Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Sustainable lead management in halide perovskite solar cells

Abstract

Despite the rapid development of perovskite solar cells (PSCs) toward commercialization, the toxic lead (Pb) ions in PSCs pose a potential threat to the environment, health and safety. Managing Pb via recycling represents a promising approach to mitigating its toxicity. However, managing Pb from commonly used organic solvents has been challenging due to the lack of suitable Pb adsorbents. Here, we report a new adsorbent for both separation and recovery of Pb from PSC pollutants. The synthesized iron-incorporated hydroxyapatite possesses a strongly negatively charged surface that improves electrostatic interaction through surface-charge delocalization, thus leading to enhanced Pb adsorption. We demonstrate the feasibility of a complete Pb management process, including the purification of Pb-containing non-aqueous solvents below 15 parts per 109, a level compliant with the standards of the US Environmental Protection Agency, as well as recycling of 99.97% of Pb ions by forming lead iodide.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

All prices are NET prices.

Fig. 1: Synthesis of magnetic hollow HAP/Fe composite and its properties for Pb absorption.
Fig. 2: Impact of Fe incorporating on surface properties of HAP.
Fig. 3: Fe effects on HAP for Pb capturability.
Fig. 4: Illustration of the use of HAP/Fe composite for treating a Pb-containing solution pollutant and PbI2 regaining process after Pb removal/separation.

Data availability

The data that support the findings of this study are available within the Article and its Supplementary Information file and from the corresponding author upon reasonable request. Any available information on data resources used in or produced for the paper is provided.

References

  1. Jeon, N. J. et al. A fluorene-terminated hole-transporting material for highly efficient and stable perovskite solar cells. Nat. Energy 3, 682–689 (2018).

    Article  CAS  Google Scholar 

  2. Yang, W. S. et al. Iodide management in formamidinium-lead-halide-based perovskite layers for efficient solar cells. Science 356, 1376–1379 (2017).

    Article  CAS  Google Scholar 

  3. Christians, J. A. et al. Tailored interfaces of unencapsulated perovskite solar cells for >1,000 hour operational stability. Nat. Energy 3, 68–74 (2018).

    Article  CAS  Google Scholar 

  4. Deng, Y. H. et al. Surfactant-controlled ink drying enables high-speed deposition of perovskite films for efficient photovoltaic modules. Nat. Energy 3, 560–566 (2018).

    Article  CAS  Google Scholar 

  5. Yang, M. J. et al. Highly efficient perovskite solar modules by scalable fabrication and interconnection optimization. ACS Energy Lett. 3, 322–328 (2018).

    Article  CAS  Google Scholar 

  6. Kim, D. H., Whitaker, J. B., Li, Z., van Hest, M. F. A. M. & Zhu, K. Outlook and challenges of perovskite solar cells toward terawatt-scale photovoltaic module technology. Joule 2, 1437–1451 (2018).

    Article  CAS  Google Scholar 

  7. Babayigit, A., Ethirajan, A., Muller, M. & Conings, B. Toxicity of organometal halide perovskite solar cells. Nat. Mater. 15, 247–251 (2016).

    Article  CAS  Google Scholar 

  8. Kim, B. J. et al. Selective dissolution of halide perovskites as a step towards recycling solar cells. Nat. Commun. 7, 11735 (2016).

    Article  CAS  Google Scholar 

  9. Park, N.-G., Grätzel, M., Miyasaka, T., Zhu, K. & Emery, K. Towards stable and commercially available perovskite solar cells. Nat. Energy 1, 16152 (2016).

    Article  CAS  Google Scholar 

  10. Abate, A. Perovskite solar cells go lead free. Joule 1, 659–664 (2017).

    Article  CAS  Google Scholar 

  11. Lin-Fu, J. S. Vulnerability of children to lead exposure and toxicity (second of two parts). N. Engl. J. Med. 289, 1289–1293 (1973).

    Article  CAS  Google Scholar 

  12. Matlock, M. M., Howerton, B. S. & Atwood, D. A. Chemical precipitation of lead from lead battery recycling plant wastewater. Ind. Eng. Chem. Res. 41, 1579–1582 (2002).

    Article  CAS  Google Scholar 

  13. Bolisetty, S. & Mezzenga, R. Amyloid-carbon hybrid membranes for universal water purification. Nat. Nanotechnol. 11, 365–371 (2016).

    Article  CAS  Google Scholar 

  14. Dabrowski, A., Hubicki, Z., Podkościelny, P. & Robens, E. Selective removal of the heavy metal ions from waters and industrial wastewaters by ion-exchange method. Chemosphere 56, 91–106 (2004).

    Article  CAS  Google Scholar 

  15. Ali, I. & Gupta, V. K. Advances in water treatment by adsorption technology. Nat. Protoc. 1, 2661–2667 (2006).

    Article  CAS  Google Scholar 

  16. Zhao, J. et al. Facile preparation of a self-assembled Artemia cyst shell–TiO2–MoS2 porous composite structure with highly efficient catalytic reduction of nitro compounds for wastewater treatment. Nanotechnology 31, 085603 (2020).

    Article  CAS  Google Scholar 

  17. Yuan, Q. L. et al. Facet-dependent selective adsorption of Mn-doped alpha-Fe2O3 nanocrystals toward heavy-metal ions. Chem. Mater. 29, 10198–10205 (2017).

    Article  CAS  Google Scholar 

  18. Huang, X. et al. Facile preparation of hierarchical AgNP-loaded MXene/Fe3O4/polymer nanocomposites by electrospinning with enhanced catalytic performance for wastewater treatment. ACS Omega 4, 1897–1906 (2019).

    Article  CAS  Google Scholar 

  19. Wang, C. et al. Facile preparation and catalytic performance characterization of AuNPs-loaded hierarchical electrospun composite fibers by solvent vapor annealing treatment. Colloids Surf. A 61, 283–291 (2019).

    Google Scholar 

  20. Bailliez, S., Nzihou, A., Bèche, E. & Flamant, G. Removal of lead (Pb) by hydroxyapatite sorbent. Process Saf. Environ. Prot. 82, 175–180 (2004).

    Article  CAS  Google Scholar 

  21. Meski, S., Ziani, S. & Khireddine, H. Removal of lead ions by hydroxyapatite prepared from the egg shell. J. Chem. Eng. Data 55, 3923–3928 (2010).

    Article  CAS  Google Scholar 

  22. Elliott, J. C. Structure and Chemistry of the Apatites and Other Calcium Orthophosphates (Elsevier, 1994).

  23. Ignjatović, N. L. et al. Rare-earth (Gd3+,Yb3+/Tm3+, Eu3+) co-doped hydroxyapatite as magnetic, up-conversion and down-conversion materials for multimodal imaging. Sci. Rep. 9, 16305 (2019).

    Article  Google Scholar 

  24. Lai, W. et al. Hydrothermal fabrication of porous hollow hydroxyapatite microspheres for a drug delivery system. Mat. Sci. Eng. C. 62, 166–172 (2016).

    Article  CAS  Google Scholar 

  25. Wang, Y. S., Moo, Y. X., Chen, C., Gunawan, P. & Xu, R. Fast precipitation of uniform CaCO3 nanospheres and their transformation to hollow hydroxyapatite nanospheres. J. Colloid Interface Sci. 352, 393–400 (2010).

    Article  CAS  Google Scholar 

  26. Park, S. Y. et al. Osteoinductive superparamagnetic Fe nanocrystal/calcium phosphate heterostructured microspheres. Nanoscale 9, 19145–19153 (2017).

    Article  CAS  Google Scholar 

  27. Singh., N. et al. Polydopamine modified superparamagnetic iron oxide nanoparticles as multifunctional nanocarrier for targeted prostate cancer treatment. Nanomaterials 9, 138 (2019).

    Article  CAS  Google Scholar 

  28. Iannotti, V. et al. Fe-doping-induced magnetism in nano-hydroxyapatites. Inorg. Chem. 56, 4446–44583 (2017).

    Article  Google Scholar 

  29. Kawabata, S. et al. Synthesis and Characterization of Wet Chemically Derived Magnetite‐HAP Hybrid Nanoparticles (American Ceramic Society, 2010).

  30. Hailegnaw, B., Kirmayer, S., Edri, E., Hodes, G. & Cahen, D. Rain on methylammonium lead iodide based perovskites: possible environmental effects of perovskite solar cells. J. Phys. Chem. Lett. 6, 1543–1547 (2015).

    Article  CAS  Google Scholar 

  31. Lead Laws and Regulations (EPA, 2015).

  32. Babayigit, A. et al. Assessing the toxicity of Pb- and Sn-based perovskite solar cells in model organism Danio rerio. Sci. Rep. 6, 18721 (2016).

    Article  CAS  Google Scholar 

  33. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Article  CAS  Google Scholar 

  34. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

    Article  Google Scholar 

  35. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    Article  CAS  Google Scholar 

  36. Grimme, S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J. Comput. Chem. 27, 1787–1799 (2006).

    Article  CAS  Google Scholar 

  37. Markovic, M., Flowler, B. O. & Tung, M. S. Preparation and comprehensive characterization of a calcium hydroxyapatite reference material. J. Res. Natl Inst. Stand. Technol. 109, 553–568 (2004).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Global Frontier R&D Program on Center for Multiscale Energy System funded by the National Research Foundation (under contract no. 2012M3A6A7054855), the Alchemist project of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) granted financial resource from the Ministry of Trade, Industry & Energy (20193091010310), and the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIP) (NRF-2018M3C1B7021994 and 2019R1F1A1064095). This research was partially supported by the Ministry of Science, ICT and the Future Planning as Global Frontier Project (CAMM-2019M3A6B3030638). This research was also supported by the Defense Challengeable Future Technology Program of the Agency for Defense Development, Republic of Korea. The work at the National Renewable Energy Laboratory (NREL) was supported by the De-Risking Halide Perovskite Solar Cells programme of the National Center for Photovoltaics, funded by the Office of Energy Efficiency and Renewable Energy, Solar Energy Technologies Office, US Department of Energy (DOE) under contract no. DE-AC36-08GO28308 with the Alliance for Sustainable Energy, a Limited Liability Company (LLC), and the Manager and Operator of NREL. The views expressed in the article do not necessarily represent the views of the DOE or the US Government. Via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), this work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk).

Author information

Authors and Affiliations

Authors

Contributions

H.S.J. and D.H.K. supervised this work. S.Y.P. and D.H.K. conceived the idea and designed the experiments. S.Y.P., D.H.K. and J.-S.P. discussed the mechanism and designed the experiment and theoretical calculations. S.Y.P. carried out the synthesis and characterization of materials and the Pb-management test. S.Y.P. and H.L. conducted the magnetic analysis of materials. J.-S.P. and A.W. designed and performed the theoretical calculations. B.J.K., D.H.K. and K.Z. performed the device fabrication and analysis. S.Y.P., J.-S.P., K.Z., D.H.K. and H.S.J. wrote the first draft of the manuscript, and all authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Dong Hoe Kim or Hyun Suk Jung.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–15, Tables 1–3 and refs. 1–10.

Reporting Summary

Supplementary Video 1

Protocol of Pb-purification in non-aqueous solvent using HAP/Fe composites.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Park, S.Y., Park, JS., Kim, B.J. et al. Sustainable lead management in halide perovskite solar cells. Nat Sustain 3, 1044–1051 (2020). https://doi.org/10.1038/s41893-020-0586-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41893-020-0586-6

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing