An Integrated Chemicals-Free Circular Model for Lithium Recovery From Spent Batteries to Direct Lithium Extraction From Brines

Abstract

The growing demand for lithium calls for integrated strategies that combine resource recovery with sustainable material synthesis. Here, we demonstrate a patented chemicals-free circular approach that converts real spent lithium-ion battery black mass into functional lithium–aluminum layered double hydroxide (Li/Al-LDH). The process integrates a 5-min microwave-assisted carbothermic treatment, water-only leaching, and spontaneous precipitation, enabling the formation of crystalline Li/Al-LDHs alongside high-purity Li₂CO₃ without the use of added chemical reagents. Structural characterization by synchrotron pair distribution function analysis, XRD, and SEM confirms the formation of phase-pure LDHs with a hierarchical nanosheet-based morphology and an exceptionally high surface area (more than 400 m² g^-1). Preliminary adsorption–desorption experiments demonstrate the ability of the synthesized Li/Al-LDHs to reversibly exchange lithium ions, supporting their potential application as sorbents for lithium recovery from aqueous systems. The sustainability analysis reveals a reduction of 60%–90% in environmental impacts, including embodied energy and carbon footprint, compared to conventional LDH synthesis routes. This work establishes for the first time a direct link between battery recycling and lithium extraction technologies, providing a scalable pathway toward a circular and low-carbon lithium economy.

Keywords

layered double hydroxides / LDH / LIBs / lithium-ion battery / recycle

References

[1] Y. Zha, Y. Li, Z. Fei, et al., “Leaching Li From Mixed Cathode Materials of Spent Lithium-Ion Batteries via Carbon Thermal Reduction,” Dalton Transactions 53 (2024): 5592–5600.

[2] IEA, Global EV Outlook 2024 (IEA, 2024), https://www.iea.org/reports/global-ev-outlook-2024.

[3] H. Tong, Z. Liu, Y. Li, et al., “Sustainable Recovery of Spent Ternary Cathode Materials via Wasted Asphalt Pyrolysis in Closed-Loop Recycling,” Sustainable Materials and Technologies 44 (2025): e01343.

[4] Y. Zhang, Y. Hu, L. Wang, and W. Sun, “Systematic Review of Lithium Extraction From Salt-Lake Brines via Precipitation Approaches,” Minerals Engineering 139 (2019): 105868.

[5] R. Krishnan and G. Gopan, “A Comprehensive Review of Lithium Extraction: From Historical Perspectives to Emerging Technologies, Storage, and Environmental Considerations,” Cleaner Engineering and Technology 20 (2024): 100749.

[6] Y. Ran, S. Yoon, D. M. Jöckel, et al., “Reviving Spent Lithium-Ion Batteries: The Advancements and Challenges of Sustainable Black Mass Recovery,” Battery Energy 3 (2024): 20230059.

[7] J. Zhong, S. Lin, and J. Yu, “Effects of Excessive Lithium Deintercalation on Li⁺ Adsorption Performance and Structural Stability of Lithium/Aluminum Layered Double Hydroxides,” Journal of Colloid and Interface Science 572 (2020): 107–113.

[8] K. Jayanthi, M. P. Paranthaman, B. T. Manard, and A. Navrotsky, “Effect of Anions on the Delithiation of [Li–Al] Layered Double Hydroxides: Thermodynamic Insights,” Journal of Physical Chemistry C 127 (2023): 23879–23886.

[9] Z. Wu, Z. Xie, J. Wang, et al., “Lithium-Salt-Containing Ionic Liquid-Incorporated Li-Al-Layered Double Hydroxide-Based Solid Electrolyte With High-Performance and Safety in Solid-State Lithium Batteries,” ACS Sustainable Chemistry & Engineering 8 (2020): 12378–12387.

[10] Y. Tian, C. Wang, F. Zhang, L. Xu, Z. Zhao, and B. Tong, “Mechanism of Lithium Adsorption by AlLi-LDH With Al–O Octahedral Ring,” Transactions of Nonferrous Metals Society of China 34 (2024): 1321–1332.

[11] A. Farhan, A. Khalid, N. Maqsood, et al., “Progress in Layered Double Hydroxides (LDHs): Synthesis and Application in Adsorption, Catalysis and Photoreduction,” Science of the Total Environment 912 (2024): 169160.

[12] A. M. Fogg and D. O'Hare, “Study of the Intercalation of Lithium Salt in Gibbsite Using Time-Resolved In Situ X-Ray Diffraction,” Chemistry of Materials 11 (1999): 1771–1775.

[13] G. R. Williams and D. O'Hare, “A Kinetic Study of the Intercalation of Lithium Salts Into Al(OH) 3,” Journal of Physical Chemistry B 110 (2006): 10619–10629.

[14] S. L. Wang, C. H. Lin, Y. Y. Yan, and M. K. Wang, “Synthesis of Li/Al LDH Using Aluminum and LiOH,” Applied Clay Science 72 (2013): 191–195.

[15] J. Wu, B. Liu, J. Qian, et al., “Facile Synthesis of Aluminum-Based Adsorbents From Spent Lithium-Ion Batteries for Efficient Li+ Extraction,” Journal of Environmental Chemical Engineering 13 (2025): 117000.

[16] A. R. Hind, S. K. Bhargava, and S. C. Grocott, “The Surface Chemistry of Bayer Process Solids: A Review,” Colloids and Surfaces, A: Physicochemical and Engineering Aspects 146 (1999): 359–374.

[17] M. Scaglia, A. Cornelio, A. Zanoletti, et al., “Microwave-Assisted Recovery of Spent LiCoO₂ Battery From the Corresponding Black Mass,” Batteries 9, no. 11 (2023): 536.

[18] A. Cornelio, E. Galli, M. Scaglia, et al., “Recovery of NMC-Lithium Battery Black Mass by Microwave Heating Processes,” Energy Storage Materials 72 (2024): 103703.

[19] A. Zanoletti, A. Cornelio, L. Borgese, et al., “Sample Preparation Procedures for Elemental Analysis of Critical Raw Materials in Lithium-Ion Battery Black Mass: Challenges Responding to the Supplementary Battery Recycling Regulation,” Journal of Environmental Management 380 (2025): 124973.

[20] P. Juhás, T. Davis, C. L. Farrow, and S. J. L. Billinge, “PDFgetX3: A Rapid and Highly Automatable Program for Processing Powder Diffraction Data Into Total Scattering Pair Distribution Functions,” Journal of Applied Crystallography 46 (2013): 560–566.

[21] J. Peng, T. A. Ablott, H. E. A. Brand, D. P. Abraham, T. Cataldo, and N. Sharma, “Thermal Stability of LiNixMnyCozO2 Cathode Materials,” Chemistry of Materials 38, no. 2 (2026): 791–807.

[22] A. Mannu, M. E. Di Pietro, V. Bosello, et al., “Selective and Sustainable Recovery of Lithium From Black Mass via Microwave and Green Leaching Techniques,” Materials Science and Engineering: B 323, no. B (2026): 118734.

[23] G. Lombardo, B. Ebin, M. R. St. J. Foreman, B.-M. Steenari, and M. Petranikova, “Incineration of EV Lithium-Ion Batteries as a Pretreatment for Recycling – Determination of the Potential Formation of Hazardous By-Products and Effects on Metal Compounds,” Journal of Hazardous Materials 393 (2020): 122372.

[24] A. Cornelio, A. Zanoletti, G. Dativo, et al., “Performance and Structural Evolution of a New Critical Raw Material-Free Catalyst, Synthesized From Spent Lithium-Ion Batteries, for Solar-Driven CO₂ Conversion,” Green Chemistry 27 (2025): 10132–10144.

[25] B. K. Biswal, B. Zhang, P. Thi Minh Tran, J. Zhang, and R. Balasubramanian, “Recycling of Spent Lithium-Ion Batteries for a Sustainable Future: Recent Advancements,” Chemical Society Reviews 53 (2024): 5552–5592.

[26] E. Mousa, X. Hu, L. Ånnhagen, et al., “Characterization and Thermal Treatment of the Black Mass From Spent Lithium-Ion Batteries,” Sustain 15 (2023): 15.

[27] A. Cornelio, A. Zanoletti, M. Scaglia, et al., “Thermal Approaches Based on Microwaves to Recover Lithium From Spent Lithium-Ion Batteries,” RSC Sustainability 2 (2024): 2505–2514.

[28] E. Epifano and D. Monceau, “Ellingham Diagram: A New Look at an Old Tool,” Corrosion Science 217 (2023): 111113.

[29] M. Inaba, Y. Iriyama, Z. Ogumi, Y. Todzuka, and A. Tasaka, “Raman Study of Layered Rock-Salt LiCoO₂ and Its Electrochemical Lithium Deintercalation,” Journal of Raman Spectroscopy 28 (1997): 613–617.

[30] T. Gao, H. Fjellvåg, and P. Norby, “A Comparison Study on Raman Scattering Properties of α- and Β-MnO₂,” Analytica Chimica Acta 648, no. 2 (2009): 235–239.

[31] V. G. Hadjiev, M. N. Iliev, and I. V. Vergilov, “The Raman Spectra of Co₃O₄,” Journal of Physics C: Solid State Physics 21, no. 7 (1988): L199–L201.

[32] Z.-L. Jiang, G.-L. Xu, Z. Yu, et al., “High Rate and Long Cycle Life in Li–O₂ Batteries With Highly Efficient Catalytic Cathode Configured With Co₃O₄ Nanoflower,” Nano Energy 64 (2019): 103896.

[33] C. M. Julien and A. Mauger, “In Situ Raman Analyses of Electrode Materials for Li-Ion Batteries,” AIMS Materials Science 5, no. 4 (2018): 650–698.

[34] A. Fahimi, I. Alessandri, A. Cornelio, et al., “A Microwave-Enhanced Method Able to Substitute Traditional Pyrometallurgy for the Future of Metals Supply From Spent Lithium-Ion Batteries,” Resources, Conservation And Recycling 194 (2023): 106989.

[35] J. P. Thiel, C. K. Chiang, and K. R. Poeppelmeier, “Structure of Lithium Aluminum Hydroxide Dihydrate (LiAl₂(OH)7.2H₂O),” Chemistry of Materials 5 (1993): 297–304.

[36] T. R. Graham, J. Z. Hu, X. Zhang, et al., “Unraveling Gibbsite Transformation Pathways Into LiAl-LDH In Concentrated Lithium Hydroxide,” Inorganic Chemistry 58 (2019): 12385–12394.

[37] H. A. Van Straten, B. T. W. Holtkamp, and P. L. de Bruyn, “Precipitation From Supersaturated Aluminate Solutions,” Journal of Colloid and Interface Science 98 (1984): 342–362.

[38] A. C. Carrasco, V. Rodríguez-Fanjul, A.- Habtemariam, and A. M. Pizarro, “Structurally Strained Half-Sandwich Iridium(III) Complexes as Highly Potent Anticancer Agents,” Journal of Medicinal Chemistry 63, no. 8 (2020): 4005–4021.

[39] M. Dong, Q. Luo, J. Li, Z. Wu, and Z. Liu, “Lithium Adsorption Properties of Porous LiAl-Layered Double Hydroxides Synthesized Using Surfactants,” Journal of Saudi Chemical Society 26 (2022): 101535.

[40] K. Jayanthi, T. N. Lamichhane, V. Roy, et al., “Integrated Circular Economy Model System for Direct Lithium Extraction: From Minerals to Batteries Utilizing Aluminum Hydroxide,” ACS Applied Materials & Interfaces 15 (2023): 58984–58993.

[41] J. Xu, X. Wei, J. Han, and W. Qin, “Synthesis and Optimisation Mechanism of Functionalised Adsorption Materials for Lithium-Ion Extraction From Salt Water: A Review,” Separation and Purification Technology 339 (2024): 126237.

[42] N. P. Kotsupalo, A. D. Ryabtsev, I. A. Poroshina, et al., “Effect of Structure on the Sorption Properties of Chlorine-Containing Form of Double Aluminum Lithium Hydroxide,” Russian Journal of Applied Chemistry 86 (2013): 482–487.

[43] P. Chen, S. Wang, T. R. Graham, et al., “Unraveling Anion-Specific Inhibition and Structural Modulation of Gibbsite Crystallization: Implications for Aluminum Mobility in Natural and Engineered Systems,” ACS Applied Materials & Interfaces 17, no. 46 (2025): 63987–63995.

[44] S. Nikfar, A. Fahimi, and E. Vahidi, “Unlocking Sustainable Lithium: A Comparative Life Cycle Assessment of Innovative Extraction Methods From Brine,” Resources, Conservation And Recycling 212 (2025): 107977.

[45] E. Bontempi, “A New Approach for Evaluating the Sustainability of Raw Materials Substitution Based on Embodied Energy and the CO₂ Footprint,” Journal of Cleaner Production 162 (2017): 162–169.

[46] S. Ducoli, A. Fahimi, E. Mousa, et al., “ESCAPE Approach for the Sustainability Evaluation of Spent Lithium-Ion Batteries Recovery: Dataset of 33 Available Technologies,” Data in Brief 42 (2022): 108018.

[47] J. Bare, “TRACI 2.0: The Tool for the Reduction and Assessment of Chemical and Other Environmental Impacts 2.0,” Clean Technologies and Environmental Policy 13 (2011): 687–696.

RIGHTS & PERMISSIONS

2026 The Author(s). Battery Energy published by Xijing University and John Wiley & Sons Australia, Ltd.