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LiMnO2 cathode stabilized by interfacial orbital ordering for sustainable lithium-ion batteries

Nature Sustainability volume 4, pages 392–401 (2021)Cite this article

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Abstract

Global lithium-ion battery deployments stand poised to grow substantially in the coming years, but it will be necessary to include sustainability considerations in the design of electrode materials. The current cathode chemistry relies heavily on cobalt, which, due to its scarcity and the environmental abuse and violation of human rights during its mining, must be replaced by abundant and environmentally friendly elements such as redox-active manganese. LiMnO2 is a strong contender for sustainable cathodes but cycles poorly because the Jahn–Teller distorted Mn3+ ions destabilize the lattice framework. Here, we report a LiMnO2 cathode design with interwoven spinel and layered domains. At the interface between these two domains, the Mn dz2 orbitals are oriented perpendicular to each other, giving rise to interfacial orbital ordering, which suppresses the otherwise cooperative Jahn–Teller distortion and Mn dissolution. As a result, the heterostructured cathode delivers enhanced structural and electrochemical cycling stability. This work provides a new strategy for interface engineering, possibly stimulating more research on Mn-rich cathode materials for sustainable lithium-ion batteries.

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Fig. 1: Jahn–Teller distortion correlated with orbital ordering in LiMnO2.
Fig. 2: Phases and atomic structure of SPL–LMO.
Fig. 3: Formation of the spinel–layered heterostructure.
Fig. 4: Li storage behaviour and rate and cycle performance.
Fig. 5: Structure evolution on Li intercalation/deintercalation.

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Data availability

The data that support the findings detailed in this study are available in the Article and its Supplementary Information or from the corresponding authors upon reasonable request.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant nos 51972174, 51772154, 51672307, 51421002, 51672307, 51991344 and 11704019), the Natural Science Foundation of Jiangsu Province (grant no. BK20170036), the National Key R&D Program of China (2020YFB2007400), the Fundamental Research Funds for the Central Universities (no. 30920041118), Beijing Natural Science Foundation (grant no. Z190010) and Frontier Key Research Projects of the Chinese Academy of Science (grant no. QYZDB-SSW-JSC035). Q.L. acknowledges support from the Shenzhen Science and Technology Innovation Commission under the grant Shenzhen-Hong Kong Innovation Circle Category D Project: SGDX 2019081623240948. H.X. thanks the following synchrotron light source for the XRD characterization: Beamline BL14B1 of the Shanghai Synchrotron Radiation Facility.

Author information

Author notes

  1. These authors contributed equally: Xiaohui Zhu, Fanqi Meng, Qinghua Zhang.

Authors and Affiliations

  1. School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing, China

    Xiaohui Zhu, Liang Xue, Si Lan, Jing Zhao, Yuhang Zhuang, Qiubo Guo, Bo Liu & Hui Xia

  2. Herbert Gleiter Institute of Nanoscience, Nanjing University of Science and Technology, Nanjing, China

    Xiaohui Zhu, Liang Xue, Si Lan, Jing Zhao, Yuhang Zhuang, Qiubo Guo, Bo Liu & Hui Xia

  3. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Fanqi Meng, Qinghua Zhang & Lin Gu

  4. Songshan Lake Materials Laboratory, Dongguan, China

    Fanqi Meng, Qinghua Zhang & Lin Gu

  5. School of Physical Sciences, University of Chinese Academy of Sciences, Beijing, China

    Fanqi Meng, Qinghua Zhang & Lin Gu

  6. Department of Physics, City University of Hong Kong, Hong Kong, China

    He Zhu & Qi Liu

  7. School of Materials, Sun Yat-Sen University, Guangzhou, China

    Xia Lu

  8. X-Ray Science Division, Argonne National Laboratory, Argonne, IL, USA

    Yang Ren

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Contributions

H.X. conceived the project. X.Z. synthesized the samples and performed the structural characterizations and electrochemical measurements. L.G., F.M., Q.Z. and X.L. performed the STEM measurements and structural analysis. Q.L., H.Z., Y.R. and S.L. performed the in situ synchrotron XRD and PDF data analysis. X.Z., L.X., J.Z., Y.Z., Q.G. and B.L. performed the ex situ synchrotron XRD, XPS and Raman measurements. H.X., X.Z. and Q.Z. wrote the manuscript. All authors analysed the results and commented on the manuscript.

Corresponding authors

Correspondence to Qi Liu, Lin Gu or Hui Xia.

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Peer review information Nature Sustainability thanks the anonymous reviewers for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Synthesis of SPL-LMO and SPL-LMO/Mn3O4.

a, Electrochemical conversion of Mn3O4 nanowall arrays to SPL-LMO nanowall arrays (CE, counter electrode; RE, reference electrode; WE, working electrode). b, Conversion of a powdery Mn3O4 electrode into a SPL-LMO/Mn3O4 powdery electrode.

Extended Data Fig. 2 FESEM images.

a,c, FESEM images of a sample of the Mn3O4 nanowall arrays. b,d, FESEM images of a sample of the obtained SPL-LMO nanowall arrays. Scale bars, 10 μm in a and b; 2 μm in c and d.

Extended Data Fig. 3 STEM image and EELS spectra.

a, ABF-STEM image for the SPL-LMO sample at low magnification; Scale bar, 200 nm. b, The particle size distribution histogram of the SPL-LMO sample in a. c, HAADF-STEM image for the SPL-LMO nanoparticle; Scale bar, 5 nm. d, Mn L-edge EELS spectra of the SPL-LMO sample taken from three different regions of A, B, and C in c. The Mn L-edge spectra obtained from different domains (A, B, and C) show the same L3/L2 ratio, indicating a uniform LiMnO2 composition in the two phases.

Extended Data Fig. 4 XPS and Raman spectra.

a, Ex situ core-level Mn 2p XPS spectra of the Mn3O4 nanoarray cathode at different potentials labeled as I to VI in Fig. 3a. b, Ex situ core-level O 2p XPS spectra of the Mn3O4 nanoarray cathode at different potentials labeled I to VI in Fig. 3a. c, Ex situ Raman spectra of the Mn3O4 nanoarray cathode at different potentials labeled I to VI in Fig. 3a.

Extended Data Fig. 5 NMR spectra.

a, The first charge–discharge curve of the Mn3O4 nanoarray electrode at a current density of 0.05 A g−1 in the voltage range between 2.0 and 4.5 V (vs. Li/Li+). b, Ex situ 31P NMR spectra for electrolyte solutions of Mn3O4//Li cells collected at different states. A single resonance at δ –13 (corresponding to Mn2+) can be observed in the 31P NMR spectra for the electrolytes of the Mn3O4//Li cells at different charge states except for the starting point, indicating the existence of Mn2+ in the electrolyte and Mn2+ deintercalation from the Mn3O4 electrode during the charge process.

Extended Data Fig. 6 FTIR spectra.

a, The first charge–discharge curve of the Mn3O4 nanoarray electrode at a current density of 0.05 A g−1 in the voltage range between 2.0 and 4.5 V (vs. Li/Li+). b, Ex situ FTIR spectra of the Mn3O4 nanoarray electrodes at different charge states. The peaks for the –OH group of HxMn1-x(Mn2)O4 (protonated Mn3O4) in the as-prepared Mn3O4 sample was not observed because of the final 300 °C annealing for the synthesis (Methods). Interestingly, when charged to potential I–2, three weak peaks located at 1088, 1110, and 1145 cm–1, corresponding to –OH group, were detected, indicating the Mn2+ extraction, H+ insertion, and subsequently the formation of protonated HxMn1-x(Mn2)O4.

Extended Data Fig. 7 NMR spectra after testing.

a, Cycle performances of the SPL-LMO and LiMn2O4 nanowall arrays cathodes at 55 °C between 2.0 and 4.5 V. b, 31P NMR spectrum for the electrolyte solution of the LiMn2O4//Li cell collected after 100 cycles at 55 °C in comparison with the 31P NMR spectra for the electrolyte solutions of the SPL-LMO//Li cells after 600 cycles at 55 °C and after 2000 cycles at 25 °C, respectively. It is noted that a much stronger resonance in the NMR at δ –10 (corresponding to Mn3+) is observed for the electrolyte after 600 cycles at 55 °C as compared to that for the electrolyte after 2000 cycles at 25 °C, indicating Mn dissolution is highly dependent on the testing temperature.

Extended Data Fig. 8 Heterostructured LixMnO2.

a, XRD pattern and b, cycle performance of the layered + spinel heterostructured LixMnO2 nanoarray with collinear orbital ordering. c,d, HAADF- and ABF-STEM images of the layered/spinel interface along [010] direction, showing collinear orbital ordering. Scale bars, 1 nm.

Extended Data Fig. 9 PDF analysis.

PDFs for the collinear spinel/layered LixMnO2 (Extended Data Fig. 8) and non-collinear SPL-LMO samples.

Extended Data Fig. 10 STEM image and Mn–O bonds.

a, ABF-STEM image for the SPL-LMO sample along the [010] zone axis; scale bar, 1 nm. b,d, Enlarged ABF-STEM images for spinel and layered LiMnO2 from zone A and B in a, respectively. c,e, Linear intensity profiles scanning across two elongated Mn–O bonds in b and d, respectively.

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Zhu, X., Meng, F., Zhang, Q. et al. LiMnO2 cathode stabilized by interfacial orbital ordering for sustainable lithium-ion batteries. Nat Sustain 4, 392–401 (2021). https://doi.org/10.1038/s41893-020-00660-9

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