EP-4735174-A1 - PROCESS FOR MEMBRANE-BASED RECYCLING OF BATTERY MATERIAL

Abstract

The present disclosure relates to methods for recovering metals from used lithium-ion batteries and related electronic wastes. The methods provide modular, inexpensive, and energy efficient means for recovering up to 99.9% pure lithium, nickel, cobalt, and manganese in the form of various oxides or salts, e.g., phosphates, sulfates, or hydroxides. The methods produce nearly zero waste, as many of the recovered waste products can be purified and/or recycled.

Inventors

• MILES, ROBERT
• COLEMAN, KENNETH
• GRUMBLES, William
• AYYAKUDI RAVICHANDRAN, Sankaranarayanan

Assignees

• Momentum Technologies, Inc.

Dates

Publication Date

20260506

Application Date

20240628

Claims (1)

1. CLAIMS 1. A method for recovering metals, the method comprising: forming a first mixture by contacting black mass with a first acidic solution and filtering the first mixture to collect a first filtrate and a first filter cake; contacting the first filtrate with a first basic solution to form a second mixture comprising at least precipitated metals aluminum and iron and filtering the second mixture to collect a second filtrate comprising unprecipitated metals and a second filter cake comprising at least precipitated metals aluminum and iron; contacting the second filtrate with a first organic phase comprising a first water-immiscible organic solvent and a first extractant to extract at least copper metal into the first organic phase and provide a copper-depleted second filtrate; and contacting the first organic phase comprising at least copper metal with a first acidic strip solution to extract at least copper metal into the first acidic strip solution and form a copper-enriched strip solution and a copper-depleted second filtrate. 2. The method of claim 1, further comprising adding a hydrogen peroxide solution to the first mixture. 3. The method of claim 2, wherein the hydrogen peroxide solution comprises a hydrogen peroxide concentration ranging from 1% to 32% (vol./vol) of a 32% wt./wt. standard hydrogen peroxide solution. 4. The method of claim 1, wherein the first extractant is a copper-selective extractant. 5. The method of claim 1, further comprising, after the stripping step, a second extraction step comprising contacting the copper-depleted second filtrate with a second organic phase comprising a second water-immiscible organic solvent and a second extractant to extract at least manganese, iron, and aluminum metals into the second organic phase and provide a solution that is depleted in manganese, iron, and aluminum, and enriched in cobalt, lithium, and nickel. 6. The method of claim 5, wherein the second extractant is an organophosphorus extractant. 7. The method of claim 6, wherein the organophosphorus extractant is di-(2-ethylhexyl) phosphoric acid. 8. The method of claim 5, further comprising a second stripping step comprising contacting the second organic phase comprising the at least manganese, iron, and aluminum metals with a second acidic strip solution to extract the at least manganese, iron, and aluminum into the second acidic strip solution. 9. The method of claim 8, further comprising a third extraction step comprising contacting the solution enriched in cobalt, lithium, and nickel with a third organic phase comprising a third water-immiscible organic solvent and a third extractant to extract at least cobalt metal into the third organic phase and provide a solution that enriched in lithium and nickel. 10. The method of claim 9, wherein the third extractant is a phosphinic acid-based extractant. 11. The method of claim 9, further comprising a third stripping step comprising contacting the third organic phase comprising the at least cobalt metal with a third acidic strip solution to extract at least cobalt metal into the third acidic strip solution. 13. The method of claim 11, further comprising increasing the pH of the solution that is enriched in lithium and nickel to precipitate a nickel salt and provide a lithium-enriched solution that is nickel-depleted. 14. The method of claim 13, further comprising collecting the precipitated nickel salt from the lithium-enriched solution. 15. The method of claim 14, further comprising precipitating a lithium salt from the lithium- enriched solution and collecting the precipitated lithium salt. 16. The method of claim 15, wherein precipitating a lithium salt comprises adding sodium phosphate or potassium phosphate to the lithium-enriched solution to precipitate lithium phosphate salt. 17. The method of claim 16, further comprising dissolving the lithium phosphate salt in an acidic solution and adding calcium hydroxide, magnesium hydroxide, barium hydroxide, lithium hydroxide or a combination thereof until a pH ranging between 8 and 14 is reached to provide a solution comprising lithium hydroxide and precipitated calcium sulfate. 18. The method of claim 1, wherein the extraction step and corresponding stripping step are performed in one of a hollow fiber membrane, a tubular membrane, a spiral-wound membrane, plate and frame membrane, and a separatory funnel. 19. A method for recovering metals, the method comprising: forming a first mixture by contacting black mass with a first acidic solution and filtering the first mixture to collect a first filtrate and a first filter cake; contacting the first filtrate with a first organic phase comprising a first water-immiscible organic solvent and a cobalt-selective extractant to extract at least cobalt metal into the organic phase and form a solution enriched in lithium, nickel, and cobalt; contacting the solution enriched with lithium, nickel, and cobalt with a second organic phase comprising a second water-immiscible organic solvent and a cobalt-selective extractant to extract at least cobalt metal into the second organic phase and forming a cobalt-depleted solution that is enriched in lithium and nickel. 20. The method of claim 19, further comprising collecting cobalt from the second organic phase by contacting the second organic phase with an acidic strip solution to extract cobalt from the second organic phase into the acidic strip solution. 21. The method of claim 19, further comprising increasing the pH of the cobalt-depleted solution to precipitate nickel and collecting the nickel.

Description

PROCESS FOR MEMBRANE-BASED RECYCLING OF BATTERY MATERIAL CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims priority of U.S. Provisional Application No. 63/510,873 Filed June 28, 2023, which is hereby incorporated by reference it its entirety. FIELD OF THE DISCLOSURE [0002] The disclosure relates generally to methods for the extraction and enrichment of metals from batteries and other forms of electronic waste. BACKGROUND [0003] Lithium ion batteries (LIBs) are widely used for various energy storage applications, ranging from consumer electronics to national defense. The growing popularity of hybrid and electric vehicles has led to a significant growth in the demand for LIBs, and the metals such as cobalt (Co), nickel (Ni), and lithium (Li) are critical components in LIB manufacturing. The U.S. Energy Information Administration projects that light-duty battery electric vehicles (BEV) sales in the U.S. will reach 1.3-3.43 million by 2025. Global electric vehicles (EV) sales are expected to increase from 1.1 million in 2017 to 30 million by 2030. The current state of the U.S. battery supply chain is inefficient both from a processing and logistics standpoint. One of the main challenges for the U.S. is lack of production capacity for battery materials such as Co, Li, Mn and Ni. [0004] In recent years, the widespread applications of LIBs in portable electronic devices and hybrid/electric vehicles is expected to generate millions of tons of end-of-life (EOL) LIBs in future years. Over 5 million metric tons of LIBs are expected to reach EOL by 2030 which raises serious environmental concerns. These scrap LIBs could provide a secondary source of the critical battery materials with cost-effective recovery and recycling. However, because the LIB industry lacks a clear path to large scale recycling, there are no established technologies for LIB recycling and reuse. SUMMARY [0005] This application describes methods for the recovery of valuable metals including cobalt, nickel, and lithium from used, refuse, waste LIBs and other electronic waste. The methods involve pre-processing of used, refuse, waste LIBs and other electronic waste in order to obtain an intermediate material enriched in cobalt, nickel, and lithium, followed by extraction of the desired metals from the enriched intermediate material. In existing processes, some non-target metals can interfere with metal extraction steps. The inventor has discovered that pre-processing used LIBs reduces the amount of non-target metals prior to extraction steps. By employing the pre-processing steps disclosed herein in combination with one or more metal extraction steps, the recovered metal yields are significantly greater than traditional extraction methods. [0006] The method disclosed herein employs relatively small amounts of energy, chemicals, and labor. The solvent and extractant requirements, in particular, are relatively low compared to traditional methods. This reduces the need for large inventories and associated losses, and minimizes waste generation to the point of near-zero discharge. The method disclosed herein can be used to recover up to 99.9% pure lithium, nickel, cobalt, and manganese in the form of various oxides or salts, e.g., sulfates and hydroxides. The method disclosed herein provides a modular, energy-efficient, and relatively inexpensive way to recover metals from used LIBs, and produces nearly zero waste. [0007] The recycled components recaptured through methods described herein may be used to meet the demands of individual constituent elements used in LIB manufacturing even when the LIB battery chemistry is different from the LIB battery chemistry of the LIB being recycled. [0008] Some aspects of the present disclosure are directed to a method for recovering metals. In some aspects, the method comprises a dissolution step comprising contacting black mass with a first acidic solution to provide a first mixture and filtering the first mixture to collect a first filtrate and a first filter cake, a precipitation step comprising contacting the first filtrate with a first basic solution to provide a second mixture comprising at least precipitated metals aluminum and iron and filtering the second mixture to collect a second filtrate comprising unprecipitated metals and a second filter cake comprising at least precipitated metals aluminum and iron, an extraction step comprising contacting the second filtrate with a first organic phase comprising a first water- immiscible organic solvent and a first extractant to extract at least copper metal into the first organic phase, and a stripping step comprising contacting the first organic phase comprising at least copper metal with a first acidic strip solution to extract at least copper metal into the first acidic strip solution and provide a copper-enriched strip solution. Upon extraction of the second filtrate with the first organic phase comprising the first extractant, at least co