from each other to obtain a metal hydroxide; providing a liquid comprising lithium sulfate to an electromembrane process for converting the lithium sulfate to lithium hydroxide; and recycling the lithium hydroxide obtained by the electromembrane process to react with metal sulfates.

[0008] According to another aspect, there is provided a process for preparing a metal oxide comprising at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum, comprising: reacting a metal sulfate containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum with a base and optionally a chelating agent to obtain a solid containing a metal hydroxide containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum, and a liquid containing lithium sulfate; separating the liquid and the solid from each other to obtain a metal hydroxide; providing a liquid comprising lithium sulfate to an electromembrane process for converting the lithium sulfate to lithium hydroxide; recycling at least a first portion of the lithium hydroxide obtained by the electromembrane process to react with a metal sulfate; reacting at least a second portion of the lithium hydroxide obtained by the electromembrane process with the obtained metal hydroxides to obtain a mixture of metal hydroxides; roasting the mixture of metal hydroxides to obtain metal oxides.

[0009] According to one aspect of the present disclosure, there is provided a process for preparing a metal hydroxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising the steps of: reacting a metal sulfate and / or a metal nitrate comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, with lithium hydroxide, sodium hydroxide, and / or potassium hydroxide, and optionally a chelating agent, to obtain a solid comprising the metal hydroxide and a liquid comprising at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate; separating the liquid and the solid from each other to obtain a metal hydroxide; providing a liquid comprising at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate to an electromembrane process for converting at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate to at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide; and recycling at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide obtained by the electromembrane process for reaction with a metal sulfate and / or a metal nitrate.

[0010] According to another aspect, there is provided a process for preparing a metal oxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising the steps of: reacting a metal sulfate and / or a metal nitrate comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, with lithium hydroxide, sodium hydroxide, and / or potassium hydroxide, and optionally a chelating agent, to obtain a solid comprising a metal hydroxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, and a liquid comprising at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate; separating the liquid and the solid from each other to obtain a metal hydroxide; providing a liquid comprising at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate to an electromembrane process for converting at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate to at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide; recycling at least a first portion of at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide obtained by the electromembrane process for reacting with a metal sulfate and / or a metal nitrate; reacting at least a second portion of at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide obtained by the electromembrane process with the obtained metal hydroxides to obtain a mixture of metal hydroxides; roasting the mixture of metal hydroxides to obtain metal oxides.

[0011] According to another aspect of the present disclosure, there is provided a process for preparing a metal hydroxide comprising at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum, comprising: reacting a metal sulfate and / or a metal nitrate containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum with a base and optionally a chelating agent to obtain a solid containing a metal hydroxide and a liquid containing at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate; separating the liquid and the solid from each other to obtain a metal hydroxide; providing a liquid comprising at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate to an electromembrane process for converting at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate to at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide; and recycling at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide obtained by the electromembrane process for reaction with a metal sulfate and / or a metal nitrate.

[0012] According to another aspect, there is provided a process for preparing a metal oxide comprising at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum, comprising: reacting a metal sulfate and / or a metal nitrate containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum with a base and optionally a chelating agent to obtain a solid containing a metal hydroxide containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum, and a liquid containing at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate; separating the liquid and the solid from each other to obtain a metal hydroxide; providing a liquid comprising at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate to an electromembrane process for converting at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate to at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide; recycling at least a first portion of at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide obtained by the electromembrane process for reacting with a metal sulfate and / or a metal nitrate; reacting at least a second portion of at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide obtained by the electromembrane process with the obtained metal hydroxides to obtain a mixture of metal hydroxides; roasting the mixture of metal hydroxides to obtain metal oxides.

[0013] According to another aspect of the present disclosure, there is provided a process for preparing a metal hydroxide comprising at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum, comprising: reacting a first metal sulfate and / or a first metal nitrate containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum with a base containing a second metal and optionally a chelating agent to obtain a solid containing a metal hydroxide and a liquid containing at least one of the second metal sulfate and the second metal nitrate; separating the liquid and the solid from each other to obtain a metal hydroxide; providing a liquid comprising at least one of a second metal sulfate and a second metal nitrate to an electromembrane process for converting the at least one of the second metal sulfate and the second metal nitrate to a second metal hydroxide; and recycling the second metal hydroxide obtained by the electromembrane process to react with the first metal sulfate and / or the first metal nitrate.

[0014] According to another aspect, there is provided a process for preparing a metal oxide comprising at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum, comprising: reacting a first metal sulfate and / or a first metal nitrate containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum with a base containing a second metal and optionally a chelating agent to obtain a solid containing a metal hydroxide containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum, and a liquid containing at least one of the second metal sulfate and the second metal nitrate; separating the liquid and the solid from each other to obtain a metal hydroxide; providing a liquid comprising at least one of a second metal sulfate and a second metal nitrate to an electromembrane process for converting the at least one of the second metal sulfate and the second metal nitrate to a second metal hydroxide; recycling at least a first portion of the second metal hydroxide obtained by the electromembrane process to react with the first metal sulfate and / or the first metal nitrate; reacting at least a second portion of the second metal hydroxide obtained by the electromembrane process with the obtained metal hydroxide to obtain a mixture of metal hydroxides; roasting the mixture of metal hydroxides to obtain metal oxides.

[0015] According to another aspect, there is provided a process for preparing a metal hydroxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising: reacting a metal sulfate and / or metal nitrate comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, with lithium hydroxide, sodium hydroxide, and / or potassium hydroxide, and optionally a chelating agent, to obtain a solid comprising the metal hydroxide and a liquid comprising at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate; separating the liquid and the solid from each other to obtain a metal hydroxide; providing a liquid comprising at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate to an electromembrane process for converting at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate to at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide; and recycling at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide obtained by the electromembrane process for reaction with a metal sulfate and / or a metal nitrate.

[0016] According to another aspect, there is provided a process for preparing a metal hydroxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising: reacting a metal sulfate comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, with lithium hydroxide, sodium hydroxide, and / or potassium hydroxide, and optionally a chelating agent, to obtain a solid comprising the metal hydroxide and a liquid comprising at least one of lithium sulfate, sodium sulfate, and potassium sulfate; separating the liquid and the solid from each other to obtain a metal hydroxide; providing a liquid comprising at least one of lithium sulfate, sodium sulfate, and potassium sulfate to an electromembrane process for converting the at least one of lithium sulfate, sodium sulfate, and potassium sulfate to at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide; and recycling at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide obtained by the electromembrane process for reaction with a metal sulfate.

[0017] According to another aspect, there is provided a process for preparing a metal hydroxide comprising at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum, comprising: reacting a metal sulfate and / or a metal nitrate containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum with a base selected from LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH), Ca(OH), Sr(OH), or Ba(OH), and optionally a chelating agent, to obtain a solid containing a metal hydroxide and a liquid containing at least one of LiSO, NaSO, KSO, RbSO, CsSO, MgSO, CaSO, SrSO, BaSO, LiNO, NaNO, KNO, RbNO, CsNO, Mg(NO), Ca(NO), Sr(NO), and Ba(NO); separating the liquid and the solid from each other to obtain a metal hydroxide; At least one of Li2SO4, Na2SO4, K2SO4, Rb2SO4, Cs2SO4, MgSO4, CaSO4, SrSO4, BaSO4, LiNO3, NaNO3, KNO3, RbNO3, CsNO3, Mg(NO3)2, Ca(NO3)2, Sr(NO3)2, and Ba(NO3)2 is added to LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2, and providing a liquid comprising at least one of LiSO, NaSO, KSO, RbSO, CsSO, MgSO, CaSO, SrSO, BaSO, LiNO, NaNO, KNO, RbNO, CsNO, Mg(NO), Ca(NO), Sr(NO), and Ba(NO); and recycling at least one of LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH), Ca(OH), Sr(OH), and Ba(OH) obtained by the electromembrane process for reaction with a metal sulfate and / or a metal nitrate.

[0018] According to another aspect, there is provided a process for preparing a metal oxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising the steps of: reacting a metal sulfate and / or a metal nitrate containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum with a base selected from LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH), Ca(OH), Sr(OH), or Ba(OH), and optionally a chelating agent, to obtain a solid containing a metal hydroxide and a liquid containing at least one of LiSO, NaSO, KSO, RbSO, CsSO, MgSO, CaSO, SrSO, BaSO, LiNO, NaNO, KNO, RbNO, CsNO, Mg(NO), Ca(NO), Sr(NO), and Ba(NO); separating the liquid and the solid from one another to obtain the metal hydroxide; At least one of Li2SO4, Na2SO4, K2SO4, Rb2SO4, Cs2SO4, MgSO4, CaSO4, SrSO4, BaSO4, LiNO3, NaNO3, KNO3, RbNO3, CsNO3, Mg(NO3)2, Ca(NO3)2, Sr(NO3)2, and Ba(NO3)2 is added to LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2, or providing said liquid comprising at least one of LiSO, NaSO, KSO, RbSO, CsSO, MgSO, CaSO, SrSO, BaSO, LiNO, NaNO, KNO, RbNO, CsNO, Mg(NO), Ca(NO), Sr(NO), and Ba(NO); recycling at least a first portion of the at least one of LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH), Ca(OH), Sr(OH), or Ba(OH) obtained by the electromembrane process for reacting with the metal sulfate; reacting at least a second portion of the at least one of LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH), Ca(OH), Sr(OH), or Ba(OH) obtained by the electromembrane process with the obtained metal hydroxide to obtain a mixture of metal hydroxides; roasting the mixture of metal hydroxides to obtain the metal oxides.

[0019] According to one aspect of the present disclosure, there is provided a process for preparing a metal carbonate comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising the steps of: reacting a metal sulfate and / or a metal nitrate comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, with lithium carbonate, sodium carbonate, and / or potassium carbonate, and optionally a chelating agent, to obtain a solid comprising the metal carbonate and a liquid comprising at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate; separating the liquid and the solid from each other to obtain a metal carbonate; providing a liquid comprising at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate to an electromembrane process for converting at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate to at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide; converting at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide to at least one of lithium carbonate, sodium carbonate, and potassium hydroxide by a carbonation process; and recycling at least one of lithium carbonate, sodium carbonate, and potassium hydroxide obtained by the carbonation process for reaction with a metal sulfate and / or a metal nitrate.

[0020] According to another aspect, there is provided a process for preparing a metal oxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising the steps of: reacting a metal sulfate and / or a metal nitrate comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, with lithium carbonate, sodium carbonate, and / or potassium carbonate, and optionally a chelating agent, to obtain a solid comprising a metal carbonate comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, and a liquid comprising at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate; separating the liquid and the solid from each other to obtain a metal carbonate; providing a liquid comprising at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate to an electromembrane process for converting at least one of lithium sulfate, lithium nitrate, sodium sulfate, sodium nitrate, potassium sulfate, and potassium nitrate to at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide; converting at least one of lithium hydroxide, sodium hydroxide, and potassium hydroxide to at least one of lithium carbonate, sodium carbonate, and potassium carbonate by a carbonation process; recycling at least a first portion of at least one of lithium carbonate, sodium carbonate, and potassium carbonate obtained by the carbonation process for reacting with a metal sulfate and / or a metal nitrate; reacting at least a second portion of at least one of lithium carbonate, sodium carbonate, and potassium carbonate obtained by the carbonation process with the obtained metal carbonate to obtain a mixture of metal carbonates; roasting the mixture of metal carbonates to obtain metal oxides.

[0021] According to another aspect of the present disclosure, there is provided a process for preparing a metal carbonate comprising at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum, comprising: reacting a first metal sulfate and / or a first metal nitrate containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum with a base containing a second metal and optionally a chelating agent to obtain a solid containing a metal carbonate and a liquid containing at least one of the second metal sulfate and the second metal nitrate; separating the liquid and the solid from each other to obtain a metal carbonate; providing a liquid comprising at least one of a second metal sulfate and a second metal nitrate to an electromembrane process for converting the at least one of the second metal sulfate and the second metal nitrate to a second metal hydroxide; converting the second metal hydroxide to a second metal carbonate, which is at least one of lithium carbonate, sodium carbonate, and potassium carbonate, by a carbonation process; and recycling the second metal carbonate obtained by the carbonation process to react with the first metal sulfate and / or the first metal nitrate.

[0022] According to another aspect, there is provided a process for preparing a metal oxide comprising at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum, comprising: reacting a first metal sulfate and / or a first metal nitrate containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum with a base containing a second metal and optionally a chelating agent to obtain a solid containing a metal carbonate containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum, and a liquid containing at least one of the second metal sulfate and the second metal nitrate; separating the liquid and the solid from each other to obtain a metal carbonate; providing a liquid comprising at least one of a second metal sulfate and a second metal nitrate to an electromembrane process for converting the at least one of the second metal sulfate and the second metal nitrate to a second metal hydroxide; converting the second metal hydroxide to a second metal carbonate, which is at least one of lithium carbonate, sodium carbonate, and potassium carbonate, by a carbonation process; recycling at least a first portion of the second metal carbonate obtained by the carbonation process to react with the first metal sulfate and / or the first metal nitrate; reacting at least a second portion of the second metal carbonate obtained by the carbonation process with the obtained metal hydroxide to obtain a mixture of metal carbonates; roasting the mixture of metal carbonates to obtain metal oxides.

[0023] According to another aspect, there is provided a process for preparing a metal hydroxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising: reacting a metal sulfate containing (i) lithium, (ii) at least one metal selected from nickel and cobalt, and optionally (iii) at least one metal selected from manganese and aluminum with sodium hydroxide and optionally a chelating agent to obtain a solid containing the metal hydroxide and a liquid containing sodium sulfate and lithium sulfate; separating the liquid and the solid from one another to obtain the metal hydroxide; providing the liquid containing sodium sulfate and lithium sulfate to an electromembrane process for converting the sodium sulfate and lithium sulfate to sodium hydroxide and lithium hydroxide; and recycling the sodium hydroxide obtained by the electromembrane process to react with the metal sulfate.

[0024] According to another aspect, there is provided a process for preparing a metal hydroxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising: reacting a metal sulfate containing (i) lithium, (ii) at least one metal selected from nickel and cobalt, and optionally (iii) at least one metal selected from manganese and aluminum with sodium hydroxide and optionally a chelating agent to obtain a solid containing the metal hydroxide and a liquid containing sodium sulfate and lithium sulfate; separating the liquid and the solid from one another to obtain the metal hydroxide; separating the sodium sulfate and lithium sulfate from each other; providing said liquid containing sodium sulfate to an electromembrane process for converting said sodium sulfate to sodium hydroxide; and recycling the sodium hydroxide obtained by the electromembrane process to react with the metal sulfate.

[0025] According to another aspect, there is provided a process for preparing a metal hydroxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising: reacting a metal sulfate containing (I) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, with sodium hydroxide and optionally a chelating agent to obtain a solid containing the metal hydroxide and a liquid containing sodium sulfate; separating the liquid and the solid from one another to obtain the metal hydroxide; providing said liquid containing sodium sulfate to an electromembrane process for converting said sodium sulfate to sodium hydroxide; and recycling the sodium hydroxide obtained by the electromembrane process to react with the metal sulfate.

[0026] According to another aspect, there is provided a process for preparing a metal carbonate comprising at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum, comprising the steps of: reacting a metal sulfate and / or a metal nitrate containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum with a base selected from Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, MgCO3, CaCO3, SrCO3, and BaCO3, and optionally a chelating agent, to obtain a solid containing a metal carbonate and a liquid containing at least one of Li2SO4, Na2SO4, K2SO4, Rb2SO4, Cs2SO4, MgSO4, CaSO4, SrSO4, BaSO4, LiNO3, NaNO3, KNO3, RbNO3, CsNO3, Mg(NO3)2, Ca(NO3)2, Sr(NO3)2, and Ba(NO3)2; separating the liquid and the solid from each other to obtain a metal hydroxide; At least one of Li2SO4, Na2SO4, K2SO4, Rb2SO4, Cs2SO4, MgSO4, CaSO4, SrSO4, BaSO4, LiNO3, NaNO3, KNO3, RbNO3, CsNO3, Mg(NO3)2, Ca(NO3)2, Sr(NO3)2, and Ba(NO3)2 is added to LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2, and providing a liquid comprising at least one of LiSO, NaSO, KSO, RbSO, CsSO, MgSO, CaSO, SrSO, BaSO, LiNO, NaNO, KNO, RbNO, CsNO, Mg(NO), Ca(NO), Sr(NO), and Ba(NO); converting at least one of LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2, and Ba(OH)2 to Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, MgCO3, CaCO3, SrCO3, and BaCO3 by a carbonation process; and recycling at least one of Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, MgCO3, CaCO3, SrCO3, and BaCO3 obtained by the carbonation process for reaction with a metal sulfate and / or a metal nitrate.

[0027] According to another aspect, there is provided a process for preparing a metal oxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising the steps of: reacting a metal sulfate and / or a metal nitrate containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum with a base selected from Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, MgCO3, CaCO3, SrCO3, and BaCO3, and optionally a chelating agent, to obtain a solid containing a metal carbonate and a liquid containing at least one of Li2SO4, Na2SO4, K2SO4, Rb2SO4, Cs2SO4, MgSO4, CaSO4, SrSO4, BaSO4, LiNO3, NaNO3, KNO3, RbNO3, CsNO3, Mg(NO3)2, Ca(NO3)2, Sr(NO3)2, and Ba(NO3)2; separating the liquid and the solid from one another to obtain the metal carbonate; At least one of Li2SO4, Na2SO4, K2SO4, Rb2SO4, Cs2SO4, MgSO4, CaSO4, SrSO4, BaSO4, LiNO3, NaNO3, KNO3, RbNO3, CsNO3, Mg(NO3)2, Ca(NO3)2, Sr(NO3)2, and Ba(NO3)2 is added to LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2, or providing said liquid comprising at least one of LiSO, NaSO, KSO, RbSO, CsSO, MgSO, CaSO, SrSO, BaSO, LiNO, NaNO, KNO, RbNO, CsNO, Mg(NO), Ca(NO), Sr(NO), and Ba(NO); converting at least one of LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2, and Ba(OH)2 to Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, MgCO3, CaCO3, SrCO3, and BaCO3 by a carbonation process; recycling at least a first portion of the at least one of Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, MgCO3, CaCO3, SrCO3, and BaCO3 obtained by the carbonation process for reaction with the metal sulfate; reacting at least a second portion of the at least one of Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, MgCO3, CaCO3, SrCO3, and BaCO3 obtained by the carbonation process with the obtained metal carbonate to obtain a mixture of metal carbonates; roasting the mixture of metal carbonates to obtain the metal oxides.

[0028] According to another aspect, there is provided a process for preparing a metal oxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising the steps of: reacting a metal sulfate containing (i) lithium, (ii) at least one metal selected from nickel and cobalt, and optionally (iii) at least one metal selected from manganese and aluminum with sodium hydroxide and optionally a chelating agent to obtain a solid containing the metal hydroxide and a liquid containing sodium sulfate and lithium sulfate; separating the liquid and the solid from one another to obtain the metal hydroxide; providing the liquid containing sodium sulfate and lithium sulfate to an electromembrane process for converting the sodium sulfate and lithium sulfate to sodium hydroxide and lithium hydroxide; separating the lithium hydroxide and the sodium hydroxide from each other; recycling at least a first portion of the sodium hydroxide obtained by the electromembrane process to react with the metal sulfate; reacting at least a first portion of the lithium hydroxide obtained by the electromembrane process with the obtained metal hydroxides to obtain a mixture of metal hydroxides; roasting the mixture of metal hydroxides to obtain the metal oxides.

[0029] According to another aspect, there is provided a process for preparing a metal oxide comprising at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum, comprising: reacting a first metal sulfate and / or a first metal nitrate containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum with a base containing a second metal and optionally a chelating agent to obtain a solid containing a metal hydroxide containing at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum, and a liquid containing at least one of the second metal sulfate and the second metal nitrate; separating the liquid and the solid from each other to obtain a metal hydroxide; providing a liquid comprising at least one of a second metal sulfate and a second metal nitrate to an electromembrane process for converting the at least one of the second metal sulfate and the second metal nitrate to a second metal hydroxide; recycling at least a first portion of the second metal hydroxide obtained by the electromembrane process to react with the first metal sulfate and / or the first metal nitrate; mixing a third metal hydroxide with the resulting metal hydroxide to obtain a mixture of metal hydroxides; roasting the mixture of metal hydroxides to obtain metal oxides.

[0030] According to another aspect of the present disclosure, there is provided a process for preparing a metal hydroxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising: reacting a metal sulfate comprising (I) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, with sodium hydroxide and optionally a chelating agent to obtain a solid comprising the metal hydroxide and a liquid comprising sodium sulfate; separating the liquid and the solid from each other to obtain a metal hydroxide; providing a liquid containing sodium sulfate to an electromembrane process for converting the sodium sulfate to sodium hydroxide; and recycling the sodium hydroxide obtained by the electromembrane process to react with metal sulfates.

[0031] According to another aspect, there is provided a process for preparing a metal oxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising the steps of: reacting a metal sulfate containing (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, with sodium hydroxide and optionally a chelating agent to obtain a solid containing a metal hydroxide containing (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, and a liquid containing lithium sulfate; separating the liquid and the solid from each other to obtain a metal hydroxide; providing a liquid containing sodium sulfate to an electromembrane process for converting the sodium sulfate to sodium hydroxide; recycling at least a first portion of the sodium hydroxide obtained by the electromembrane process for reacting with a metal sulfate; mixing another metal hydroxide with the obtained metal hydroxide to obtain a mixture of metal hydroxides; roasting the mixture of metal hydroxides to obtain metal oxides.

[0032] According to another aspect, there is provided a process for preparing a metal hydroxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising: reacting a metal sulfate comprising (i) at least one metal selected from nickel and cobalt, and optionally (iii) at least one metal selected from manganese and aluminum, with sodium hydroxide and optionally a chelating agent to obtain a solid comprising the metal hydroxide and a liquid comprising sodium sulfate and optionally lithium sulfate; separating the liquid and the solid from one another to obtain the metal hydroxide; providing said liquid comprising sodium sulfate and optionally lithium sulfate to an electromembrane process for converting said sodium sulfate and optionally lithium sulfate into sodium hydroxide and optionally lithium hydroxide; and recycling the sodium hydroxide obtained by the electromembrane process to react with the metal sulfate.

[0033] According to another aspect, there is provided a process for preparing a metal hydroxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising: reacting a metal sulfate comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, with lithium hydroxide, sodium hydroxide, and / or potassium hydroxide, and optionally a chelating agent, to obtain a solid comprising the metal hydroxide and a liquid comprising lithium sulfate, sodium sulfate, and / or potassium sulfate; separating the liquid and the solid from each other to obtain a metal hydroxide; providing a liquid containing lithium sulfate, sodium sulfate, and / or potassium sulfate to an electromembrane process for converting the lithium sulfate, sodium sulfate, and / or potassium sulfate to lithium hydroxide, sodium hydroxide, and / or potassium hydroxide, respectively; recycling the sodium hydroxide obtained by the electromembrane process to react with metal sulfates; and recycling the lithium hydroxide obtained by the electromembrane process to react with metal sulfates and / or metal hydroxides.

[0034] According to another aspect, there is provided the use of a metal hydroxide, metal carbonate, and / or metal oxide obtained from the process described in the present disclosure in the manufacture of a cathode.

[0035] According to another aspect, there is provided a method of using the metal hydroxides, metal carbonates, and / or metal oxides obtained from the processes described herein, the method comprising incorporating the metal hydroxides, metal carbonates, and / or metal hydroxides in the manufacture of a cathode. [Brief explanation of the drawings]

[0036] In the following figures, which illustrate by way of example only, various embodiments of the present disclosure:

[0037] [Figure 1] FIG. 1 is a schematic diagram of a process according to an embodiment of the present disclosure. [Figure 2] X-ray diffraction pattern of cobalt hydroxide Co(OH)2 obtained using LiOH as the base source (black) and the theoretical diffraction peaks for this compound (vertical bars). [Figure 3] X-ray diffraction pattern of cobalt hydroxide Co(OH)2 obtained using NaOH as the base source (black) and the theoretical diffraction peaks for this compound (vertical bars). [Figure 4] Figure 2 shows the X-ray diffraction pattern of LiCoO2 obtained by using Co(OH)2 (black) and the theoretical diffraction peaks of this compound (vertical bars). [Figure 5] Figure 3 shows the X-ray diffraction pattern of LiCoO2 obtained by using Co(OH)2 (black) and the theoretical diffraction peaks of this compound (vertical bars). [Figure 6] 1 is a graph showing a charge / discharge curve of LiCoO2. [Figure 7]X-ray diffraction pattern (black) of nickel-cobalt-aluminum hydroxide Ni0.8Co0.15Al0.05O2(OH)2, and theoretical diffraction peaks (vertical bars) for this compound. [Figure 8] X-ray diffraction pattern of lithiated nickel-cobalt-aluminum oxide LiNi0.8Co0.15Al0.05O2 (black) and the theoretical diffraction peaks for this compound (vertical bars). [Figure 9] 1 is a graph showing charge and discharge curves of LiNi0.8Co0.15Al0.05O2. [Figure 10] X-ray diffraction pattern (black) of nickel-manganese-cobalt hydroxide Ni0.8Mn0.1Co0.1(OH)2, and theoretical diffraction peaks (vertical bars) for this compound. [Figure 11] X-ray diffraction pattern of lithiated nickel-manganese-cobalt oxide LiNi0.8Mn0.1Co0.1O2 (black) and the theoretical diffraction peaks for this compound (vertical bars). [Figure 12] X-ray diffraction pattern (black) of nickel-manganese-cobalt hydroxide Ni0.6Mn0.2Co0.2(OH)2, and the theoretical diffraction peaks for this compound (vertical bars). [Figure 13] X-ray diffraction pattern of lithiated nickel-manganese-cobalt oxide LiNi0.6Mn0.2Co0.2O2 (black) and the theoretical diffraction peaks for this compound (vertical bars). [Figure 14] 1 is a graph showing charge / discharge curves of LiNi0.6Mn0.2Co0.2O2. [Figure 15] 1 is a plot showing the concentration of H2SO4 in the anolyte of a two-compartment cell as a function of time in the example of Li2SO4 electrolysis. [Figure 16] 1 is a plot showing the conductivity of the anolyte and catholyte in a two-compartment cell as a function of time in the example of electrolysis of Li2SO4. [Figure 17] 1 is a plot showing the temperature of the anolyte and catholyte in a two-compartment cell as a function of time in the example of electrolysis of Li2SO4. [Figure 18] 1 is a plot showing the voltage in a two-compartment cell as a function of time in the example of electrolysis of Li2SO4. [Figure 19] 1 is a plot showing the flow rate of LiOH·H2O as a function of the concentration of H2SO4 in a two-compartment cell for the example of Li2SO4 electrolysis. [Figure 20] 10 is another plot showing the flow rate of LiOH·H2O as a function of the concentration of H2SO4 in a two-compartment cell for the Li2SO4 electrolysis example. [Figure 21] 1 is a plot showing current efficiency as a function of H2SO4 concentration in a two-compartment cell for the example of Li2SO4 electrolysis. [Figure 22] 1 is a plot showing the productivity of LiOH·H2O as a function of the concentration of H2SO4 in a two-compartment cell for the example of Li2SO4 electrolysis. [Figure 23] 1 is a plot showing energy consumption as a function of H2SO4 concentration in a two-compartment cell for the example of Li2SO4 electrolysis. [Figure 24] FIG. 1 is a schematic diagram of a process according to an embodiment of the present disclosure using LiOH as a pH enhancer. [Figure 25] FIG. 1 is a schematic diagram of a process according to an embodiment of the present disclosure using NaOH as a pH enhancer. [Figure 26] FIG. 1 is a schematic diagram of a process according to an embodiment of the present disclosure using LiOH and / or NaOH as pH enhancers. [Figure 27] FIG. 1 is a schematic diagram of a process according to an embodiment of the present disclosure using NaOH as a pH enhancer for a metal sulfate solution containing lithium ions. [Figure 28] FIG. 1 is a schematic diagram of a process according to an embodiment of the present disclosure involving purification and / or concentration of the recovered sulfate solution prior to the electromembrane process. [Figure 29] FIG. 1 is a schematic diagram of a process according to an embodiment of the present disclosure involving an electromembrane process and concentration of the anolyte solution and purification and / or concentration of the recovered sulfate solution prior to addition of H2O2. [Figure 30]FIG. 1 is a schematic diagram of a process according to an embodiment of the present disclosure for core-shell synthesis using LiOH and / or NaOH as pH enhancers. [Figure 31] FIG. 1 is a schematic diagram of a process according to an embodiment of the present disclosure for the synthesis of lithiated metal oxides using Li2CO3 as a pH enhancer for the precipitation of metal carbonates. [Figure 32] FIG. 1 is a schematic diagram of a process according to an embodiment of the present disclosure using nitric acid for leaching of a transition metal source. [Figure 33] FIG. 1 is a schematic diagram of a process for producing high purity sulfate using H2SO4 to leach nickel-cobalt concentrate. [Figure 34] FIG. 1 is a schematic diagram of a process for producing high purity sulfate. [Figure 35] FIG. 1 is a schematic diagram of a process for producing high purity sulfate. DETAILED DESCRIPTION OF THE INVENTION

[0038] Unless otherwise indicated, the definitions and embodiments set forth in this and other sections are intended to be applicable to all embodiments and aspects of the application described herein for which they are suitable, as would be understood by one of ordinary skill in the art.

[0039] As used in this disclosure, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise.

[0040] In understanding the scope of the present disclosure, as used herein, the term "comprising" and its derivatives are intended to be open-ended terms specifying the presence of stated features, elements, components, groups, integers, and / or steps, but do not exclude the presence of other unstated features, elements, components, groups, integers, and / or steps. The above also applies to words of similar meaning, such as the terms "including" and "having" and their derivatives. As used herein, the term "consisting" and its derivatives are intended to be open-ended terms specifying the presence of stated features, elements, components, groups, integers, and / or steps, but exclude the presence of other unstated features, elements, components, groups, integers, and / or steps. As used herein, the term "consisting essentially of" is intended to specify the presence of stated features, elements, components, groups, integers, and / or steps, and that do not materially affect the basic and novel characteristic(s) of the features, elements, components, groups, integers, and / or steps.

[0041] As used herein, terms of degree such as "about" and "approximately" refer to a reasonable amount of deviation from the modified term so as not to significantly change the end result. If this deviation does not negate the meaning of the word it modifies, these terms of degree should be interpreted as including a deviation of ±10% from the modified term.

[0042] As used herein, the term "suitable" means that the selection of particular conditions will depend on the specific operation or operation being performed, but that the selection is within the skill of one of ordinary skill in the art. All processes described herein should be carried out under conditions sufficient to provide the desired product. Those skilled in the art will understand that all reaction conditions, including, where applicable, for example, reaction time, reaction temperature, reaction pressure, reactant ratio, flow rate, reactant purity, current density, voltage, concentration, pH, redox potential, cell area, type of membrane used, and recycle rate, can be varied to optimize the yield of the desired product, and doing so is within the skill of one of ordinary skill in the art.

[0043] As used herein, the phrase "at least substantially maintained," when referring to a pH value or pH range maintained during a process or portion thereof (e.g., electrolysis, etc.) of the present disclosure, refers to maintaining the pH value or pH range for at least 75, 80, 85, 90, 95, 96, 97, 98, or 99% of the time during the process or portion thereof.

[0044] As used herein, the phrase "at least substantially maintained," when referring to a concentration value or concentration range maintained during a process or portion thereof (e.g., electrolysis, etc.) of the present disclosure, refers to maintaining the concentration value or concentration range for at least 75, 80, 85, 90, 95, 96, 97, 98, or 99% of the time during the process or portion thereof.

[0045] As used herein, the phrase "at least substantially maintained," when referring to a temperature value or temperature range maintained during a process or portion thereof (e.g., electrolysis, etc.) of the present disclosure, refers to maintaining the temperature value or temperature range for at least 75, 80, 85, 90, 95, 96, 97, 98, or 99% of the time during the process or portion thereof.

[0046] As used herein, the phrase "at least substantially maintained," when referring to a current density value or current density range maintained during a process or portion thereof (e.g., electrolysis, etc.) of the present disclosure, refers to maintaining the current density value or current density range for at least 75, 80, 85, 90, 95, 96, 97, 98, or 99% of the time during the process or portion thereof.

[0047] As used herein, the phrase "at least substantially maintained," when referring to a current efficiency value or current efficiency range maintained during a process or portion thereof (e.g., electrolysis, etc.) of the present disclosure, refers to maintaining the current efficiency value or current efficiency range for at least 75, 80, 85, 90, 95, 96, 97, 98, or 99% of the time during the process or portion thereof.

[0048] As used herein, the phrase "at least substantially maintained," when referring to a voltage value or voltage range maintained during a process or portion thereof (e.g., electrolysis, etc.) of the present disclosure, refers to maintaining the voltage value or voltage range for at least 75, 80, 85, 90, 95, 96, 97, 98, or 99% of the time during the process or portion thereof.

[0049] As used herein, the term "electromembrane process" refers to a process that uses, for example, ion exchange membrane(s) and an electric potential difference as a driving force for ionic species. The electromembrane process can be, for example, (membrane) electrodialysis or (membrane) electrolysis. For example, the electromembrane process can be membrane electrolysis.

[0050] As used herein, the term "carbonation process" refers to a process in which, for example, a metal hydroxide is converted to a metal carbonate. For example, such a process may involve the use of gaseous CO. For example, such a process may involve bubbling CO.

[0051] The examples presented below are non-limiting and are used to better illustrate the process of the present disclosure.

[0052] For example, the hydroxide may be selected from nickel-cobalt-manganese hydroxide, nickel-cobalt-aluminum hydroxide, lithium-cobalt hydroxide, nickel hydroxide, nickel-cobalt-manganese oxyhydroxide, nickel-cobalt-aluminum oxyhydroxide, nickel oxyhydroxide, and lithium-cobalt oxyhydroxide.

[0053] For example, the oxide may be selected from nickel-cobalt-manganese oxide, nickel-cobalt-aluminum oxide, nickel oxide, lithium-nickel-cobalt-manganese oxide, lithium-nickel-cobalt-aluminum oxide, lithium-nickel oxide, and lithium-cobalt oxide.

[0054] For example, the solid is a precipitate containing a metal hydroxide, and the precipitate is obtained at a pH of about 8 to about 14.

[0055] For example, the solid is a precipitate that includes a metal hydroxide, and the precipitate is obtained at a pH of about 9 to about 13.

[0056] For example, the solid is a precipitate containing a metal hydroxide, and the precipitate is obtained at a pH of about 10 to about 12.

[0057] For example, the process further includes washing the metal hydroxide.

[0058] For example, the process further includes drying the metal hydroxide at a temperature of from about 80°C to about 130°C or from 90°C to about 120°C.

[0059] For example, metal sulfates react with lithium hydroxide and ammonia as chelating agents.

[0060] For example, metal sulfates react with lithium carbonate and ammonia as chelating agents.

[0061] For example, metal sulfates react with chelating agents that are lithium carbonate and ammonia bicarbonate.

[0062] For example, the first metal may be selected from nickel, cobalt, manganese, lithium, and aluminum.

[0063] For example, the base can include at least one of LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2, and Ba(OH)2.

[0064] For example, the base may include at least one of Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, MgCO3, CaCO3, SrCO3, and BaCO3.

[0065] For example, the base can include at least one of LiHCO3, NaHCO3, KHCO3, RbHCO3, CsHCO3, Mg(HCO3)2, Ca(HCO3)2, Sr(HCO3)2, and Ba(HCO3)2.

[0066] For example, the metal hydroxide may include at least one of LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2, and Ba(OH)2.

[0067] For example, the second metal can be Li, Na, K, Rb, Cs, Mg, Ca, Sr, or Ba.

[0068] For example, the third metal can be Li, Na, Ni, Co, Mn, Al, K, Rb, Cs, Mg, Ca, Sr, or Ba.

[0069] For example, the third metal hydroxide can be LiOH.

[0070] For example, the other metal can be Li, Na, Ni, Co, Mn, Al, K, Rb, Cs, Mg, Ca, Sr, or Ba.

[0071] For example, another metal hydroxide can be LiOH.

[0072] For example, the base may be purified before reacting with the metal sulfate, e.g., the base may be crystallized.

[0073] For example, metal hydroxides produced by an electromembrane process can be purified before reacting with metal sulfates, e.g., the metal hydroxides can be crystallized.

[0074] For example, before providing a liquid containing sulfate to an electromembrane to obtain hydroxide, the sulfate may be purified and / or concentrated.

[0075] For example, the chelating agent may be selected from NH3, NH4OH, acetylacetone, 5-sulfosalicylic acid, oxalic acid.

[0076] For example, the chelating agent may be selected from EDTA (ethylenediaminetetraacetic acid), NTA (nitrilotriacetic acid), DCTA (trans-1,2-diaminocyclohexanetetraacetic acid), DTPA (diethylene-triaminepentaacetic acid), and EGTA (ethylene glycol bis(2-aminoethyl ether)-N,N,N′,N′-tetraacetic acid).

[0077] For example, a chelating agent may be present.

[0078] For example, if the electromembrane process is a Na-based process, a purification step may be performed to separate the lithium (in solution as lithium sulfate) from the sodium sulfate solution.

[0079] For example, sodium sulfate and lithium sulfate can be separated from each other.

[0080] For example, sodium sulfate and lithium sulfate can be separated from each other by crystallization.

[0081] For example, the metal hydroxide can be NiCoAl(OH)2 or NiMnCo(OH)2.

[0082] For example, metal hydroxides include Ni 0.8 Co 0.15 Al 0.05 (OH)2, Ni 0.8 Mn 0.1 Co 0.1 (OH)2, and Ni 0.6 Mn 0.2 Co 0.2 (OH)2.

[0083] For example, the metal oxide can be of the formula LiMO2, where M is at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum.

[0084] For example, the metal oxide can be of the formula LiM2O4, where M is at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum.

[0085] For example, the metal hydroxide or metal oxide may be of the core-shell type.

[0086] For example, the metal oxide is LiNi 0.33 Mn 0.33 Co 0.33 O2, LiNi 0.5 Mn 0.3 Co 0.2 O2, LiNi 0.6 Mn 0.2 Co 0.2 O2, LiNi 0.8 Mn 0.1 Co 0.1 O2, and LiNi 0.8 Co 0.15 Al 0.05 O2, or [LiNi x M1 y M2 z O2] コア / [LiNi a M1 b M2 c O2]シェル where M1=Mn, Co, or Al, M2=Mn, Co, or Al, x+y+z=1, and a+b+c=1.

[0087] For example, metal oxides, when lithium-rich, have the formula LiMO2, or Li(1+x)M(1- x) In case of O2 and Li deficiency, Li (1-z) M (1+z) O2, where M can be at least one metal selected from nickel, cobalt, manganese, lithium, and aluminum.

[0088] For example, lithium hydroxide obtained by the electromembrane process can be used directly in an aqueous composition to react with the obtained metal hydroxides to obtain a mixture of metal hydroxides.

[0089] For example, lithium hydroxide obtained by an electromembrane process may crystallize before reacting with the resulting metal hydroxide to obtain a mixture of metal hydroxides.

[0090] For example, lithium hydroxide obtained by an electromembrane process may crystallize and then dissolve before reacting with the resulting metal hydroxide to obtain a mixture of metal hydroxides.

[0091] For example, roasting the mixture of metal hydroxides includes roasting at a first temperature of at least 350° C. for a period of at least about 4 hours.

[0092] For example, roasting the mixture of metal hydroxides includes roasting at a first temperature of at least about 400° C. for a period of at least about 6 hours.

[0093] For example, the process may further include roasting the mixture of metal hydroxides, including roasting at a second temperature of at least about 600° C. for a period of at least about 6 hours.

[0094] For example, the process may further include roasting the mixture of metal hydroxides, including roasting at a second temperature of at least about 700° C. for a period of at least about 8 hours.

[0095] For example, the process may further include roasting the mixture of metal hydroxides, including roasting at a second temperature of at least about 500° C. for a period of at least about 8 hours.

[0096] For example, NH3 can be recovered in situ during mixture formation.

[0097] For example, the electromembrane process for converting LiSO to LiOH may be selected from electromembrane processes such as those described in any one of WO2013 / 159194, WO2013 / 177680, WO2014 / 138933, WO2015 / 058287, WO2015 / 058288, WO2015 / 123762, and WO2017 / 031595, which are incorporated herein by reference in their entireties.

[0098] For example, carbonation may be carried out as described in WO2013 / 177680 or WO2015 / 058287, which are incorporated herein by reference in their entireties.

[0099] The process of the present disclosure can be operated, for example, as a batch process, or alternatively, the process of the present disclosure can be operated as a semi-continuous or continuous process.

[0100] It will be understood by those skilled in the art that one or more parameters of the processes of the present disclosure, such as, but not limited to, pH, temperature, current density, voltage, current efficiency, and concentration, can be monitored, for example, by means known in the art. The selection of suitable means for monitoring a particular parameter in the processes of the present disclosure can be performed by those skilled in the art. Such parameters can also be maintained and / or changed, for example, by those skilled in the art in light of their general knowledge and with reference to the present disclosure.

[0101] Those skilled in the art will understand that a variety of different sources can be used for the metal sulfate. The metal sulfate(s) can be purchased. The metal sulfate can also be obtained by leaching a metal or mixture of metals with H2SO4. The metal sulfate(s) can be obtained by leaching spent lithium-ion batteries. The metal sulfate(s) can be obtained by leaching the residue obtained after crushing spent lithium-ion batteries. The metal sulfate(s) can be obtained by leaching the residue after processing spent lithium-ion batteries. The metal sulfate(s) can be obtained, for example, from a leached mixture of transition metals. The metal sulfate(s) can be provided from concentrates extracted from mining companies. The metal sulfate(s) can be obtained by leaching nickel ore containing cobalt.

[0102] For example, during the electromembrane process, the consumption of lithium sulfate to prepare lithium hydroxide may proceed to a certain extent.

[0103] For example, a composition that includes lithium sulfate may also include H2SO4.

[0104] For example, in the process of the present disclosure, an aqueous composition containing lithium sulfate is provided to an electromembrane process under suitable conditions for the conversion of lithium sulfate to lithium hydroxide to proceed to a predetermined extent. Selection of a suitable predetermined extent for a particular process of the present disclosure can be made by one of ordinary skill in the art. For example, an aqueous composition containing lithium sulfate is provided to an electromembrane process under suitable conditions for the consumption of lithium sulfate to prepare lithium hydroxide until one or more competing side reactions proceed to a predetermined extent, e.g., to the extent that the preparation of lithium hydroxide is no longer efficient.

[0105] For example, the electromembrane process is a two-compartment monopolar or bipolar membrane electrolysis process carried out in an electrochemical cell including an anolyte compartment separated from the catholyte compartment by a cation exchange membrane, and the conversion of lithium sulfate to lithium hydroxide can proceed until the hydroxide current efficiency is no longer efficient, e.g., until the hydroxide current efficiency is at least substantially no longer maintained and decreases. For example, the electromembrane process is a two-compartment monopolar or bipolar membrane electrolysis process carried out in an electrochemical cell including an anolyte compartment separated from the catholyte compartment by a cation exchange membrane, and the conversion of lithium sulfate to lithium hydroxide can proceed until the pH in the anolyte compartment reaches a value of about 0.3 to about 1.4, about 0.4 to about 1.2, about 0.4 to about 1.2, about 0.5 to about 0.8, about 0.5 to about 0.7, or about 0.6.

[0106] For example, an electromembrane process is a two-compartment monopolar or bipolar membrane electrolysis process carried out in an electrochemical cell including an anolyte compartment separated from a catholyte compartment by a cation exchange membrane, and the conversion of lithium sulfate to lithium hydroxide may proceed until a certain amount of lithium sulfate contained within the aqueous composition is consumed.

[0107] For example, the predetermined level may include a consumption of about 30 to about 60 wt % or about 30 to about 50 wt % of the lithium sulfate contained in the aqueous composition, based on the total amount of lithium sulfate contained in the aqueous composition. For example, the predetermined level may include a consumption of about 35 to about 45 wt % of the lithium sulfate contained in the aqueous composition.

[0108] For example, the electromembrane process may comprise, consist essentially of, or consist of a three-compartment membrane electrolysis process, for example, a three-compartment monopolar or bipolar membrane electrolysis process.

[0109] For example, an electromembrane process may comprise, consist essentially of, or consist of a two-compartment membrane electrolysis process, such as a two-compartment monopolar or bipolar membrane electrolysis process.

[0110] For example, the electromembrane process may comprise, consist essentially of, or consist of a three-compartment membrane electrolysis process, such as a three-compartment bipolar membrane electrolysis process.

[0111] For example, the electromembrane process may comprise, consist essentially of, or consist of a two-compartment membrane electrolysis process, such as a two-compartment bipolar membrane electrolysis process.

[0112] For example, a two-compartment membrane electrolysis process, such as a two-compartment monopolar or bipolar membrane electrolysis process, can be carried out in an electrochemical cell that includes an anolyte compartment separated from a catholyte compartment by a cation exchange membrane.

[0113] For example, the cation exchange membrane is Nafion (商標) 324 (or perfluorinated sulfonic acids), cation exchange membranes used in caustic concentration such as FuMA-Tech FKB or Astom CMB cation exchange membranes or other membranes. Selection of a suitable cation exchange membrane for a particular process of the present disclosure can be performed by one skilled in the art.

[0114] For example, during a two-compartment membrane electrolysis process, such as a two-compartment monopolar or bipolar membrane electrolysis process, an aqueous stream containing lithium sulfate can be introduced into the anolyte compartment, a first lithium-depleted aqueous stream can be removed from the anolyte compartment, and a first lithium hydroxide-enriched aqueous stream can be removed from the catholyte compartment.

[0115] For example, in the catholyte compartment of a two-compartment monopolar or bipolar membrane electrolysis process, lithium hydroxide can be at least substantially maintained at a concentration of about 1 M to about 4 M, about 2 M to about 4 M, about 2 M to about 3 M, about 2.5 to about 3.5 M, about 2.8 to about 3.2 M, or about 3 M.

[0116] For example, during a two-compartment monopolar or bipolar membrane electrolysis process, an aqueous stream containing lithium sulfate can be introduced into the anolyte compartment at a temperature of about 10°C to about 100°C, about 10°C to about 100°C, about 10°C to about 90°C, about 20°C to about 85°C, about 40°C to about 80°C, about 40°C to about 70°C, about 45°C to about 60°C, about 45°C to about 55°C, or about 50°C.

[0117] For example, during a two-compartment monopolar or bipolar membrane electrolysis process, the first lithium-depleted aqueous stream can be removed from the anolyte compartment at a temperature of about 20°C to about 100°C, about 20°C to about 85°C, about 50°C to about 85°C, about 55°C to about 65°C, about 45°C to about 60°C, about 60°C to about 85°C, about 70°C to about 85°C, or about 80°C.

[0118] For example, during a two-compartment monopolar or bipolar membrane electrolysis process, the temperature within the electrochemical cell may be at least substantially maintained at a value of about 60°C to about 110°C, about 60°C to about 100°C, about 60°C to about 90°C, about 60°C to about 85°C, about 50°C to about 85°C, about 50°C to about 70°C, about 55°C to about 65°C, about 75°C to about 85°C, or about 80°C.

[0119] For example, in a two-compartment monopolar or bipolar membrane electrolysis process, the current density is at least substantially about 0.1 kA / m 2 ~about 8000kA / m 2 , 0.5kA / m 2 ~ approx. 6kA / m 2 , about 1kA / m 2 ~ approx. 6kA / m 2 , about 2kA / m 2 ~ approx. 6kA / m 2 , or about 3 kA / m 2 ~about 5kA / m 2 For example, the current density may be at least substantially maintained at a value of about 3 kA / m 2 , about 4kA / m 2 , and approximately 5 kA / m 2 For example, the current density may be maintained at a value selected from at least substantially about 4 kA / m 2 may be maintained at a value of

[0120] For example, in a two-compartment monopolar or bipolar membrane electrolysis process, the voltage may be at least substantially maintained at a value of about 3 V to about 8 V, about 5 V to about 10 V, about 4 V to about 6 V, about 4 to about 5, or about 4.5.

[0121] For example, an electrochemical cell is approximately 0.2 m 2 ~about 4m 2 , about 0.5m 2 ~about 3.5m 2 , about 1 m 2 ~about 3m 2 , or about 1 m 2 ~about 2m 2 may have a surface area of

[0122] For example, an electromembrane process may comprise, consist essentially of, or consist of a two-compartment membrane electrolysis process, such as a two-compartment monopolar or bipolar membrane electrolysis process.

[0123] For example, the electromembrane process may comprise, consist essentially of, or consist of a three-compartment membrane electrolysis process, for example, a three-compartment monopolar or bipolar membrane electrolysis process.

[0124] For example, a three-compartment membrane electrolysis process, such as a three-compartment monopolar or bipolar membrane electrolysis process, can be carried out in an electrochemical cell that includes an anolyte compartment separated from a central compartment by an anion exchange membrane and a catholyte compartment separated from the central compartment by a cation exchange membrane.

[0125] For example, the cation exchange membrane is Nafion (商標) The cation exchange membrane may comprise, consist essentially of, or consist of a perfluorosulfonic acid, such as the 324 cation exchange membrane, or other membranes used in caustic concentration, such as the FuMA-Tech FKB or Astom CMB cation exchange membranes. Selection of a suitable cation exchange membrane for a particular process of the present disclosure can be performed by one of ordinary skill in the art.

[0126] For example, during a three-compartment membrane electrolysis process, such as a three-compartment monopolar or bipolar membrane electrolysis process, a first lithium-depleted aqueous stream can be introduced into the central compartment, a second lithium-depleted aqueous stream can be removed from the central compartment, and a second lithium hydroxide-enriched aqueous stream can be removed from the catholyte compartment.

[0127] For example, a three-compartment membrane electrolysis process, such as a three-compartment monopolar or bipolar membrane electrolysis process, may further include generating an acid, such as sulfuric acid, in the anolyte compartment and removing an acid-containing aqueous stream, such as a sulfuric acid-containing aqueous stream, from the anolyte compartment.

[0128] The selection of a suitable anion exchange membrane for a particular process of the present disclosure can be performed by one skilled in the art. For example, it is understood by those skilled in the art that a proton blocking membrane can be useful in a process that co-produces an acid, such as sulfuric acid. For example, in a three-compartment monopolar or bipolar membrane electrolysis process, the anion exchange membrane can be a proton blocking membrane. For example, the proton blocking membrane can be a Fumatech FAB, Astom ACM, or Asahi AAV anion exchange membrane, etc.

[0129] For example, in the anolyte compartment of a three-compartment monopolar or bipolar membrane electrolysis process, the acid, such as sulfuric acid, can be at least substantially maintained at a concentration of the acid, such as sulfuric acid, of about 0.1 M to about 2 M. For example, in the anolyte compartment of a three-compartment monopolar or bipolar membrane electrolysis process, the sulfuric acid can be at least substantially maintained at a concentration of sulfuric acid, which can be about 0.5 M to about 1.5 M, about 0.7 M to about 1.2 M, or about 0.8 M.

[0130] For example, in the catholyte compartment of a three-compartment membrane electrolysis process, lithium hydroxide may be at least substantially maintained at a concentration of about 1 M to about 5.0 M, about 1 M to about 4.0 M, about 1 M to about 3.0 M, about 2 M to about 3.0 M, about 1.5 M to about 2.5 M, about 1.8 M to about 2.2 M, or about 2 M.

[0131] For example, during a three-compartment monopolar or bipolar membrane electrolysis process, the first lithium-depleted aqueous stream can be introduced into the central compartment at a temperature of about 20°C to about 85°C, about 40°C to about 85°C, about 40°C to about 75°C, about 50°C to about 70°C, about 50°C to about 65°C, or about 60°C.

[0132] For example, during a three-compartment monopolar or bipolar membrane electrolysis process, the second lithium-depleted aqueous stream can be removed from the anolyte compartment at a temperature of about 20°C to about 80°C, about 30°C to about 70°C, about 40°C to about 80°C, or about 60°C.

[0133] For example, during a three-compartment monopolar or bipolar membrane electrolysis process, the temperature within the second electrochemical cell can be at least substantially maintained at a value of about 30°C to about 90°C, about 40°C to about 85°C, about 50°C to about 80°C, about 50°C to about 70°C, about 50°C to about 65°C, about 50°C to about 70°C, about 55°C to about 65°C, or about 60°C.

[0134] For example, in a three-compartment monopolar or bipolar membrane electrolysis process, the current density is at least substantially about 0.5 kA / m 2 ~about 5kA / m 2 , about 1kA / m 2 ~about 2kA / m 2 , about 3kA / m 2 ~about 5kA / m 2 , about 4kA / m 2 or approximately 1.5 kA / m 2 may be maintained at a value of

[0135] For example, in a three-compartment monopolar or bipolar membrane electrolysis process, the voltage may be at least substantially maintained at a value of about 5V to about 9V, about 6V to about 8V, about 6.5V to about 7.5V, or about 7V.

[0136] For example, an electrochemical cell is approximately 0.2 m 2 ~about 4m 2 , about 0.5m 2 ~about 3.5m 2 , about 1 m 2 ~about 3m 2 , or about 1 m 2 ~about 2m 2 The cell area may be .gtoreq.1.

[0137] Alternatively, for example, in the processes of the present disclosure, the three-compartment monopolar or bipolar membrane electrolysis process may further include introducing ammonia into the anolyte compartment, producing an ammonium compound, such as ammonium sulfate, in the anolyte compartment, and removing an ammonium compound-containing aqueous stream, such as an ammonium sulfate-containing aqueous stream, from the anolyte compartment.

[0138] The selection of a suitable anion exchange membrane for a particular process of the present disclosure can be performed by one skilled in the art. For example, in a process that does not co-produce an acid such as sulfuric acid, it is understood by one skilled in the art that an anion exchange membrane that is not a proton-blocking membrane may be useful because it may be able to withstand higher temperatures and / or have lower resistance than a proton-blocking membrane. For example, in a three-compartment monopolar or bipolar membrane electrolysis process, the anion exchange membrane may not be a proton-blocking membrane. For example, the anion exchange membrane may be an Astom AHA anion exchange membrane or a FuMA-Tech FAP, etc.

[0139] For example, in the anolyte compartment of a three-compartment monopolar or bipolar membrane electrolysis process, the ammonium compound, such as ammonium sulfate, can be at least substantially maintained at a concentration of ammonium compound, such as ammonium sulfate, of about 0.5 M to about 5 M, about 1 M to about 4 M, or about 3 M.

[0140] For example, in the catholyte compartment of a three-compartment monopolar or bipolar membrane electrolysis process, lithium hydroxide can be at least substantially maintained at a concentration of about 1 M to about 4.0 M, about 1.5 M to about 2.5 M, or about 2 M.

[0141] For example, the pH in the anolyte compartment of a two-compartment monopolar or bipolar membrane electrolysis process and / or the central compartment of a three-compartment monopolar or bipolar membrane electrolysis process can be at least substantially maintained by adjusting at least one of the current density of a two-compartment monopolar or bipolar membrane electrolysis process, the current density of a three-compartment monopolar or bipolar membrane electrolysis process, the flow rate of the first lithium-depleted aqueous stream, and the flow rate of the second lithium-depleted aqueous stream.

[0142] For example, during a two-compartment monopolar or bipolar membrane electrolysis process, the conversion of lithium sulfate to lithium hydroxide may proceed to a certain extent.

[0143] For example, during a two-compartment monopolar or bipolar membrane electrolysis process, an aqueous stream containing lithium sulfate may be introduced into the anolyte compartment, a first lithium-depleted aqueous stream may be removed from the anolyte compartment, and a first lithium hydroxide-enriched aqueous stream may be removed from the catholyte compartment; during a three-compartment monopolar or bipolar membrane electrolysis process, a first lithium-depleted aqueous stream may be introduced into the center compartment, a second lithium-depleted aqueous stream may be removed from the center compartment, and a second lithium hydroxide-enriched aqueous stream may be removed from the catholyte compartment.

[0144] For example, the process may further include recycling at least a portion of the second lithium-depleted aqueous stream to the two-compartment monopolar or bipolar membrane electrolysis process.

[0145] Those skilled in the art will also understand that using the examples discussed herein, the process can be modified as needed.

[0146] For example, at least a portion of the process of the present disclosure can be operated as a batch process. Alternatively, for example, the process can be operated as a continuous or semi-continuous process. For example, it will be understood by those skilled in the art that the pH in the anolyte compartment of a two-compartment monopolar or bipolar membrane electrolysis process and / or the central compartment of a three-compartment monopolar or bipolar membrane electrolysis cell can be at least substantially maintained by, for example, adjusting the current density of the two-compartment monopolar or bipolar membrane electrolysis process and / or the three-compartment monopolar or bipolar membrane electrolysis process as described herein and / or the flow rate of the streams passing through the process.

[0147] For example, the pH in the anolyte compartment of a two-compartment monopolar or bipolar membrane electrolysis process and / or the central compartment of a three-compartment monopolar or bipolar membrane electrolysis process may be at least substantially maintained.

[0148] For example, the pH can be at least substantially maintained by adjusting at least one of the current density of a two-compartment monopolar or bipolar membrane electrolysis process, the current density of a three-compartment monopolar or bipolar membrane electrolysis process, the flow rate of the first lithium-depleted aqueous stream, and the flow rate of the second lithium-depleted aqueous stream.

[0149] Selection of a suitable means for measuring and / or monitoring pH can be performed by one skilled in the art. Selection of a suitable current density and / or a suitable flow rate can be performed by one skilled in the art.

[0150] For example, the process may further include removing the first hydrogen-containing stream from the catholyte compartment of the electrochemical cell. For example, the process may further include removing the oxygen-containing stream from the anolyte compartment of the electrochemical cell.

[0151] For example, the electrochemical cell may further include means for measuring pH in the anolyte compartment, and the system configured to convey the first lithium-depleted aqueous stream when the pH in the anolyte compartment is below a predetermined value.

[0152] For example, the electrochemical cell may further include means for measuring the pH within the central compartment, and the system is configured to carry un-converted lithium sulfate out of the central compartment of the electrochemical cell if the pH within the central compartment exceeds a predetermined value.

[0153] For example, the electrochemical cell may further include means for measuring the concentration of lithium hydroxide within the catholyte compartment of a second electrochemical cell. <当

[0154] For example, lithium hydroxide may be crystallized as lithium hydroxide monohydrate, optionally dried, and reacted in the solid state with a metal hydroxide to obtain a mixture of metal hydroxides.

[0155] For example, the metal sulfate may be obtained by leaching a battery.

[0156] For example, the battery may include LFP (LiFePO4).

[0157] For example, lithium hydroxide may be concentrated before reacting it with a metal hydroxide to form a mixture of metal hydroxides.

[0158] ) For example, the concentration may be carried out by using reverse osmosis or by heating.

[0159] For example, lithium hydroxide may be crystallized before reacting it with a metal hydroxide to form a mixture of metal hydroxides.

[0160] For example, the metal oxide may have a lamellar structure Li(M 2+ )O2.

[0161] For example, the metal oxide may have a spinel structure Li(M x+ )2O4, with 3 < X < 4.

[0162] For example, the lithium hydroxide composition may be concentrated before reacting with the metal sulfate.

[0163] For example, concentration can be carried out by using reverse osmosis or by heating.

[0164] For example, the chelating agent can be NH3.

[0165] For example, LiOH can be concentrated and then reacted directly with a metal hydroxide without crystallization.For example, LiOH can be concentrated, crystallized, optionally dried, and then reacted directly with a metal hydroxide.

[0166] For example, LiOH can be treated in a flash dryer.

[0167] For example, LiOH and a metal hydroxide can be reacted together to give a mixture that is then heated together.

[0168] For example, LiOH and a metal hydroxide can be reacted together to give a mixture that is then heated together in a spray dryer.

[0169] For example, lithium sulfate monohydrate crystals can be inserted into the cell to increase the Li2SO4 concentration.

[0170] For example, the sulfates or hydroxides can be purified by solvent extraction. For example, the solvent used in solvent extraction can be based on phosphorous acid, such as Cyanex 272, Cyanex 301, Cyanex 302, di-(2-ethylhexyl)phosphoric acid (D2EHPA), DEHTPA, Baysolvex DEDP, Ionquest 801, Hoe F 3787, MEHPA, P204, PC88A, P507, or hydroxy-oxime extractants (e.g., Acorga P50, Acorga K2000, LIX 84-I, SME 529, LIX 65N, LIX 64, LIX 70, LIX 860, LIX 622), or β-diketone metal cation extractants (e.g., LIX 54, XI-N54, XI-55, XI-57) [Source: Solvent extraction: the coordination chemistry behind extractive metallurgy metallurgy).Chem.Soc.Rev.,2014,43,123].

[0171] For example, the filtered sulfate solution after hydroxide co-precipitation can optionally be purified and / or concentrated before entering the membrane electrolysis.

[0172] For example, the leached solution may be purified prior to co-precipitation of hydroxides. Examples of purification may involve selective separation of metals, such as hydroxide precipitation, insoluble salt precipitation, oxidative precipitation, ion exchange, solvent extraction, electrochemical plating, crystallization.

[0173] For example, selective precipitation can be carried out by the addition of, for example, O2, SO2 or H2SO5, persulfate ((NH4)2S2O8), ammonium oxalate (NH4)2C2O4, chlorine, chlorine compounds (HCl, ClO2, HClO3), O3, NaOCl, CoS, Na2S, NaHS, CaCO3, Na3PO4.

[0174] For example, hydroxide precipitation can be obtained by addition of, for example, LiOH, NaOH, NH4OH.

[0175] For example, precipitation of insoluble salts can be obtained by addition of dimethylglyoxime.

[0176] For example, the LiPF6 electrolyte can be recovered.

[0177] For example, the solid / liquid (grams of material / volume of liquid) ratio in g / L for the leaching step can be comprised between 1:5 and 1:100.

[0178] For example, the leaching solution can be a mixture of at least one of H2SO4, H2O2, HNO3, HCl, nitric acid, citric acid, oxalic acid, aspartic acid, ascorbic acid, glucose.

[0179] For example, metal sulfates M(SO4) (where M = Ni, Co, Mn) and / or Al2(SO4)3 may optionally be crystallized before being used as precursors in the synthesis of hydroxides.

[0180] For example, even though the final material here was obtained using a co-precipitation method, any other type of synthesis method that leads to the synthesis of a layered oxide material with the recycling of a lithium-containing sulfate solution is encompassed within the scope of the present disclosure.

[0181] According to one example, a process according to the present disclosure is presented in FIG. 1. As can be seen from FIG. 1, nickel sulfate, cobalt sulfate, and manganese sulfate can be mixed together to obtain a composition containing various metal sulfates. Such a composition can be an aqueous composition, e.g., an acidic aqueous composition. For example, a material containing at least one metal can be leached with H2SO4 to obtain a desired metal sulfate composition. Alternatively, various metal sulfates can be reacted with an aqueous acidic composition to obtain a desired metal sulfate composition. LiOH and a chelating agent (e.g., NH3) are then added to the mixture to form a mixture that ultimately precipitates the desired metal hydroxide. LiOH acts as a pH enhancer because the metal sulfate reaction begins at high pH, ​​and NH3 can act as a chelating agent. Once the reaction begins, a solid phase precipitates (i.e., hydroxide compounds) and can be separated from the liquid phase at a high pH, ​​e.g., 10≦pH≦13. This solid precipitate is then washed with water and dried in air at 120°C for 8 hours. The hydroxide phase NMC(OH)2 is then obtained. The previously collected liquid phase contains dissolved Li2SO4, which can be recovered after liquid phase filtration. This Li2SO4 lithium sulfate can be electrolyzed in a membrane electrolyzer to lithium hydroxide LiOH, which can be used as a pH improver to form another mixture.

[0182] Those skilled in the art will appreciate that electromembrane processes can be carried out in many different ways and according to a variety of different parameters. For example, such electromembrane processes can be carried out as defined in any one of the following references: WO2013 / 159194, WO2013 / 177680, WO2014 / 138933, WO2015 / 058287, WO2015 / 058287, WO2015 / 123762, WO2017 / 031595, and WO2018 / 035618, which are incorporated herein by reference in their entireties.

[0183] The hydroxide phase NMC(OH)2 can further be used and mixed with LiOH obtained from the electrolysis of Li2SO4 to obtain a mixture of metal hydroxides. For example, this mixture of metal hydroxides can be roasted at different temperatures. For example, it can be roasted in air at a first temperature of 450 °C for about 8 hours and then roasted in air at 800 °C for 12 hours. Then, it is crushed, sieved, washed with water, and finally dried in air at 600 °C for about 8 hours. Then, nickel-manganese-cobalt lithium oxide Li-(Ni x Mn y Co z )O2, where 👇0 < x, y, z < 1 and x + y + z = 1 is obtained. [LiNi x M1 y M2 z O2] コア / [LiNi a M1 b M2 c O2] シェル A core-shell material having a gradient concentration from the core to the surface for different metals, such as 👇x + y + z = 1, a + b + c = 1, M1 = Mn, Co, or Al, M2 = Mn, Co, or Al, for example, when Ni is different, a ≠ x, can also be obtained and can result in a concentration gradient in the final material.

[0184] For example, the metal source can be at least substantially pure metal leached by electrochemically generated sulfuric acid.

[0185] For example, the metal source can be nickel concentrate (containing cobalt and possibly other elements in some cases) leached by electrochemically generated sulfuric acid.

[0186] For example, the metal source can be a nickel-cobalt-containing material (such as nickel oxide ore, nickel matte, nickel sulfide, mixed sulfide of nickel and cobalt, crude nickel sulfate generated from a copper smelting process, and nickel oxide) leached by electrochemically generated sulfuric acid.

[0187] Note: In the translation, the mathematical expressions "0 < x, y, z < 1" and "x + y + z = 1" etc. are directly translated as they are in the context of patent text. The specific meaning and interpretation of these expressions usually rely on the relevant technical knowledge and context of the patent. If there are specific requirements for further clarification or standardization of such mathematical expressions in a particular technical field, additional adjustments might be needed according to relevant norms. Also, the angle brackets with 7 - digit numbers are preserved as they are as per the instruction.For example, the metal source can be an aqueous nickel-cobalt solution, such as the solutions designated C or D in Figures 31, 32, and 33, leached with electrochemically generated sulfuric acid.

[0188] For example, the metal source may be an organic solution containing nickel (and cobalt, and possibly other elements) that can be stripped by electrochemically generated sulfuric acid.

[0189] For example, the metal source can be a spent battery or a component thereof (e.g., cathode, anode, black mass, slag, or mixtures thereof) (e.g., cathode only, or both anode and cathode or black mass, etc.) leached with electrochemically generated sulfuric acid.

[0190] Those skilled in the art will appreciate that the process shown in Figure 1 may vary according to the nature of the at least one metal sulfate used as a starting material. Accordingly, various metals and various mixtures thereof may be used as starting materials. [Example]

[0191] Synthesis of oxides at high potentials for cathode materials in lithium-ion batteries

[0192] Cathode materials are synthesized to form a cathode with a specific formula, Li p Ni x Mn y Co z Al q The lithium transition metal oxides with O2 were produced. The formula has specific proportions to reach specific types of materials in the industry. The resulting cathode materials are LiCoO2, LiNi 0.8 Co 0.15 Al 0.05 O2, LiNi 0.8 Mn 0.1 Co 0.1 O2, and LiNi 0.6 Mn 0.2 Co 0.2 It is O2.

[0193] Example 1 Synthesis of Co(OH) 28.11 g of CoSO4·7H2O (Strem Chemicals, inc.) was dissolved in 100 mL of distilled water to produce a 1 M solution (pH approximately 4-5). 10.49 g of LiOH·H2O (Sigma-Aldrich) was dissolved in 250 mL of distilled water to produce a 1 M solution (pH greater than 12). 5.841 mL was taken from a 28-30% by volume solution of ammonia (Sigma-Aldrich) to produce a 2 M solution (pH > 12).

[0194] The montage was made in a four-necked round-bottom flask (Dima glass inc.). One of the necks was used for nitrogen flow to create an inert atmosphere inside the flask. The other two necks were used to pour in LiOH and NH3, and the fourth neck was dedicated to collecting NH3 through a condenser.

[0195] A montage was set up with a solution of CoSO4 at the bottom of the flask. 10 mL of 1 M CoSO4 solution was first degassed completely with a nitrogen stream, and the system was maintained under nitrogen flow for 15 minutes. The temperature was adjusted to 60 °C. 20 mL of NH3 and 25 mL of LiOH were introduced dropwise, and the solution was kept in the flask under constant stirring. The reaction started when the pH of the solution reached 10. Once the product had reacted (i.e., after 10 minutes), the solution was stirred for another 20 minutes. The substrate was filtered and washed three times with distilled water.

[0196] After filtration, the sample was heated at 120°C for 8 hours. 1 g of Co(OH)2 was then recovered (pink color). The overall reaction is given by Equation 1: CoSO4+2LiOH+NH3→Co(OH)2+Li2SO4+NH3 formula 1

[0197] In this scheme, all reagents are in aqueous solution. The product of the reaction in scheme 1, cobalt hydroxide, is used as a precursor for the synthesis of cobalt oxide (see Example 2). In the mother liquor, LiSO 4のThe aqueous solution was mixed with the remaining LiOH in excess during the reaction. To convert all the LiOH to lithium sulfate, the solution was neutralized using H2SO4, as shown in Equation 2. 2LiOH+H2SO4 → Li2SO4·H2O+H2O formula 2

[0198] The filtered Li2SO4 can be electrolyzed and converted to LiOH·H2O. X-ray diffraction was performed on the compound to highlight its high purity.

[0199] Figure 2 shows the X-ray diffraction pattern of Co(OH)2. It can be indexed with the theoretical diffraction peaks of cobalt hydroxide. In addition, a small intensity peak is observed at 20°, indicating an impurity. In the hydroxide synthesis reaction, LiOH is used as a pH enhancer source because the hydroxide formation reaction begins at high pH. For example, LiOH can be replaced with NaOH, and X-ray diffraction was performed on the compound to highlight its high purity. In such cases, an electromembrane process can be used to convert Na2SO4 to NaOH.

[0200] Figure 3 shows the X-ray diffraction pattern of Co(OH)2 synthesized with NaOH as the pH enhancer. The X-ray diffraction pattern of this compound can be indexed with the theoretical diffraction peaks of cobalt hydroxide. In addition, as observed in the LiOH diffractogram, a small intensity peak at 20° is observed, suggesting an impurity.

[0201] This Co(OH)2 material, based on NaOH or LiOH as a source of pH enhancer, was a precursor to a variety of potential products (see below).

[0202] Example 2 Synthesis of LiCoO The previously obtained cobalt hydroxide was used as a precursor for the synthesis of lithium cobalt oxide, LiCoO. Here, the first step was to mix LiOH·H2O with Co(OH)2. This was a stoichiometric reaction, as shown in Equation 3. Co(OH)2+LiOH·H2O+0.25O2→LiCoO2+2.5H2O formula 3

[0203] The precursors were mixed, crushed, and pelletized before heat treatment. These pellets were placed in a furnace in air at 450°C for 8 hours. After this step, the pellets were crushed and returned to the pelletizer. The furnace was set in air at 800°C for 12 hours. The pellets were crushed again and then washed with water. The suspension was filtered, and the powder was recovered and pressed into pellets again. The final step consisted of another heat treatment in air at 600°C for 8 hours.

[0204] The X-ray diffraction pattern confirmed the high purity of the lithium cobalt oxide.

[0205] Figure 4 shows the X-ray diffraction pattern of lithium cobalt oxide. An impurity, possibly a residue of cobalt hydroxide, can be seen at 20° (the same impurity was observed). This impurity has already been reported several times in the literature.

[0206] Lithiated cobalt oxide can also be produced from cobalt hydroxide obtained with NaOH. The X-ray diffraction of such a compound can be seen in Figure 5, and it is noted that no differences are observed depending on the nature of the base source during hydroxide synthesis.

[0207] The next step was to characterize the LiCoO electrochemically. A cathode electrode was prepared by mixing 83 wt% LiCoO, 9 wt% Timcal C65 carbon black, and 8 wt% polyvinylidene difluoride (PVDF) in n-methylpyrrolidone (NMP) solvent to form a slurry. The slurry was mixed for several hours to homogenize and then spread onto a carbon-coated aluminum foil using a doctor blade. After drying overnight at 70 °C in a vacuum oven, electrode disks with an active material loading of 0.5 ± 0.1 mg / cm were cut and calendered. Standard coin cells (2032) were assembled in an Ar-filled glovebox. Once the electrode was prepared, lithium foil was used as the anode, and 1 M LiPF was dissolved in ethylene carbonate and diethyl carbonate (1:2 volume ratio) solvent was used as the liquid electrolyte. A polypropylene membrane (Celgard Inc.) was used as the separator. Electrochemical tests were performed on the cells at 30 °C in a VMP electrochemical station (Bio-Logic, France) at a 0.1 C rate of galvanostatic cycling vs. Li / Li+ with cutoff voltages of 3 and 4.3 V. Three coin cells were prepared for each sample to ensure reproducibility of the results. The standard deviation was determined to be ±1 mAh / g.

[0208] Figure 6 shows the first five charge and discharge cycles of LiCoO2. The capacity was 175 mAhg -1 The capacity of LiCoO2 reached 1000 volts, but decreased with cycling. The capacity of LiCoO2 varies depending on the potential range, but at higher potentials, irreversible reactions may occur. However, at 4.3 V, the compound should be stable. Some optimization is required to optimize the capacity and stability of LiCoO2.

[0209] Example 3 Ni 0.8 Co 0.15 Al 0.05 Synthesis of (OH)2 2.3121 g of NiSO4·6H2O (Strem Chemicals, inc), 0.4628 g of CoSO4·6H2O (Strem Chemicals, inc), and 0.0944 g of Al2(SO4)3·H2O (Sigma-Aldrich) were dissolved in 10 mL of water.

[0210] The montage and reaction conditions were as described in Example 1. The final product was a green-colored, Ni 0.8 Co 0.15 Al 0.05 The X-ray diffraction pattern, presented in Figure 7, shows that Ni 0.8 Co 0.15 Al 0.05 The formation of hydroxide was confirmed by a match to the theoretical diffraction pattern of (OH)2 (vertical bar).

[0211] Example 4 LiNi 0.8 Co 0.15 Al 0.05 O2 synthesis The next experiment is LiNi 0.8 Co 0.15 Al 0.05 The experimental procedure was the same as in Example 1. X-ray diffraction was used to characterize the oxide formation.

[0212] Figure 8 shows the diffraction pattern of the compound LiNi 0.8 Co 0.15 Al 0.05 It is emphasized that the theoretical diffraction peaks of O2 can be matched. The final characterization was the electrochemistry of the compound.

[0213] Figure 9 shows the LiNi 0.8 Co 0.15 Al 0.05Charging and discharging of O2 was shown. The electrochemical procedure was detailed in Example 2. The theoretical capacity of this compound was 279 mAh / g, and the experimentally obtained specific capacity was 180 mAh / g. In Figure 9, two slopes can be seen in the discharge curve. This behavior can be explained by the particle size of the active material, which is wide and not optimized for electrochemical purposes.

[0214] Example 5 Ni 0.8 Mn 0.1 Co 0.1 Synthesis of (OH)2 2.3131 g of NiSO4·6H2O (Strem Chemicals, inc), 0.3092 g of CoSO4·6H2O (Strem Chemicals, inc), and 0.1859 g of MnSO4·H2O (Sigma-Aldrich) were dissolved in 10 mL of water.

[0215] The montage and reaction conditions were as described in Example 1.

[0216] Figure 10 shows the diffraction pattern of the compound. 0.8 Mn 0.1 Co 0.1 It is emphasized that the theoretical diffraction peaks of (OH)2 can be fitted.

[0217] Example 6 LiNi 0.8 Mn 0.1 Co 0.1 O2 synthesis The next step is to form the oxide LiNi 0.8 Mn 0.1 Co 0.1 The experimental setup was the same as in Example 2. X-ray diffraction was used to characterize the oxide formation.

[0218] Figure 11 shows the diffraction pattern of the compound LiNi 0.8 Mn 0.1 Co 0.1 It is emphasized that the theoretical diffraction peaks of O2 can be fitted.

[0219] Capacity: 175mAhg-1 The capacity of LiCoO2 varies depending on the potential range, but at higher potentials, irreversible reactions can occur.

[0220] Example 7 Ni 0.6 Mn 0.2 Co 0.2 Synthesis of (OH)2 1.7348 g of NiSO4·6H2O (Strem Chemicals, inc), 0.6184 g of CoSO4·6H2O (Strem Chemicals, inc), and 0.3674 g of MnSO4·H2O (Sigma-Aldrich) were dissolved in 10 mL of water.

[0221] The montage and reaction conditions were as described in Example 1.

[0222] Figure 12 shows the diffraction pattern of the compound. 0.6 Mn 0.2 Co 0.2 The theoretical diffraction peaks of (OH)2 can be fitted to highlight the peaks.

[0223] Example 8 LiNi 0.6 Mn 0.2 Co 0.2 O2 synthesis The next step is to form the oxide LiNi 0.6 Mn 0.2 Co 0.2 The experimental procedure was the same as in Example 2. X-ray diffraction was used to characterize the oxide formation.

[0224] Figure 13 shows the diffraction pattern of the compound LiNi 0.6 Mn 0.2 Co 0.2 It is emphasized that the theoretical diffraction peaks of O2 can be fitted.

[0225] Figure 14 shows the charge / discharge curves of LiNi0.6Mn0.2Co0.2O2 at a 0.1 C rate. The electrochemical measurement equipment and method were as described in Example 2. The theoretical capacity of this compound was 275 mAh / g, and the experimentally obtained specific capacity was 170 mAh / g. In Figure 14, two slopes can be seen in the discharge curve. This behavior can be explained by the particle size of the active material, which is wide and not optimized for electrochemical purposes.

[0226] Example 9 Electrolysis of Lithium Sulfate and Its Conversion to Lithium Hydroxide The electrolysis of lithium sulfate was carried out in a two-compartment cell ICI FM-21 (similar to the cell in Figure 2 of WO2015 / 058287) according to the general procedure described in Example 1 of WO2015 / 058287. The experimental conditions were as follows: Cell: FM-21 2400cm 2 Current density: 4.0kA / m 2 Temperature: 60℃ Li2SO4: 300g / L (batch) LiOH·H2O:2M

[0227] The results obtained were as follows: Conversion rate: 40% H2SO4: 10.2% Current efficiency: 76.9% LiOH flow rate: 14.4L / hour Productivity: 4.75 kg LiOH·H2O / h / m 2 Voltage (at cell): 4.39V Energy: 3678kWh / TM LiOH·H2O

[0228] Figures 15 to 22 show the results obtained during the electrolysis of Li2SO4.

[0229] FIG. 15 is a plot showing sulfuric acid concentration in the anolyte stream as a function of batch time. FIG. 16 is a plot showing anolyte and catholyte conductivity as a function of batch time. FIG. 17 is a plot showing anolyte and catholyte temperature as a function of batch time. FIG. 18 is a plot showing voltage at the cell and current generator as a function of batch time. FIG. 19 is a plot showing productivity in milliliters of lithium hydroxide monohydrate equivalent per minute as a function of sulfuric acid concentration in the anolyte. FIG. 20 is a plot showing productivity in liters of lithium hydroxide monohydrate equivalent per hour as a function of sulfuric acid concentration in the anolyte. FIG. 21 is a plot showing current efficiency as a function of sulfuric acid concentration in the anolyte. FIG. 22 is a plot showing productivity in kilograms of lithium hydroxide monohydrate equivalent per hour per square meter of electroactive area as a function of sulfuric acid concentration in the anolyte. FIG. 23 is a plot showing the electrical energy consumption associated with the electrochemical conversion of lithium hydroxide monohydrate equivalent in kilowatt-hours per metric ton as a function of sulfuric acid concentration in the anolyte.

[0230] As shown in Figure 24, LiOH can be added as a pH enhancer source to a mixture of metal sulfate(s) for precipitation of the metal hydroxide(s). After precipitation of the metal hydroxide(s), Li2SO4 can be recovered as dissolved species in aqueous solution and inserted into a membrane electrolyzer, converted to LiOH, and optionally evaporated, crystallized, dried, and then reacted with the metal hydroxide(s) to form the metal oxide(s). Sulfuric acid is used to leach a transition metal source, generating the metal as dissolved species in the form of sulfate salts.

[0231] As shown in Figure 25, NaOH can be added as a pH enhancer source to a mixture of metal sulfate(s) for precipitation of the metal hydroxide(s). After precipitation of the metal hydroxide(s), Na2SO4 can be recovered as a dissolved species in aqueous solution and inserted into the membrane electrolyzer. LiOH can react with the metal hydroxide(s) to form the metal oxide(s). If lithium is present in the transition metal source, it can be carried out in a metal sulfate solution, and the resulting Li2SO4 can be separated from Na2SO4 to purify the Na2SO4 solution before insertion into the membrane electrolyzer. The LiOH used to react with the lithiated metal oxide can be from another electromembrane process or can be commercially available LiOH.

[0232] As shown in FIG. 26, a mixture of NaOH and LiOH is used as a pH enhancer source to a mixture of metal sulfate(s) for precipitation of metal hydroxide(s). After precipitation of the metal hydroxide(s), the mixture of LiSO and NaSO can be recovered as dissolved species in aqueous solution and inserted into a membrane electrolyzer, where LiSO can be converted to LiOH and react with the metal hydroxide(s) to form metal oxide(s). LiOH can be separated from NaOH. For example, LiOH can be substantially selectively precipitated on NaOH (e.g., via evaporation, crystallization, and drying steps) and thus separated therefrom. LiSO can also be optionally separated from NaSO before reacting in the electromembrane process. The resulting LiOH can be reacted and ultimately used to generate metal oxide(s) by reacting with metal hydroxide(s) to form metal oxide(s).

[0233] As shown in FIG. 27, NaOH can be added as a pH enhancer source to a mixture of metal sulfate(s) for precipitation of metal hydroxide(s). For example, NaOH can be used instead of LiOH as a pH enhancer for economic reasons. After precipitation of the metal hydroxide(s), the mixture of LiSO and NaSO can be recovered as dissolved species in aqueous solution and inserted into a membrane electrolyzer, where LiSO can be converted to LiOH and react with the metal hydroxide(s) to form the metal oxide(s). LiOH can be substantially selectively precipitated on NaOH (e.g., via evaporation, crystallization, and drying processes). The resulting LiOH can be reacted and ultimately used to generate the metal oxide(s) by reacting with the metal hydroxide(s) to form the metal oxide(s). Those skilled in the art will appreciate that, for example, if the transition metal source is a spent battery, 100% of the lithium contained therein may not necessarily be electrolyzed, and therefore an external source of LiSO may be provided to the electromembrane process to be converted to LiOH.

[0234] As shown in Figure 28, the LiOH used for hydroxide precipitation can optionally be crystallized. Furthermore, the lithium sulfate solution can be purified and concentrated before being inserted into the electromembrane process. For example, in this case, an external source of Li2SO4 can be provided. Indeed, an external source of Li2SO4 can be provided, since the generated LiOH is used (i) to react with the metal sulfate and (ii) to mix with the resulting metal hydroxide(s).

[0235] As shown in FIG. 29, the electrochemically generated sulfuric acid solution, called the anolyte solution, can be concentrated to leach a source of transition metals, e.g., battery active materials.

[0236] The anolyte concentration process described in FIG. 29 may be carried out by a method or process such as those described in any one of WO2015 / 123762, WO2017 / 031595, and WO2018 / 035618, which are incorporated herein by reference in their entireties. Those skilled in the art will appreciate that the anolyte concentration process of FIG. 29 may therefore be applied to any of FIGS. 24-28. The anolyte solution after concentration is depleted of lithium, and the LiSO4-rich solution is re-introduced into the electromembrane system to be treated. The lithium sulfate solution obtained after anolyte concentration may be mixed with the LiSO4 solution recovered after hydroxide precipitation, as described in FIG. 29. Such a mixture of LiSO4 solutions may be returned to the electromembrane process.

[0237] Figure 30 illustrates the synthesis of core-shell designed materials. Metal hydroxides with core-shell designs can be precipitated as described in Figures 24-29, and core-shell oxides of lithiated materials can be obtained after the addition of LiOH.

[0238] 28-29, one skilled in the art will understand that optionally, crystallized LiOH can be replaced by NaOH or a mixture of both to increase the pH. The same applies to LiSO, which can be replaced by NaSO or a mixture of both. One skilled in the art will also understand that the concentration and purification of sulfate solutions as described in FIG. 29 can be applied to any of the processes in FIGS. 24-30.

[0239] Figure 31 illustrates the precipitation of metal carbonates instead of metal hydroxides. To do so, LiOH generated from membrane electrolysis can be carbonated to form LiCO. For example, carbonation can be carried out as described in WO 2013 / 177680, WO 2006 / 104367, WO 2018 / 134536, or WO 2015 / 058287, which are incorporated herein by reference in their entireties. This lithium carbonate can react with metal sulfates to form metal carbonates. The lithium sulfate solution can be recovered as described in Figures 24-30.

[0240] Those skilled in the art will appreciate that all possible embodiments described in FIGS. 24-31 can also be applied to FIG. 32, with the substitution of sulfates with nitrates (e.g., concentrating the LiSO solution and / or adding LiSO 4 , and mixtures with Na2SO4).

[0241] Additionally, one skilled in the art will understand that LiOH may be replaced by NaOH or a mixture of both in any of Figures 24-31. The same is true for LiSO, which may be replaced by NaSO or a mixture of both.

[0242] 24-31, various acid solution sources can be used to react with the transition metal source, such as sulfuric acid solution (FIG. 24), lithium sulfate solution (FIG. 29), and anolyte solution. For example, these various acid solution sources for the leach solution can be (A) an electrochemically generated sulfuric acid solution, referred to as the anolyte solution; (B) a partially concentrated sulfuric acid solution generated by membrane electrolysis, referred to as the (diluted) lithium sulfate solution; or (C) sulfuric acid. (a) Anolyte solution refers to an electrochemically generated sulfuric acid solution from membrane electrolysis, having a chemical composition as presented in Table 1. The concentration of this solution is approximately 1.5 M H2SO4. [Table 1]

[0243] (b) The partially concentrated sulfuric acid solution generated by membrane electrolysis, called (diluted) lithium sulfate solution, consists of the previous anolyte solution, which is depleted in lithium, concentrated and then diluted with water to reach a concentration of ≈1 M H2SO4.

[0244] From Figure 32, nitric acid can be generated from the salt decomposition of LiNO3, which is used instead of Li2SO4. Leaching of a transition metal source with nitric acid results in the production of metal nitrates dissolved in solution. LiOH can then be added for hydroxide precipitation, and the lithiated nitrate solution can be filtered. This LiNO3 solution can enter an electromembrane process and be converted to LiOH and HNO3. When replacing sulfates with Figure 32, all of the embodiments from Figures 24 to 31 apply herein.

[0245] The overall protocol, starting from Ni and Co concentrates, is illustrated in Figures 33, 34, and 35 and can result in the production of high-purity Co and Ni aqueous phases (referred to as solutions A and B in Figures 33, 34, and 35), high-purity Co or Ni aqueous phases (referred to as solutions C and D), or cobalt sulfate or nickel sulfate crystalline salts (referred to as E and F). For example, the pH can be increased from solution A to B to ensure maximum recovery of cobalt in the organic phase. For example, the lithium sulfate solution can be provided by the anolyte solution generated by the electromembrane process and concentrated as described in Figure 29.

[0246] 33-35, various acid solution sources can be used to leach the Li-Co concentrate, for example, it can be a sulfuric acid solution (FIG. 33), a lithium sulfate solution (FIG. 34), and an anolyte solution (FIG. 35).

[0247] Those skilled in the art will understand that, for example, the embodiments provided in Figures 33-35 can be applied to the processes shown in Figures 24-31, and the metal sulfates obtained in Figures 33-35 can be the transition metal source boxes of Figures 24-31. Additionally, the sulfuric acid source used in the leaching of Figures 33-35 can be replaced with nitric acid to obtain the transition metal source in the form of the nitrate salt described in Figure 32.

[0248] Those skilled in the art will understand that the LiOH used in Figures 24-30 and 34 to react with the metal hydroxide / carbonate to form the lithiated metal oxide(s) can be carbonated to generate Li2CO3, which reacts with the metal hydroxide / carbonate to form the lithiated metal oxide(s). Other carbonates described in this disclosure, such as Na2CO3, K2CO3, Rb2CO3, Cs2CO3, MgCO3, CaCO3, SrCO3, or BaCO3, can also be used.

[0249] Those skilled in the art will understand that the nitrates used in FIG. 35 may be a substitute for the sulfates as presented in FIGS. 24-34, and all of the processes presented in FIGS. 24-34 may be used with the sulfates replaced with nitrates.

[0250] For example, the conversion of metal carbonates to lithium oxide is described in WO2006 / 104367, which is incorporated herein by reference in its entirety.

[0251] For example, the electrochemically generated sulfuric acid (HSO solution) generated in Figures 24-28 may contain lithium sulfate, sodium sulfate, and / or potassium sulfate. HSO can be separated from the lithium sulfate, sodium sulfate, and / or potassium sulfate through anolyte concentration, as shown in Figure 29. For example, such separation can be achieved by selective crystallization of sulfate monohydrate. For example, anolyte concentration can be performed by selective sulfate precipitation, such as described in any one of WO2015 / 123762, WO2017 / 031595, and WO2018 / 035618, all of which are incorporated herein by reference in their entireties.

[0252] Additionally, one skilled in the art will appreciate that the acidic solution generated by the electromembrane process of FIGS. 24-35 can be replaced by an anolyte solution and concentration step, as presented in FIG.

[0253] Those skilled in the art will understand that all possible embodiments described in FIGS. 24 to 34 can also be applied to FIG. 35 (for example, concentration of the Li2SO4 solution and / or mixture of Li2SO4 and Na2SO4).

[0254] Example 10 Core-Shell Synthesis Core [LiNi x M1 y M2 z O2], x + y + z = 1, and shell [LiNi a M1 b M2 c O2], a + b + c = 1, for the synthesis of a gradient concentration material of composition Li[Ni d M1 e M2 f O2, d + e + f = 1, where M1 = Mn, Co, or Al, M2 = Mn, Co, or Al, and x < d < a, y < e < b, z < f < c. To prepare such spherical core-shell materials, it is necessary to first obtain a hydroxide precursor, which can be synthesized via coprecipitation. In such a synthesis method, an aqueous solution of a certain amount of NiSO4·6H2O (and optionally, M1 at a given concentration and M2 at different concentrations) was used as the starting material for the core composition Ni x M1 y M2 z (OH)2. The metal aqueous solution was continuously fed into a batch reactor already filled with a certain amount of deionized water, NaOH as a pH improver (水溶液) , and NH4OH as a chelating agent (水溶液) under a nitrogen atmosphere. At the same time, a predetermined concentration of NaOH and an appropriate amount of NH4OH (水溶液) were pumped into the reactor. When the precursor Ni x M1 y M2 z (OH)2 was formed in the solution, an aqueous solution of a second solution, the desired metal Ni a M1 b M2 c (OH)2 (for example, M1 and M2 = Ni, Mn, Co, Al) was introduced into the reactor. The resulting Ni d M1 e M2f (OH)2 (where x < d < a, y < e < b, z < f < c) powder was filtered, washed, and dried at 110 °C for 12 hours under vacuum. Li[Ni d M1 e M2 f O2 was prepared by mixing the precursor Ni d M1 e M2 f (OH)2 with LiOH·H2O and calcining at 700 °C for 10 hours in an oxygen atmosphere.

[0255] For example, the metal source can be a used battery or its components (e.g., cathode, anode, black mass, slag, or mixtures thereof) leached by electrochemically generated sulfuric acid (e.g., only the cathode, or both the anode and cathode or black mass, etc.).

[0256] The leached metal sulfate solution can contain metals recovered from used batteries (e.g., Li, Ni, Co, and / or Al, and / or Mn). For example, NaOH can be added as a pH improver source to a mixture of metal sulfates (if any) for the precipitation of metal hydroxide(s). After the precipitation of metal hydroxide(s), the mixture of Li2SO4 and Na2SO4 can be recovered as seeds dissolved in an aqueous solution and inserted into a membrane electrolytic cell. Li2SO4 can be converted to LiOH and react with metal hydroxide(s) to form metal oxide(s).

[0257] Those skilled in the art will understand that another base can be used instead of NaOH. For example, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2, or Ba(OH)2 can be used.

[0258] The embodiments of paragraphs

[0036] to

[0291] of the present disclosure are presented in this manner in order to demonstrate all possible combinations of embodiments, where applicable. Accordingly, these embodiments are presented in the description in a manner equivalent to making dependent claims of all embodiments dependent on any preceding claim (including previously presented embodiments), thereby demonstrating that they may all be combined together in any possible manner. For example, where applicable, all possible combinations between the embodiments of paragraphs

[0036] to

[0291] and the processes of paragraphs

[0005] to

[0035] are hereby encompassed by the present disclosure.

[0259] The present disclosure has been described with reference to specific examples. The description is intended to aid in understanding the disclosure, not to limit its scope. It will be apparent to those skilled in the art that various modifications can be made to the present disclosure without departing from the scope of the disclosure set forth herein, and such modifications are intended to be encompassed by this document.

[0260] All publications, patents, and patent applications are herein incorporated by reference in their entirety to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference in its entirety. In the event that a term in this disclosure is found to be defined differently in a document incorporated herein by reference, the definition provided herein shall serve as the definition of that term.

Claims

1. 1. A process for the preparation of a metal hydroxide comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, comprising: reacting a metal sulfate comprising (i) at least one metal selected from nickel and cobalt, and optionally (ii) at least one metal selected from manganese, lithium, and aluminum, with sodium hydroxide and optionally a chelating agent to obtain a solid comprising the metal hydroxide and a liquid comprising sodium sulfate; separating the liquid and the solid from each other to obtain the metal hydroxide; providing said sodium sulfate containing liquid to an electromembrane process for converting said sodium sulfate to sodium hydroxide; and recycling the sodium hydroxide obtained by the electromembrane process to react with the metal sulfate.

2. 2. The process of claim 1, wherein the solid is a precipitate comprising the metal hydroxide, and the precipitate is obtained at a pH of 8 to 14.

3. 2. The process of claim 1, wherein the solid is a precipitate comprising the metal hydroxide, and the precipitate is obtained at a pH of 9 to 13.

4. The process of claim 1 further comprising washing the metal hydroxide.

5. 5. The process of claim 4, further comprising drying the metal hydroxide.

6. The process of claim 5, wherein drying the metal hydroxide comprises drying at a temperature of at least 80°C for a period of 1 to 4 hours.

7. The process of claim 1, wherein the chelating agent is present.

8. 8. The process of claim 7, wherein the chelating agent is ammonia.

9. The process of claim 1 , wherein the electromembrane process comprises an electrolytic membrane process.

10. The process of claim 1 , wherein the electromembrane process comprises an electrodialysis process.

11. The chelating agent is NH ３ , N.H. ４ OH, acetylacetone, 5-sulfosalicylic acid, oxalic acid.

12. 2. The process of claim 1, wherein the chelating agent is selected from EDTA (ethylenediaminetetraacetic acid), NTA (nitrilotriacetic acid), DCTA (trans-1,2-diaminocyclohexanetetraacetic acid), DTPA (diethylene-triaminepentaacetic acid), and EGTA (ethylene glycol bis(2-aminoethyl ether)-N,N,N',N'-tetraacetic acid).

13. The metal hydroxide is NiCoAl(OH) ２ or NiMnCo(OH) ２ 2. The process of claim 1, wherein

14. The metal hydroxide is Ni ０．８ Co ０．１５ Al ０．０５ (OH) ２ , Ni ０．８ Mn ０．１ Co ０．１ (OH) ２ , and Ni ０．６ Mn ０．２ Co ０．２ (OH) ２ The process of claim 1 , wherein the compound is selected from the group consisting of:

15. 10. The process of claim 1, wherein the sodium hydroxide obtained by the electromembrane process is used directly in an aqueous composition to react with the obtained metal hydroxides to obtain a mixture of metal hydroxides.

16. 10. The process of claim 1, wherein the sodium hydroxide obtained by the electromembrane process is crystallized before reacting with the obtained metal hydroxides to obtain a mixture of metal hydroxides.

17. 10. The process of claim 1, wherein the sodium hydroxide obtained by the electromembrane process crystallizes and then dissolves before reacting with the obtained metal hydroxides to obtain a mixture of metal hydroxides.

18. 2. The process of claim 1, wherein the process comprises providing the liquid containing the metal sulfate to the electromembrane process for converting the metal sulfate to the metal hydroxide to generate sulfuric acid.

19. The anolyte of the electromembrane process is treated by selectively precipitating sulfate therefrom, thereby reducing H ２ SO ４ 20. The process of claim 18, wherein the concentration is increased.

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