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Lithium-free transition metal monoxides for positive electrodes in lithium-ion batteries


Lithium-ion batteries based on intercalation compounds have dominated the advanced portable energy storage market. The positive electrode materials in these batteries belong to a material group of lithium-conducting crystals that contain redox-active transition metal and lithium. Materials without lithium-conducting paths or lithium-free compounds could be rarely used as positive electrodes due to the incapability of reversible lithium intercalation or the necessity of using metallic lithium as negative electrodes. These constraints have significantly limited the choice of materials and retarded the development of new positive electrodes in lithium-ion batteries. Here, we demonstrate that lithium-free transition metal monoxides that do not contain lithium-conducting paths in their crystal structure can be converted into high-capacity positive electrodes in the electrochemical cell by initially decorating the monoxide surface with nanosized lithium fluoride. This unusual electrochemical behaviour is attributed to a surface conversion reaction mechanism in contrast with the classic lithium intercalation reaction. Our findings will offer a potential new path in the design of positive electrode materials in lithium-ion batteries.

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Figure 1: Transition of metal monoxide from negative electrode to positive electrode material.
Figure 2: Electrochemical profiles of LiF–MO nanocomposites as a positive electrode.
Figure 3: Electrochemical response of the LiF–MnO nanocomposite.
Figure 4: Mn redox reaction and fluorine ion contribution.
Figure 5: Surface-concentrated F ion interaction including structural evolution.
Figure 6: Capacity-tunable LiF–C/Mn3O4 nanocomposite cathode materials.


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This work was supported by Samsung Research Funding Centre of Samsung Electronics under Project Number SRFC-TA1403-03. Also, this work was supported by Project Code (IBS-R006-G1). S.-K.J., H.K., K.-Y.P. and K.K. are grateful for the financial support from IBS.

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Authors and Affiliations



S.-K.J. conceived the research and carried out the synthesis, electrochemical test, and characterization. H.K. performed the overall X-ray absorption spectroscopy experiment and analyses. M.G.C. synthesized the Mn3O4 nanoparticle and performed TEM work for the LiF–C/Mn3O4 system. S.-P.C. conducted TEM and STEM–EELS measurements for the LiF–MnO nanocomposite. B.L. and G.Y. conducted the DFT calculations and developed the theoretical model. W.-S.Y. and K.K. supervised the overall research. All authors discussed the experiments and final manuscript.

Corresponding authors

Correspondence to Won-Sub Yoon or Kisuk Kang.

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The authors declare no competing financial interests.

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Supplementary Figures 1–35, Supplementary Tables 1–3, Supplementary Discussion, Supplementary Methods, Supplementary References (PDF 3825 kb)

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Jung, SK., Kim, H., Cho, M. et al. Lithium-free transition metal monoxides for positive electrodes in lithium-ion batteries. Nat Energy 2, 16208 (2017).

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