Critical Material Recovery from Salt-Lakes and Spent Batteries with Membranes and Solvents
The sustainable extraction and recovery of critical metals such as lithium, cobalt, and rare earth elements are essential for advancing renewable energy technologies, electric vehicles, and modern electronics. This thesis addresses the significant environmental, economic, and logistical challenges a...
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| Format: | Thesis |
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Massachusetts Institute of Technology
2025
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| Online Access: | https://hdl.handle.net/1721.1/158322 https://orcid.org/0000-0002-7474-7065 |
| _version_ | 1826194717215293440 |
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| author | Foo, Zi Hao |
| author2 | Lienhard, John H. |
| author_facet | Lienhard, John H. Foo, Zi Hao |
| author_sort | Foo, Zi Hao |
| collection | MIT |
| description | The sustainable extraction and recovery of critical metals such as lithium, cobalt, and rare earth elements are essential for advancing renewable energy technologies, electric vehicles, and modern electronics. This thesis addresses the significant environmental, economic, and logistical challenges associated with traditional methods of extracting these metals from primary sources like spodumene ores and continental salt lakes, and secondary sources like spent battery and magnet leachates. Conventional extraction processes from primary sources are highly energy-intensive, environmentally taxing, and pose substantial water usage concerns. In contrast, while secondary sources such as spent lithium-ion batteries offer a promising avenue to alleviate environmental impacts and secure a stable supply chain, they still pose challenges in terms of high chemical usage and waste acid management. This research focuses on advancing three innovative processes: nanofiltration, electrodialysis, and solvent-driven fractional crystallization, aiming to enhance the efficiency and sustainability of metal recovery from both primary and secondary sources. The thesis findings are supported by direct experimental measurements and extensive computation involving multi-ionic and mixed-solvent activity and fugacity coefficient models, fundamental molecular dynamics simulation, multicomponent continuum dynamics ion transport models across nanofiltration and ion exchange membranes, and techno-economic analysis of membrane and solvent processes. First, advancements in nanofiltration technology are explored to pre-treat salt-lake brines for improved lithium extraction efficiency and purity. Positively charged nanofiltration membranes demonstrate enhanced monovalent selectivity through Donnan exclusion, effectively removing multivalent cations and improving lithium purity in the feed brine. Our results show that the Li/Mg selectivity can be enhanced by 13 times with Donnan-enhanced nanofiltration membranes. Our experiments exemplify the Donnan-enhanced membrane’s ability to reduce magnesium concentrations to 0.14 % from salt lakes in a single filtration stage. This method not only increases the yield and quality of extracted lithium but also reduces the environmental impact by minimizing additional purification steps. Second, electrodialysis is investigated for the selective recovery of lithium from complex mixtures like battery leachates. This technique leverages ion mobility differences to retain lithium ions while separating other cations. Bipolar membrane electrodialysis further converts lithium chloride into high-purity lithium hydroxide and hydrochloric acid, which can be recycled, thereby supporting a circular economy in battery recycling. Experimental results demonstrate that selective electrodialysis can achieve ∼99 % lithium purity with 68.8 % lithium retention from Ni-Mn-Co battery leachates. The techno-economic analysis projects LiOH production costs between USD 1.1 to 3.6 per kilogram, approximately an order of magnitude lower than prevailing market prices. Third, the use of dimethyl ether (DME) in solvent-driven fractional crystallization is examined as an innovative method for extracting critical metals. DME’s properties allow for efficient water extraction from aqueous solutions, causing the crystallization of metals like cobalt and nickel. Our computational analysis reveals that DME-based solvent-driven water extraction can concentrate an input saline feed to 5.5 M and regenerate over 99 % of the DME using ultra-low-grade heat below 50°C, with a DME/water selectivity ratio of 125. This process ensures high purity and reduces post-processing needs, offering a more environmentally friendly alternative to traditional solvent extraction techniques. The findings of this thesis underscore the potential of advanced variants of nanofiltration, electrodialysis, and solvent-driven fractional crystallization technologies in promoting sustainable and economically viable critical metal recovery processes. By addressing the pressing issues of environmental degradation and resource scarcity, this research supports the development of a circular resource economy, where waste materials are continuously reused and recycled, contributing to a sustainable energy future. |
| first_indexed | 2025-03-10T08:23:18Z |
| format | Thesis |
| id | mit-1721.1/158322 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2025-03-10T08:23:18Z |
| publishDate | 2025 |
| publisher | Massachusetts Institute of Technology |
| record_format | dspace |
| spelling | mit-1721.1/1583222025-03-05T15:27:40Z Critical Material Recovery from Salt-Lakes and Spent Batteries with Membranes and Solvents Foo, Zi Hao Lienhard, John H. Massachusetts Institute of Technology. Department of Mechanical Engineering The sustainable extraction and recovery of critical metals such as lithium, cobalt, and rare earth elements are essential for advancing renewable energy technologies, electric vehicles, and modern electronics. This thesis addresses the significant environmental, economic, and logistical challenges associated with traditional methods of extracting these metals from primary sources like spodumene ores and continental salt lakes, and secondary sources like spent battery and magnet leachates. Conventional extraction processes from primary sources are highly energy-intensive, environmentally taxing, and pose substantial water usage concerns. In contrast, while secondary sources such as spent lithium-ion batteries offer a promising avenue to alleviate environmental impacts and secure a stable supply chain, they still pose challenges in terms of high chemical usage and waste acid management. This research focuses on advancing three innovative processes: nanofiltration, electrodialysis, and solvent-driven fractional crystallization, aiming to enhance the efficiency and sustainability of metal recovery from both primary and secondary sources. The thesis findings are supported by direct experimental measurements and extensive computation involving multi-ionic and mixed-solvent activity and fugacity coefficient models, fundamental molecular dynamics simulation, multicomponent continuum dynamics ion transport models across nanofiltration and ion exchange membranes, and techno-economic analysis of membrane and solvent processes. First, advancements in nanofiltration technology are explored to pre-treat salt-lake brines for improved lithium extraction efficiency and purity. Positively charged nanofiltration membranes demonstrate enhanced monovalent selectivity through Donnan exclusion, effectively removing multivalent cations and improving lithium purity in the feed brine. Our results show that the Li/Mg selectivity can be enhanced by 13 times with Donnan-enhanced nanofiltration membranes. Our experiments exemplify the Donnan-enhanced membrane’s ability to reduce magnesium concentrations to 0.14 % from salt lakes in a single filtration stage. This method not only increases the yield and quality of extracted lithium but also reduces the environmental impact by minimizing additional purification steps. Second, electrodialysis is investigated for the selective recovery of lithium from complex mixtures like battery leachates. This technique leverages ion mobility differences to retain lithium ions while separating other cations. Bipolar membrane electrodialysis further converts lithium chloride into high-purity lithium hydroxide and hydrochloric acid, which can be recycled, thereby supporting a circular economy in battery recycling. Experimental results demonstrate that selective electrodialysis can achieve ∼99 % lithium purity with 68.8 % lithium retention from Ni-Mn-Co battery leachates. The techno-economic analysis projects LiOH production costs between USD 1.1 to 3.6 per kilogram, approximately an order of magnitude lower than prevailing market prices. Third, the use of dimethyl ether (DME) in solvent-driven fractional crystallization is examined as an innovative method for extracting critical metals. DME’s properties allow for efficient water extraction from aqueous solutions, causing the crystallization of metals like cobalt and nickel. Our computational analysis reveals that DME-based solvent-driven water extraction can concentrate an input saline feed to 5.5 M and regenerate over 99 % of the DME using ultra-low-grade heat below 50°C, with a DME/water selectivity ratio of 125. This process ensures high purity and reduces post-processing needs, offering a more environmentally friendly alternative to traditional solvent extraction techniques. The findings of this thesis underscore the potential of advanced variants of nanofiltration, electrodialysis, and solvent-driven fractional crystallization technologies in promoting sustainable and economically viable critical metal recovery processes. By addressing the pressing issues of environmental degradation and resource scarcity, this research supports the development of a circular resource economy, where waste materials are continuously reused and recycled, contributing to a sustainable energy future. Ph.D. 2025-03-05T15:27:33Z 2025-03-05T15:27:33Z 2024-09 2025-03-03T16:17:56.927Z Thesis https://hdl.handle.net/1721.1/158322 https://orcid.org/0000-0002-7474-7065 In Copyright - Educational Use Permitted Copyright retained by author(s) https://rightsstatements.org/page/InC-EDU/1.0/ application/pdf Massachusetts Institute of Technology |
| spellingShingle | Foo, Zi Hao Critical Material Recovery from Salt-Lakes and Spent Batteries with Membranes and Solvents |
| title | Critical Material Recovery from Salt-Lakes and Spent Batteries with Membranes and Solvents |
| title_full | Critical Material Recovery from Salt-Lakes and Spent Batteries with Membranes and Solvents |
| title_fullStr | Critical Material Recovery from Salt-Lakes and Spent Batteries with Membranes and Solvents |
| title_full_unstemmed | Critical Material Recovery from Salt-Lakes and Spent Batteries with Membranes and Solvents |
| title_short | Critical Material Recovery from Salt-Lakes and Spent Batteries with Membranes and Solvents |
| title_sort | critical material recovery from salt lakes and spent batteries with membranes and solvents |
| url | https://hdl.handle.net/1721.1/158322 https://orcid.org/0000-0002-7474-7065 |
| work_keys_str_mv | AT foozihao criticalmaterialrecoveryfromsaltlakesandspentbatterieswithmembranesandsolvents |