Integrated Circular Economy Model System for Direct Lithium Extraction: From Minerals to Batteries Utilizing Aluminum Hydroxide

Jayanthi, K.; Lamichhane, Tej N.; Roy, Venkat; Zhao, Fu; Navrotsky, Alexandra; Moyer, Bruce A.; Paranthaman, Mariappan Parans

doi:10.1021/acsami.3c12070

Integrated Circular Economy Model System for Direct Lithium Extraction: From Minerals to Batteries Utilizing Aluminum Hydroxide

Journal Article · Mon Dec 04 23:00:00 EST 2023 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.3c12070· OSTI ID:2281971

^[1]; Lamichhane, Tej N. ^[1]; Roy, Venkat ^[2]; ^[2]; ^[3]; ^[1]; ^[1]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Purdue Univ., West Lafayette, IN (United States)
Arizona State Univ., Tempe, AZ (United States)

Aluminum hydroxide, an abundant mineral found in nature, exists in four polymorphs: gibbsite, bayerite, nordstrandite, and doyleite. Among these polymorphs gibbsite, bayerite, and commercially synthesized amorphous aluminum hydroxide have been investigated as sorbent materials for lithium extraction from sulfate solutions. The amorphous form of Al(OH)₃ exhibits a reactivity higher than that of the naturally occurring crystalline polymorphs in terms of extracting Li⁺ ions. This study employed high-temperature oxide melt solution calorimetry to explore the energetics of the sorbent polymorphs. The enthalpic stability order was measured to be gibbsite > bayerite > amorphous Al(OH)₃. The least stable form, amorphous Al(OH)₃, undergoes a spontaneous reaction with lithium, resulting in the formation of a stable layered double hydroxide phase. Consequently, amorphous Al(OH)₃ shows promise as a sorbent material for selectively extracting lithium from clay mineral leachate solutions. Further, this research demonstrates the selective direct extraction of Li⁺ ions using amorphous aluminum hydroxide through a liquid–solid lithiation reaction, followed by acid-free delithiation and relithiation processes, achieving an extraction efficiency of 86%, and the maximum capacity was 37.86 mg·g^–1 in a single step during lithiation. With high selectivity during lithiation and nearly complete recoverability of the sorbent material during delithiation, this method presents a circular economy model. Furthermore, a life cycle analysis was conducted to illustrate the environmental advantages of replacing the conventional soda ash-based precipitation process with this method, along with a simple operational cost analysis to evaluate reagent and fuel expenses.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Sponsoring Organization:: USDOE Office of Science (SC); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Materials & Manufacturing Technologies Office (AMMTO); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2281971

Alternate ID(s):: OSTI ID: 2439892

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 50 Vol. 15; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (35)

Why is aluminum‐based lithium adsorbent ineffective in Li⁺ extraction from sulfate‐type brines Chen, Jun; Huang, Kai; Du, Jianglong AIChE Journal, Vol. 69, Issue 10 https://doi.org/10.1002/aic.18176	journal	July 2023
Progress and new directions in high temperature calorimetry Navrotsky, Alexandra Physics and Chemistry of Minerals, Vol. 2, Issue 1-2 https://doi.org/10.1007/bf00307526	journal	January 1977
Progress and new directions in high temperature calorimetry revisited Navrotsky, Alexandra Physics and Chemistry of Minerals, Vol. 24, Issue 3 https://doi.org/10.1007/s002690050035	journal	April 1997
Benefication technology for lithium-containing hydrogenic mineral products Ryabtsev, A. D. Journal of Mining Science, Vol. 41, Issue 6 https://doi.org/10.1007/s10913-006-0021-z	journal	November 2005
Recovery and regeneration of LiFePO4 from spent lithium-ion batteries via a novel pretreatment process Yang, Cheng; Zhang, Jia-liang; Jing, Qian-kun International Journal of Minerals, Metallurgy and Materials, Vol. 28, Issue 9 https://doi.org/10.1007/s12613-020-2137-6	journal	September 2021
Environmental and economic assessment of structural repair technologies for spent lithium-ion battery cathode materials Lin, Jiao; Wu, Jiawei; Fan, Ersha International Journal of Minerals, Metallurgy and Materials, Vol. 29, Issue 5 https://doi.org/10.1007/s12613-022-2430-7	journal	April 2022
Major geochemical characteristics of geothermal brines from the Upper Rhine Graben granitic basement with constraints on temperature and circulation Sanjuan, B.; Millot, R.; Innocent, Ch. Chemical Geology, Vol. 428 https://doi.org/10.1016/j.chemgeo.2016.02.021	journal	June 2016
Structure and stability of aluminium trihydroxides bayerite and gibbsite: A quantum mechanical ab initio study with the Crystal06 code Demichelis, Raffaella; Civalleri, Bartolomeo; Noel, Yves Chemical Physics Letters, Vol. 465, Issue 4-6 https://doi.org/10.1016/j.cplett.2008.09.070	journal	November 2008
Ion-fractionation of lithium ions from magnesium ions by electrodialysis using monovalent selective ion-exchange membranes Nie, Xiao-Yao; Sun, Shu-Ying; Sun, Ze Desalination, Vol. 403 https://doi.org/10.1016/j.desal.2016.05.010	journal	February 2017
Extraction of lithium from salt lake brine containing boron using multistage centrifuge extractors Shi, Dong; Zhang, Licheng; Peng, Xiaowu Desalination, Vol. 441 https://doi.org/10.1016/j.desal.2018.04.029	journal	September 2018
Lithium recovery from brine: Recent developments and challenges Khalil, Abdullah; Mohammed, Shabin; Hashaikeh, Raed Desalination, Vol. 528 https://doi.org/10.1016/j.desal.2022.115611	journal	April 2022
A review of energy storage types, applications and recent developments Koohi-Fayegh, S.; Rosen, M. A. Journal of Energy Storage, Vol. 27 https://doi.org/10.1016/j.est.2019.101047	journal	February 2020
Lithium-rich geothermal brines in Europe: An up-date about geochemical characteristics and implications for potential Li resources Sanjuan, Bernard; Gourcerol, Blandine; Millot, Romain Geothermics, Vol. 101 https://doi.org/10.1016/j.geothermics.2022.102385	journal	May 2022
Regulating lithium extraction based on intercalated SO42− in Li/Al-LDHs Chen, Jun; Yuan, Hengfeng; Yu, Jianguo Journal of Colloid and Interface Science, Vol. 649 https://doi.org/10.1016/j.jcis.2023.06.165	journal	November 2023
Global lithium resources: Relative importance of pegmatite, brine and other deposits Kesler, Stephen E.; Gruber, Paul W.; Medina, Pablo A. Ore Geology Reviews, Vol. 48 https://doi.org/10.1016/j.oregeorev.2012.05.006	journal	October 2012
The lithium industry: Its recent evolution and future prospects Ebensperger, Arlene; Maxwell, Philip; Moscoso, Christian Resources Policy, Vol. 30, Issue 3 https://doi.org/10.1016/j.resourpol.2005.09.001	journal	September 2005
Study of energy storage systems and environmental challenges of batteries Dehghani-Sanij, A. R.; Tharumalingam, E.; Dusseault, M. B. Renewable and Sustainable Energy Reviews, Vol. 104 https://doi.org/10.1016/j.rser.2019.01.023	journal	April 2019
Lithium extraction from low-grade salt lake brine with ultrahigh Mg/Li ratio using TBP – kerosene – FeCl3 system Shi, Dong; Cui, Bin; Li, Lijuan Separation and Purification Technology, Vol. 211 https://doi.org/10.1016/j.seppur.2018.09.087	journal	March 2019
Recovery of Lithium from Geothermal Brine with Lithium–Aluminum Layered Double Hydroxide Chloride Sorbents Paranthaman, Mariappan Parans; Li, Ling; Luo, Jiaqi Environmental Science & Technology, Vol. 51, Issue 22 https://doi.org/10.1021/acs.est.7b03464	journal	November 2017
Role of Anions in Stabilizing the [Zn–Al] Layered Double Hydroxides: A Thermodynamic Study Jayanthi, K.; Neilsen, Grace; Gibson, Alexis The Journal of Physical Chemistry C, Vol. 127, Issue 7 https://doi.org/10.1021/acs.jpcc.2c08217	journal	February 2023
Effect of Anions on the Delithiation of [Li–Al] Layered Double Hydroxides: Thermodynamic Insights Jayanthi, K.; Paranthaman, Mariappan Parans; Manard, Benjamin T. The Journal of Physical Chemistry C, Vol. 127, Issue 49 https://doi.org/10.1021/acs.jpcc.3c05676	journal	December 2023
Neutron Spectroscopic and Thermochemical Characterization of Lithium–Aluminum-Layered Double Hydroxide Chloride: Implications for Lithium Recovery Wu, Lili; Evans, Samuel F.; Cheng, Yongqiang The Journal of Physical Chemistry C, Vol. 123, Issue 34 https://doi.org/10.1021/acs.jpcc.9b04340	journal	July 2019
Synthesis of lithium dialuminate by salt imbibition Poeppelmeier, K. R.; Hwu, S. J. Inorganic Chemistry, Vol. 26, Issue 20 https://doi.org/10.1021/ic00267a017	journal	October 1987
Structure of Bayerite-Based Lithium−Aluminum Layered Double Hydroxides (LDHs): Observation of Monoclinic Symmetry Britto, Sylvia; Kamath, P. Vishnu Inorganic Chemistry, Vol. 48, Issue 24 https://doi.org/10.1021/ic9016728	journal	December 2009
The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms Barrett, Elliott P.; Joyner, Leslie G.; Halenda, Paul P. Journal of the American Chemical Society, Vol. 73, Issue 1 https://doi.org/10.1021/ja01145a126	journal	January 1951
Adsorption of Gases in Multimolecular Layers Brunauer, Stephen; Emmett, P. H.; Teller, Edward Journal of the American Chemical Society, Vol. 60, Issue 2, p. 309-319 https://doi.org/10.1021/ja01269a023	journal	February 1938
Environmental impact of direct lithium extraction from brines Vera, María L.; Torres, Walter R.; Galli, Claudia I. Nature Reviews Earth & Environment, Vol. 4, Issue 3 https://doi.org/10.1038/s43017-022-00387-5	journal	February 2023
Future material demand for automotive lithium-based batteries Xu, Chengjian; Dai, Qiang; Gaines, Linda Communications Materials, Vol. 1, Issue 1 https://doi.org/10.1038/s43246-020-00095-x	journal	December 2020
Observation of cation ordering and anion-mediated structure selection among the layered double hydroxides of Cu(ii) and Cr(iii) Jayanthi, K.; Kamath, P. Vishnu Dalton Transactions, Vol. 42, Issue 36 https://doi.org/10.1039/c3dt50678a	journal	January 2013
Energy storage emerging: A perspective from the Joint Center for Energy Storage Research Trahey, Lynn; Brushett, Fikile R.; Balsara, Nitash P. Proceedings of the National Academy of Sciences, Vol. 117, Issue 23 https://doi.org/10.1073/pnas.1821672117	journal	June 2020
Progress and New Directions in Calorimetry: A 2014 Perspective Navrotsky, Alexandra Journal of the American Ceramic Society, Vol. 97, Issue 11 https://doi.org/10.1111/jace.13278	journal	October 2014
Lithium aluminum‐layered double hydroxide chlorides ( LDH ): Formation enthalpies and energetics for lithium ion capture Wu, Lili; Li, Ling; Evans, Samuel F. Journal of the American Ceramic Society https://doi.org/10.1111/jace.16150	journal	October 2018
Cryogenic heat capacity measurements and thermodynamic analysis of lithium aluminum layered double hydroxides (LDHs) with intercalated chloride Jayanthi, K.; Neilsen, Grace; Rosen, Peter F. American Mineralogist, Vol. 107, Issue 4 https://doi.org/10.2138/am-2021-7935	journal	April 2022
Mineral commodity summaries 2018 Ober, Joyce A. https://doi.org/10.3133/70194932	report	January 2018
A Review on the Role of Amorphous Aluminum Compounds in Catalysis: Avenues of Investigation and Potential Application in Petrochemistry and Oil Refining Mukhamed’yarova, Aliya N.; Gareev, Bulat I.; Nurgaliev, Danis K. Processes, Vol. 9, Issue 10 https://doi.org/10.3390/pr9101811	journal	October 2021

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