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Synthesis of [100]-only LiFePO4 nanosheets for efficient electrochemical lithium extraction from low-grade brines

Nature Water volume 3, pages 1449–1458 (2025) Cite this article

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Abstract

Efficient lithium extraction is crucial for advancing the global energy transition, yet selective extraction from unconventional resources with high Mg/Li and Na/Li molar ratios remains challenging. Here we report the synthesis of highly oriented [100]-only LiFePO4 (LFP) nanosheets through an orbital-shielding strategy. This approach employs crown ether molecules to selectively shield specific d orbitals of the central Fe atoms, generating precisely oriented nanosheets with nearly (100) lattice planes. Lithium extraction performance was thoroughly investigated using the representative brines with varying lithium concentrations and interference ion levels from diverse water sources. The Li/Mg and Li/Na selectivity values reach as high as 1,866 and 42,162, with lithium-extraction rates ranging from 1.29 to 7.45 µmol cm−2 h−1. To explore the industrial potential and scalability of the [100]-only LFP nanosheets, an in situ Fe-induced conversion reaction was introduced to replace expensive crown ethers with cost-effective diethylene glycol, enabling kilogram-scale production. A pilot-scale test was conducted using Dead Sea Water brine. The molar Mg/Li and Na/Li were reduced from 800 and 18 to 2.44 × 10−2 and 3.38 × 10−2, respectively, and 44.4 g of battery-grade Li2CO3 was produced during the test. Our orbital-shielding strategy, validated here with LFP, not only provides a potential method for precisely engineering crystal growth such as metal–organic frameworks and Prussian blue analogues but also makes a significantly advanced selective lithium-extraction industry.

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Fig. 1: Anisotropic ion diffusion for LFP.
The alternative text for this image may have been generated using AI.
Fig. 2: Oriented growth of [100]-only LFP.
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Fig. 3: Lithium-extraction performance.
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Fig. 4: Lithium extraction on a pilot scale.
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Data availability

The data supporting the findings of this study are available in the paper and its Supplementary Information. All data are available in the Dryad data repository40.

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Acknowledgements

We gratefully acknowledge support from the KAUST Competitive Grant URF/1/4713-01-01 (to Z. Lai) and the Center of Excellence Grant FCC/1/5937-04-01 (to Z. Lai). We also thank the Core Laboratories at KAUST for their valuable assistance with material characterizations.

Author information

Author notes

  1. These authors contributed equally: Shuhao An, Zhen Li.

Authors and Affiliations

  1. Center of Excellence for Renewable Energy and Storage Technologies (CREST), Division of Physical Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal, Kingdom of Saudi Arabia

    Shuhao An, Zhen Li, Xin Wang, Ting Xu, Liang Feng & Zhiping Lai

Authors
  1. Shuhao An
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  2. Zhen Li
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  3. Xin Wang
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Contributions

Z. Lai and Z. Li conceived of the concept. S.A. and Z. Li jointly devised and conducted the experimental programme. X.W. contributed to the discussion regarding the crystal growth section. T.X. performed the NMR and mass spectrum analysis experiments. L.F. performed experiments with characterizations. S.A., Z. Li and Z. Lai analysed all the results and co-wrote the paper with contributions and input from all co-authors.

Corresponding authors

Correspondence to Zhen Li or Zhiping Lai.

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The authors declare no competing interests.

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Peer review information

Nature Water thanks Xiwang Zhang, Haoshen Zhou and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information (download PDF )

Supplementary Figs. 1–22, Tables 1–6, Methods and References.

Reporting Summary (download PDF )

Supplementary Data (download ZIP )

Source data for Supplementary Figs. 1–11, 13–15, 17 and 20–22.

Source data

Source Data Fig. 1 (download XLSX )

Raw data for ion migration energy barriers.

Source Data Fig. 2 (download XLSX )

Raw data for electron occupancy probabilities for d orbitals of Fe atoms. Original XRD diffraction profiles and pole figure XRD diffraction profiles.

Source Data Fig. 3 (download XLSX )

Raw data for the ion concentrations, lithium extraction rates and ion-extraction selectivities.

Source Data Fig. 4 (download XLSX )

Raw data for 1H NMR spectra and XRD diffraction profiles. Raw data for the polarization curves and the corresponding ion concentrations in the extraction solution, the lithium concentration in the remaining feed solution and ion-extraction selectivities at different cycles.

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An, S., Li, Z., Wang, X. et al. Synthesis of [100]-only LiFePO4 nanosheets for efficient electrochemical lithium extraction from low-grade brines. Nat Water 3, 1449–1458 (2025). https://doi.org/10.1038/s44221-025-00533-5

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