Abstract
As the most abundant and renewable biopolymer, cellulose has found applications in a range of fields such as healthcare, packaging, electronics and environmental remediation, contributing to the transition towards sustainability. Here we apply a green and scalable process transforming cellulose to a robust electrolyte exhibiting lithium (Li) ion conductivity of 1.09 × 10−3 S cm−1 with a transference number of 0.81 and mechanical strength of 12 MPa. Our process takes advantage of the rich hydroxyl groups in the cellulose which are replaced by phthalic anhydride through an esterification reaction to form cellulose phthalate (CP). Combined experimental and theoretical analyses reveal that the introduction of phthalate groups is essential to not only ensure effective multi-oxygen interaction with Li ions to create fast ion transportation channels, but also facilitates the intermolecular hydrogen bond responsible for the impressive mechanical properties. The CP biopolymer film is even compatible with most commercial cathode materials, and our solid-state Li/CP/LiFePO4 cells show better performance and notably good stability over 1,000 cycles than that of a baseline Li-ion cell with a flammable organic liquid electrolyte. Our study unlocks the enormous potential of cellulose utilization in batteries and opens an avenue for the development of abundant and sustainable solid-state electrolytes.
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Data availability
The authors declare that the data supporting the findings of this study are available within the Article and its Supplementary Information file. Should any raw data files be needed in another format, they are available from the corresponding authors upon reasonable request.
Code availability
The input files for ORCA, VASP, Chargemol, LAMMPS, CHGNet and ASE used in this study are available from the corresponding authors by request. All the codes used are either commercial or open source and can be accessed through their homepages.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (grant nos 22025507 and 21931012), the Key Research Program of Frontier Sciences, CAS (ZDBS-LYSLH020), the Beijing National Laboratory for Molecular Sciences (BNLMS-CXXM-202010), the RGC General Research Fund (grant no. 17309620), Seed Fund of the University of Hong Kong (project code: 2201101550) and Hong Kong Quantum AI Lab Limited, Air @ InnoHK of Hong Kong Government. We thank Q. Li, A. Guan, N. Wu and J. Xiang from the Center for Physiochemical Analysis and Measurement in the Institute of Chemistry (CAS) for the NMR test. The authors also thank N. Grundish for polishing the manuscript to improve its readability.
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J.L. synthesized and characterized the cellulose-based electrolytes; Z.H., S.C. and G.H.C. carried out the theoretical analysis and the related discussions; S.Z., H.Z. and S.G. participated in the test and discussion of the electrochemical characterizations; G.Z and Z.P. performed the NMR characterization; Y.Q. and Y.L. contributed to the design of cellulose-based electrolytes; A.-M.C. supervised the project; and Y.L., Y.Q., J.L. and A.-M.C. wrote the manuscript. All authors commented on the manuscript.
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Li, J., Hu, Z., Zhang, S. et al. Molecular engineering of renewable cellulose biopolymers for solid-state battery electrolytes. Nat Sustain 7, 1481–1491 (2024). https://doi.org/10.1038/s41893-024-01414-7
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DOI: https://doi.org/10.1038/s41893-024-01414-7
