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Spatially separated crystallization for selective lithium extraction from saline water


Limited lithium supply is hindering the global transformation towards electrification and decarbonization. Current lithium mining can be energy, chemical and land intensive. Here we present an efficient and self-concentrating crystallization method for the selective extraction of lithium from both brine and seawater. The sequential and separable crystallization of cation species with different concentrations and solubilities was enabled by a twisted and slender 3D porous natural cellulose fibre structure via capillary and evaporative flows. The process exhibited an evaporation rate as high as 9.8 kg m2 h−1, and it selectively concentrated lithium by orders of magnitude. The composition and spatial distribution of crystals were characterized, and a transport model deciphered the ion re-distribution process in situ. We also demonstrated system scalability via a 100-crystallizer array.

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Fig. 1: Interfacial crystallization and spatial distribution of ion products on the twisted 3D fibre structure.
Fig. 2: Li is concentrated at the top of the fibre crystallizer.
Fig. 3: Li is concentrated at the centre of the fibre crystallizer.
Fig. 4: Twist fibre structures achieve high water lifting and faster evaporation from brine water.
Fig. 5: Practical feasibility of the spatial crystallization system using simulated seawater.

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All data are presented in the article and its Supplementary Information. Source data are provided with this paper.


  1. Goldthau, A. & Hughes, L. Protect global supply chains for low-carbon technologies. Nature 585, 28–30 (2020).

    Article  CAS  PubMed  Google Scholar 

  2. Greim, P., Solomon, A. A. & Breyer, C. Assessment of lithium criticality in the global energy transition and addressing policy gaps in transportation. Nat. Commun. 11, 1–11 (2020).

    Article  Google Scholar 

  3. Sun, X., Liu, Z., Zhao, F. & Hao, H. Global competition in the lithium-ion battery supply chain: a novel perspective for criticality analysis. Environ. Sci. Technol. 55, 12180–12190 (2021).

    Article  CAS  PubMed  Google Scholar 

  4. Raw materials for a truly green future. Nat. Rev. Mater. 6, 455 (2021).

  5. Miatto, A., Wolfram, P., Reck, B. K. & Graedel, T. E. Uncertain future of American lithium: a perspective until 2050. Environ. Sci. Technol. 55, 16184–16194 (2021).

    Article  CAS  PubMed  Google Scholar 

  6. Lithium. TRADING ECONOMICS (2023).

  7. Azevedo, M., Baczynska, M., Hoffman, K. & Krauze, A. Lithium mining: how new production technologies could fuel the global EV revolution. McKinsey & Company (2022).

  8. Jaskula, B.W. USGS: 2015 Minerals Yearbook: lithium [advanced released]. (2017).

  9. Yao, S. Lithium costs up in 2021, continuing to surge in 2022. S&P Global Market Intelligence. (2022).

  10. Murodjon, S., Yu, X., Li, M., Duo, J. & Deng, T. Lithium recovery from brines including seawater, salt lake brine, underground water and geothermal water. Thermodyn. Energy Eng. (2020).

  11. He, X., Kaur, S. & Kostecki, R. Mining lithium from seawater. Joule 4, 1357–1358 (2020).

    Article  CAS  Google Scholar 

  12. Grosjean, C., Herrera Miranda, P., Perrin, M. & Poggi, P. Assessment of world lithium resources and consequences of their geographic distribution on the expected development of the electric vehicle industry. Renew. Sustain. Energy Rev. 16, 1735–1744 (2012).

    Article  Google Scholar 

  13. Yang, S., Zhang, F., Ding, H., He, P. & Zhou, H. Lithium metal extraction from seawater. Joule 2, 1648–1651 (2018).

    Article  Google Scholar 

  14. Xu, J. et al. A green and sustainable strategy toward lithium resources recycling from spent batteries. Sci. Adv. 8, eabq7948 (2022).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  15. Lithium MarketIndustry Analysis and Forecast (2022–2029) (Maximize Market Research Pvt, 2019).

  16. Sociedad Química y Minera de Chile S.A. (SQM 2021): Annual Reports (2021).

  17. Gutiérrez, J. S., Navedo, J. G. & Soriano-Redondo, A. Atacama imperilled by lithium mining. Nature (2018).

  18. Lèbre, É. et al. The social and environmental complexities of extracting energy transition metals. Nat. Commun. (2020).

  19. Amoatey, P. et al. A critical review of environmental and public health impacts from the activities of evaporation ponds. Sci. Total Environ. 796, 149065 (2021).

    Article  CAS  PubMed  Google Scholar 

  20. Safari, S., Lottermoser, B. G. & Alessi, D. S. Metal oxide sorbents for the sustainable recovery of lithium from unconventional resources. Appl. Mater. Today 19, 100638 (2020).

    Article  Google Scholar 

  21. Stringfellow, W. T. & Dobson, P. F. Technology for lithium extraction in the context of hybrid geothermal power. Proc. 46th Work. Geotherm. Reserv. Eng. 46, 1–20 (2021).

    Google Scholar 

  22. Li, X. et al. Membrane-based technologies for lithium recovery from water lithium resources: a review. J. Memb. Sci. 591, 117317 (2019).

    Article  CAS  Google Scholar 

  23. Liu, G., Zhao, Z. & Ghahreman, A. Novel approaches for lithium extraction from salt-lake brines: a review. Hydrometallurgy 187, 81–100 (2019).

    Article  CAS  Google Scholar 

  24. Sun, Y., Wang, Q., Wang, Y., Yun, R. & Xiang, X. Recent advances in magnesium/lithium separation and lithium extraction technologies from salt lake brine. Sep. Purif. Technol. 256, 117807 (2021).

    Article  CAS  Google Scholar 

  25. Zhao, X., Yang, H., Wang, Y. & Sha, Z. Review on the electrochemical extraction of lithium from seawater/brine. J. Electroanal. Chem. 850, 113389 (2019).

    Article  CAS  Google Scholar 

  26. Parsa, N., Moheb, A., Mehrabani-Zeinabad, A. & Masigol, M. A. Recovery of Lithium Ions from Sodium-Contaminated Lithium Bromide Solution by Using Electrodialysis Process. Chemical Engineering Research and Design vol. 98 (Institution of Chemical Engineers, 2015).

  27. Hoshino, T. Preliminary studies of lithium recovery technology from seawater by electrodialysis using ionic liquid membrane. Desalination 317, 11–16 (2013).

    Article  CAS  Google Scholar 

  28. Warnock, S. J. et al. Engineering Li/Na selectivity in 12-Crown-4-functionalized polymer membranes. Proc. Natl Acad. Sci. USA 118, 1–8 (2021).

    Article  Google Scholar 

  29. Habata, Y., Ikeda, M. & Akabori, S. Lithium ion selective dibenzo-14-crown-4 possessing a phosphoric acid functional group as a pendant. Tetrahedron Lett. 33, 3157–3160 (1992).

    Article  CAS  Google Scholar 

  30. Hano, T., Matsumoto, M., Ohtake, T., Egashira, N. & Hori, F. Recovery of lithium from geothermal water by solvent extraction technique. Solvent Extr. Ion Exch. 10, 195–206 (1992).

    Article  CAS  Google Scholar 

  31. Swain, B. Separation and purification of lithium by solvent extraction and supported liquid membrane, analysis of their mechanism: a review. J. Chem. Technol. Biotechnol. 91, 2549–2562 (2016).

    Article  CAS  Google Scholar 

  32. Yim, C.-H. & Abu-Lebdeh, Y. A. Connection between phase diagram, structure and ion transport in liquid, aqueous electrolyte solutions of lithium chloride. J. Electrochem. Soc. 165, A547–A556 (2018).

    Article  CAS  Google Scholar 

  33. Report, O. & Atacama, S. D. E. Technical Report Summary Operation Report Salar de Atacama (2022).

  34. Kuznetsov, G. V. et al. Evaporation modes of LiBr, CaCl2, LiCl, NaCl aqueous salt solution droplets on aluminum surface. Int. J. Heat Mass Transf. 126, 161–168 (2018).

    Article  CAS  Google Scholar 

  35. Lu, L. et al. Unbiased solar H2 production with current density up to 23 mA cm−2 by Swiss-cheese black Si coupled with wastewater bioanode. Energy Environ. Sci. 12, 1088–1099 (2019).

    Article  CAS  Google Scholar 

  36. Chen, X. et al. Sustainable off-grid desalination of hypersaline waters using Janus wood evaporators. Energy Environ. Sci. 14, 5347–5357 (2021).

    Article  CAS  Google Scholar 

  37. Zheng, S. et al. Upscaling 3D engineered trees for off-grid desalination. Environ. Sci. Technol. 56, 1289–1299 (2022).

    Article  CAS  PubMed  Google Scholar 

  38. Jiang, J., Chen, X., Chen, X. & Ren, Z. J. Energy-efficient microbial electrochemical lignin and alkaline hydroxide recovery from DMR black liquor. Resour. Conserv. Recycl. 186, 106529 (2022).

    Article  CAS  Google Scholar 

  39. Guglielmini, L., Gontcharov, A., Aldykiewicz, A. J. & Stone, H. A. Drying of salt solutions in porous materials: intermediate-time dynamics and efflorescence. Phys. Fluids 20, 077101 (2008).

    Article  Google Scholar 

  40. Li, C. et al. Mapping techniques for the design of lithium-sulfur batteries. Small 18, 1–14 (2022).

    Google Scholar 

  41. Adhitama, E. et al. Pre‐lithiation of silicon anodes by thermal evaporation of lithium for boosting the energy density of lithium ion cells. Adv. Funct. Mater. 32, 2201455 (2022).

    Article  CAS  Google Scholar 

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The authors appreciate the support from Princeton Catalysis Initiative (PCI), and we acknowledge the use of Princeton’s Imaging and Analysis Center, which is partially supported through the Princeton Center for Complex Materials (PCCM), a National Science Foundation (NSF)-MRSEC programme (DMR-2011750). F.T.-C. and S.Z. gratefully acknowledge the Distinguished Postdoctoral Fellowships from the Andlinger Center for Energy and the Environment.

Author information

Authors and Affiliations



X.C. conceived the initial idea with the input from group members. X.C., M.Y., S.Z., Z.J.R. and L.H. contributed to the experimental design. Z.J.R. supervised the study. X.C., M.Y. and S.Z. conducted materials preparation and system operation. F.T.-C. and H.A.S. carried out model development. X.C., G.C. and N.Y. conducted material characterization. X.C., M.Y. and S.Z. contributed to experimental analysis. X.C. and Q.D. contributed to schematics design. X.C., M.Y., F.T.-C. and Z.J.R. wrote the paper, and all authors commented on the final manuscript.

Corresponding author

Correspondence to Zhiyong Jason Ren.

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Competing interests

X.C., S.Z. and Z.R. are authors on a patent application (PCT/US22/50915) for fibre evaporators. The other authors declare no competing interests.

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Peer review information

Nature Water thanks Ping He and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Notes 1–4 and Figs. 1–20, and captions for Supplementary Movies 1–3.

Supplementary Movie 1

Easy peeling of the Na-rich salt shell for Na separation, sampled after 5 days’ spatial crystallization for Li extraction from seawater.

Supplementary Movie 2

3D structure of the four-strings-twisted fibre crystallizer. Movie constructed by AVIZO software upon 3D X-ray scanning images.

Supplementary Movie 3

Time lapse video records the growth of the crystals during the operation. From left to right, the saline water contains 10, 40, 70 and 100 g l−1 NaCl, respectively. Visible salt crystalized at different heights, with the lower concentration crystalized at a higher position.

Supplementary Data 1

Data of supplementary figures.

Source data

Source Data Fig. 1

Statistical source data of Fig. 1.

Source Data Fig. 4

Statistical source data of Fig. 4.

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Chen, X., Yang, M., Zheng, S. et al. Spatially separated crystallization for selective lithium extraction from saline water. Nat Water 1, 808–817 (2023).

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