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.
Subscribe to Journal
Get full journal access for 1 year
only $8.25 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
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.
Goodenough, B. & Park, K. S. The Li-ion rechargeable battery: a perspective. J. Am. Chem. Soc. 135, 1167–1176 (2013).
Tarascon, J. M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).
Abakumov, A. M., Fedotov, S. S., Antipov, E. V. & Tarascon, J. M. Solid state chemistry for developing better metal-ion batteries. Nat. Commun. 11, 4976 (2020).
Armstrong, A. R. & Bruce, P. G. Synthesis of layered LiMnO2 as an electrode for rechargeable lithium batteries. Nature 381, 499–500 (1996).
Gummow, R. J. & Thackeray, M. M. An investigation of spinel-related and orthorhombic LiMnO2 cathodes for rechargeable lithium batteries. J. Electrochem. Soc. 141, 1178–1182 (1994).
Koetschau, I., Richard, M. N., Dahn, J. R., Soupart, J. B. & Rousche, J. C. Orthorhombic LiMnO2 as a high capacity cathode for Li-ion cells. J. Electrochem. Soc. 142, 2906–2910 (1995).
Manthiram, A. A reflection on lithium-ion battery cathode chemistry. Nat. Commun. 11, 1550 (2020).
Okubo, M. et al. Fast Li-ion insertion into nanosized LiMn2O4 without domain boundaries. ACS Nano 4, 741–752 (2010).
Thackeray, M. M., Johnson, P. J., De Picciotto, L. A., Bruce, P. G. & Goodenough, J. B. Electrochemical extraction of lithium from LiMn2O4. Mater. Res. Bull. 19, 179–187 (1984).
Armstrong, A. R. et al. Combined neutron diffraction, NMR, and electrochemical investigation of the layered-to-spinel transformation in LiMnO2. Chem. Mater. 16, 3106–3118 (2004).
Huang, Y. et al. Lithium manganese spinel cathodes for lithium-ion batteries. Adv. Energy Mater. https://doi.org/10.1002/aenm.202000997 (2020).
Asl, H. Y. & Manthiram, A. Reining in dissolved transition-metal ions. Science 369, 140–141 (2020).
Ji, H. et al. Ultrahigh power and energy density in partially ordered lithium-ion cathode materials. Nat. Energy 5, 213–221 (2020).
Zuo, C. et al. Double the capacity of manganese spinel for lithium-ion storage by suppression of cooperative Jahn–Teller distortion. Adv. Energy Mater. 10, 2000363 (2020).
Kang, K., Meng, Y. S., Breger, J., Grey, C. P. & Ceder, G. Electrodes with high power and high capacity for rechargeable lithium batteries. Science 311, 977–980 (2006).
Choi, J. & Manthiram, A. Role of chemical and structural stabilities on the electrochemical properties of layered LiNi1/3Mn1/3Co1/3O2 cathodes. J. Electrochem. Soc. 152, A1714–A1718 (2005).
Deng, Y. P. et al. Layer-based heterostructured cathodes for lithium-ion and sodium-ion batteries. Adv. Funct. Mater. 29, 1808522 (2019).
Ma, C. et al. Exploring oxygen activity in the high energy P2-type Na0.78Ni0.23Mn0.69O2 cathode material for Na-ion batteries. J. Am. Chem. Soc. 139, 4835–4845 (2017).
Kim, S. et al. Direct observation of an anomalous spinel-to-layered phase transition mediated by crystal water intercalation. Angew. Chem. Int. Ed. 54, 15094–15099 (2015).
Lyon, D. K. et al. Highly oxidation resistant inorganic-porphyrin analogue polyoxometalate oxidation catalysts. 1. The synthesis and characterization of aqueous-soluble potassium salts of α2-P2W17O61 (Mn+∙OH2)(n−10) and organic solvent soluble tetra-n-butylammonium salts of α2-P2W17O61 (Mn+∙Br)(n−11) (M = Mn3+, Fe3+, Co2+, Ni2+, Cu2+). J. Am. Chem. Soc. 113, 7209–7221 (1991).
Li, Q. et al. Both cationic and anionic co-(de) intercalation into a metal-oxide material. Joule 2, 1134–1145 (2018).
Assat, G. & Tarascon, J. M. Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries. Nat. Energy 3, 372–386 (2018).
Yang, W. & Devereaux, T. P. Anionic and cationic redox and interfaces in batteries: advances from soft X-ray absorption spectroscopy to resonant inelastic scattering. J. Power Sources 389, 188–197 (2018).
Li, N. et al. Unraveling the cationic and anionic redox reactions in a conventional layered oxide cathode. ACS Energy Lett. 4, 2836–2842 (2019).
Wu, J. et al. Fingerprint oxygen redox reactions in batteries through high-efficiency mapping of resonant inelastic X-ray scattering. Condens. Matter 4, 5 (2019).
Kirillov, S. A. et al. Oxidation of synthetic hausmannite (Mn3O4) to manganite (MnOOH). J. Mol. Struct. 928, 89–94 (2009).
Yang, E. et al. Origin of unusual spinel-to-layered phase transformation by crystal water. Chem. Sci. 9, 433–438 (2018).
Li, Y. F. & Liu, Z. P. Active site revealed for water oxidation on electrochemically induced δ-MnO2: role of spinel-to-layer phase transition. J. Am. Chem. Soc. 140, 1783–1792 (2018).
Robertson, A. D. et al. Layered LixMn1−yCoyO2 intercalation electrodes—influence of ion exchange on capacity and structure upon cycling. Chem. Mater. 13, 2380–2386 (2001).
Robertson, A. D. et al. The layered intercalation compounds Li(Mn1−yCoy)O2: positive electrode materials for lithium-ion batteries. J. Solid State Chem. 145, 549–556 (1999).
Bianchini, M. et al. Spinel materials for Li-ion batteries: new insights obtained by operando neutron and synchrotron X-ray diffraction. Acta Crystallogr. B 71, 688–701 (2015).
Mobah, A., Verbaere, A. & Tournoux, M. LixMnO2–lambda phases related to the spinel type. Mater. Res. Bull. 18, 1375–1381 (1983).
Van der Ven, A., Marianetti, C., Morgan, D. & Ceder, G. Phase transformations and volume changes in spinel LixMn2O4. Solid State Ion. 135, 21–32 (2000).
Seymour, I. D. et al. Preventing structural rearrangements on battery cycling: a first principles investigation of the effect of dopants on the migration barriers in layered Li0.5MnO2. J. Phys. Chem. C 120, 19521–19530 (2016).
Xia, H. et al. A monoclinic polymorph of sodium birnessite for ultrafast and ultrastable sodium ion storage. Nat. Commun. 9, 5100 (2018).
Seo, W. S. et al. Size-dependent magnetic properties of colloidal Mn3O4 and MnO nanoparticles. Angew. Chem. Int. Ed. 43, 1115–1117 (2004).
Xu, J. et al. Elucidating anionic oxygen activity in lithium-rich layered oxides. Nat. Commun. 9, 947 (2018).
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.
The authors declare no competing interests.
Peer review information Nature Sustainability thanks the anonymous reviewers for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
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.
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.
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.
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.
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.
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.
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.
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  direction, showing collinear orbital ordering. Scale bars, 1 nm.
PDFs for the collinear spinel/layered LixMnO2 (Extended Data Fig. 8) and non-collinear SPL-LMO samples.
a, ABF-STEM image for the SPL-LMO sample along the  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.
About this article
Cite this article
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
Nature Sustainability (2021)
Carbon Nanotube Supported Li-Excess Cation-Disordered Li1.24Fe0.38Ti0.38O2 Cathode with Enhanced Lithium-Ion Storage Performance
Journal of Electronic Materials (2021)