# US 12,006,231 B2 · Processes for preparing hydroxides and oxides of various metals and derivatives thereof

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- Number: US 12,006,231 B2
- Document ID: US12006231B2
- Status: Granted
- Kind: B2
- Application number: 18/090,322
- Filed: 2022-12-28
- Published: 2023-05-25
- Granted: 2024-06-11
- Earliest claimed: 2017-11-22
- Assignees: Nemaska Lithium Inc.
- Applicants: Nemaska Lithium Inc.
- Inventors: Guy Bourassa; Jean-François Magnan; Nicolas Laroche; Thomas Bibienne; Mathieu Charbonneau; Mickaël Dollé
- Web page: https://patentgrep.com/patent/US12006231B2

## CPC

- C01G 53/84: Hydroxides
- B01D 61/423: {comprising multiple electrodialysis steps}
- B01D 61/445: {with bipolar membranes; Water splitting}
- C01D 1/28: Purification; Separation
- C01D 15/02: Oxides; Hydroxides
- C01G 51/04: Oxides
- C01G 51/05: Hydroxides; Oxyhydroxides
- C01G 51/42: containing alkali metals, e.g. LiCoO2
- C01G 51/50: of the type (MnO2)n-, e.g. Li(CoxMn1-x)O2 or Li(MyCoxMn1-x-y)O2
- C01G 53/04: Oxides
- C01G 53/42: containing alkali metals, e.g. LiNiO2
- C01G 53/50: of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
- C01G 53/504: with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5
- C01G 53/506: with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.8, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.8
- C01G 53/82: Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/54: Reclaiming serviceable parts of waste accumulators
- B01D 2311/2642: Aggregation, sedimentation, flocculation, precipitation or coagulation
- B01D 2311/2643: Crystallisation
- B01D 2311/2673: Evaporation
- B01D 2311/2699: Drying
- C01P 2002/54: one element only
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2006/40: Electric properties
- Y02E 60/10: Energy storage using batteries
- Y02E 60/36: Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
- Y02W 30/84: Recycling of batteries or fuel cells
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C01D: COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts of peroxyacids C01B15/00; sulfides C01B17/22; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds other than ammonia and cyanogen, containing nitrogen and other non-metals C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; phosphides C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; cyanides C01C3/08; salts of cyanic acid C01C3/14; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02W: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT

## Abstract

A process for preparing a metal hydroxide comprising (i) at least one metal chosen from nickel and cobalt and optionally (ii) at least one metal chosen from manganese, lithium and aluminum. The process comprises: reacting a metal sulfate comprising (i) at least one metal chosen from nickel and cobalt and optionally (iii) 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 the sodium sulfate into sodium hydroxide; and reusing the sodium hydroxide obtained by the electromembrane process for reacting with the metal sulfate.

## Claims

### Claim 1

A process for preparing a metal hydroxide comprising (i) at least one metal chosen from nickel and cobalt and optionally (ii) at least one metal chosen from manganese, lithium and aluminum, said process comprising:
reacting a metal sulfate comprising (i) at least one metal chosen from nickel and cobalt and optionally (iii) at least one metal chosen from manganese and aluminum with sodium hydroxide and optionally a chelating agent in order to obtain a solid comprising said metal hydroxide and a liquid comprising sodium sulfate;
separating said liquid and said solid from one another to obtain said metal hydroxide;
submitting said liquid comprising sodium sulfate to an electromembrane process for converting said sodium sulfate into sodium hydroxide; and
reusing said sodium hydroxide obtained by said electromembrane process for reacting with said metal sulfate.

### Claim 2 (depends on 1)

The process of claim 1, wherein said solid is a precipitate comprising said metal hydroxide, said precipitate being obtained at a pH of about 8 to about 14.

### Claim 3 (depends on 1)

The process of claim 1, wherein said solid is a precipitate comprising said metal hydroxide, said precipitate being obtained at a pH of about 9 to about 13 or about 10 to about 12.

### Claim 4 (depends on 1)

The process of claim 1, further comprising washing said metal hydroxide.

### Claim 5 (depends on 4)

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

### Claim 6 (depends on 5)

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

### Claim 7 (depends on 1)

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

### Claim 8 (depends on 7)

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

### Claim 9 (depends on 1)

The process of claim 1, wherein said electromembrane process comprises an electrolysis membrane process.

### Claim 10 (depends on 1)

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

### Claim 11 (depends on 1)

The process of claim 1, wherein the chelating agent is chosen from NH3, NH4OH, acetylacetone, 5-sulfosalicylic acid, oxalic acid.

### Claim 12 (depends on 1)

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

### Claim 13 (depends on 12)

The process of claim 12, wherein said chelating agent is present.

### Claim 14 (depends on 1)

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

### Claim 15 (depends on 1)

The process of claim 1, wherein said metal hydroxide is chosen from Ni0.8Co0.15Al0.05(OH)2, Ni0.8Mn0.1Co0.1(OH)2 and Ni0.6Mn0.2Co0.2(OH)2.

### Claim 16 (depends on 1)

The process of claim 1, wherein said sodium hydroxide obtained by said electromembrane process is used as is in aqueous composition and reacted with said obtained metal hydroxide to obtain a mixture of metal hydroxides.

### Claim 17 (depends on 1)

The process of claim 1, wherein said sodium hydroxide obtained by said electromembrane process is crystallized before being reacted with said obtained metal hydroxide to obtain a mixture of metal hydroxides.

### Claim 18 (depends on 1)

The process of claim 1, wherein said sodium hydroxide obtained by said electromembrane process is crystallized and then dissolved before being reacted with said obtained metal hydroxide to obtain a mixture of metal hydroxides.

### Claim 19 (depends on 1)

The process of claim 1, wherein said process comprises submitting said liquid comprising said sodium sulfate to said electromembrane process for converting said sodium sulfate into said hydroxide and to generate sulfuric acid.

### Claim 20 (depends on 19)

The process of claim 19, wherein an anolyte of said electromembrane process is treated by substantially selectively precipitating a sodium sulfate therefrom, thereby increasing H2SO4 concentration.