Abstract
In conventional intercalation cathodes, alkali metal ions can move in and out of a layered material with the charge being compensated for by reversible reduction and oxidation of the transition metal ions. If the cathode material used in a lithium-ion or sodium-ion battery is alkali-rich, this can increase the battery’s energy density by storing charge on the oxide and the transition metal ions, rather than on the transition metal alone1,2,3,4,5,6,7,8,9,10. There is a high voltage associated with oxidation of O2− during the first charge, but this is not recovered on discharge, resulting in reduced energy density11. Displacement of transition metal ions into the alkali metal layers has been proposed to explain the first-cycle voltage loss (hysteresis)9,12,13,14,15,16. By comparing two closely related intercalation cathodes, Na0.75[Li0.25Mn0.75]O2 and Na0.6[Li0.2Mn0.8]O2, here we show that the first-cycle voltage hysteresis is determined by the superstructure in the cathode, specifically the local ordering of lithium and transition metal ions in the transition metal layers. The honeycomb superstructure of Na0.75[Li0.25Mn0.75]O2, present in almost all oxygen-redox compounds, is lost on charging, driven in part by formation of molecular O2 inside the solid. The O2 molecules are cleaved on discharge, reforming O2−, but the manganese ions have migrated within the plane, changing the coordination around O2− and lowering the voltage on discharge. The ribbon superstructure in Na0.6[Li0.2Mn0.8]O2 inhibits manganese disorder and hence O2 formation, suppressing hysteresis and promoting stable electron holes on O2− that are revealed by X-ray absorption spectroscopy. The results show that voltage hysteresis can be avoided in oxygen-redox cathodes by forming materials with a ribbon superstructure in the transition metal layers that suppresses migration of the transition metal.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Rent or buy this article
Prices vary by article type
from$1.95
to$39.95
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
Supporting research data have been deposited in the Oxford Research Archive and will be available at https://ora.ox.ac.uk/objects/uuid:646b18a1-88b0-4575-8282-2bcdcbe20a7d.
References
Lu, Z., Beaulieu, L. Y., Donaberger, R. A., Thomas, C. L. & Dahn, J. R. Synthesis, structure, and electrochemical behavior of Li[NixLi1/3−2x/3Mn2/3−x/3]O2. J. Electrochem. Soc. 149, A778–A791 (2002).
Johnson, C. S. et al. The significance of the Li2MnO3 component in ‘composite’ xLi2MnO3·(1 − x)LiMn0.5Ni0.5O2 electrodes. Electrochem. Commun. 6, 1085–1091 (2004).
Koga, H. et al. Reversible oxygen participation to the redox processes revealed for Li1.20Mn0.54Co0.13Ni0.13O2. J. Electrochem. Soc. 160, A786–A792 (2013).
Luo, K. et al. Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen. Nat. Chem. 8, 684–691 (2016).
Seo, D.-H. et al. The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials. Nat. Chem. 8, 692–697 (2016).
Saubanère, M., McCalla, E., Tarascon, J.-M. & Doublet, M.-L. The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries. Energy Environ. Sci. 9, 984–991 (2016).
Oishi, M. et al. Direct observation of reversible oxygen anion redox reaction in Li-rich manganese oxide, Li2MnO3, studied by soft X-ray absorption spectroscopy. J. Mater. Chem. A 4, 9293–9302 (2016).
Sathiya, M. et al. Reversible anionic redox chemistry in high-capacity layered-oxide electrodes. Nat. Mater. 12, 827–835 (2013).
Hong, J. et al. Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides. Nat. Mater. 18, 256–265 (2019).
Mortemard de Boisse, B. et al. Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode. Nat. Commun. 7, 11397 (2016).
Lu, Z. & Dahn, J. R. Understanding the anomalous capacity of Li/Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 cells using in situ X-ray diffraction and electrochemical studies. J. Electrochem. Soc. 149, A815 (2002).
Gent, W. E. et al. Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides. Nat. Commun. 8, 2091 (2017).
Croy, J. R. et al. First-charge instabilities of layered-layered lithium-ion-battery materials. Phys. Chem. Chem. Phys. 17, 24382–24391 (2015).
Du, K. et al. Exploring reversible oxidation of oxygen in a manganese oxide. Energy Environ. Sci. 6, 3–5 (2016).
Rong, X. et al. Structure-induced reversible anionic redox activity in Na layered oxide cathode. Joule 2, 125–140 (2018).
Pearce, P. E. et al. Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li2IrO3. Nat. Mater. 16, 580–586 (2017).
House, R. A. et al. What triggers oxygen loss in oxygen redox cathode materials? Chem. Mater. 31, 3293–3300 (2019).
Yabuuchi, N. et al. A new electrode material for rechargeable sodium batteries: P2-type Na2/3[Mg0.28Mn0.72]O2 with anomalously high reversible capacity. J. Mater. Chem. A 2, 16851–16855 (2014).
Maitra, U. et al. Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2. Nat. Chem. 10, 288–295 (2018).
Tournadre, F. et al. On the mechanism of the P2–Na0.70CoO2→O2–LiCoO2 exchange reaction—Part I: proposition of a model to describe the P2–O2 transition. J. Solid State Chem. 177, 2790–2802 (2004).
Lu, Z. & Dahn, J. R. In situ X-ray diffraction study of P2 Na2/3[Ni1/3Mn2/3]O2. J. Electrochem. Soc. 148, A1225 (2001).
Tournadre, F., Croguennec, L., Willmann, P. & Delmas, C. On the mechanism of the P2–Na0.70CoO2→O2–LiCoO2 exchange reaction—Part II: an in situ X-ray diffraction study. J. Solid State Chem. 177, 2803–2809 (2004).
Clément, R. J. et al. Direct evidence for high Na+ mobility and high voltage structural processes in P2-Nax[LiyNizMn1−y−z]O2 (x, y, z ≤ 1) cathodes from solid-state NMR and DFT calculations. J. Mater. Chem. A 5, 4129–4143 (2017).
House, R. A. et al. Lithium manganese oxyfluoride as a new cathode material exhibiting oxygen redox. Energy Environ. Sci. 11, 926–932 (2018).
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).
Xu, J. et al. Elucidating anionic oxygen activity in lithium-rich layered oxides. Nat. Commun. 9, 947 (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).
Arhammar, C. et al. Unveiling the complex electronic structure of amorphous metal oxides. Proc. Natl Acad. Sci. USA 108, 6355–6360 (2011).
McCalla, E. et al. Visualization of O–O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries. Science 350, 1516–1521 (2015).
Xie, Y., Saubanère, M. & Doublet, M.-L. Requirements for reversible extra-capacity in Li-rich layered oxides for Li-ion batteries. Energy Environ. Sci. 10, 266–274 (2017).
Wandt, J., Freiberg, A. T. S., Ogrodnik, A. & Gasteiger, H. A. Singlet oxygen evolution from layered transition metal oxide cathode materials and its implications for lithium-ion batteries. Mater. Today 21, 825–833 (2018).
Freiberg, A. T. S., Roos, M. K., Wandt, J., de Vivie-Riedle, R. & Gasteiger, H. A. Singlet oxygen reactivity with carbonate solvents used for Li-ion battery electrolytes. J. Phys. Chem. A 122, 8828–8839 (2018).
Ben Yahia, M., Vergnet, J., Saubanère, M. & Doublet, M.-L. Unified picture of anionic redox in Li/Na-ion batteries. Nat. Mater. 18, 496–502 (2019).
Mortemard de Boisse, B. et al. Highly reversible oxygen-redox chemistry at 4.1 V in Na4/7−x[□1/7Mn6/7]O2 (□: Mn vacancy). Adv. Energy Mater. 8, 1800409 (2018).
Radjenovic, P. M. & Hardwick, L. J. Evaluating chemical bonding in dioxides for the development of metal–oxygen batteries: vibrational spectroscopic trends of dioxygenyls, dioxygen, superoxides and peroxides. Phys. Chem. Chem. Phys. 21, 1552–1563 (2019).
Massiot, D. et al. Modelling one- and two-dimensional solid-state NMR spectra. Magn. Reson. Chem. 40, 70–76 (2002).
Jones, L. et al. Smart Align—a new tool for robust non-rigid registration of scanning microscope data. Adv. Struct. Chem. Imaging 1, 8 (2015).
Cococcioni, M. & de Gironcoli, S. Linear response approach to the calculation of the effective interaction parameters in the LDA + U method. Phys. Rev. B 71, 035105 (2005).
Giannozzi, P. et al. QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Matter 21, 395502 (2009).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Lee, D. H., Xu, J. & Meng, Y. S. An advanced cathode for Na-ion batteries with high rate and excellent structural stability. Phys. Chem. Chem. Phys. 15, 3304 (2013).
Schlipf, M. & Gygi, F. Optimization algorithm for the generation of ONCV pseudopotentials. Comput. Phys. Commun. 196, 36–44 (2015).
Aydinol, M. K., Kohan, A. F., Ceder, G., Cho, K. & Joannopoulos, J. Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides. Phys. Rev. B 56, 1354–1365 (1997).
Aydinol, M. K., Kohan, A. F. & Ceder, G. Ab initio calculation of the intercalation voltage of lithium–transition-metal oxide electrodes for rechargeable batteries. J. Power Sources 68, 664–668 (1997).
Acknowledgements
P.G.B. is indebted to the EPSRC, including the SUPERGEN programme, the Henry Royce Institute for Advanced Materials (EP/R00661X/1, EP/S019367/1, EP/R010145/1) and the Faraday Institution (FIRG007, FIRG008) for financial support. We thank H. Playford and R. Smith at ISIS, Harwell Campus for collecting neutron diffraction data. Support from the EPSRC (EP/K040375/1 ‘South of England Analytical Electron Microscope’) is also acknowledged. We acknowledge the use of the University of Oxford Advanced Research Computing (ARC) facility (https://doi.org/10.5281/zenodo.22558) in carrying out this work, and the resources provided by the Cambridge Tier-2 system operated by the University of Cambridge Research Computing Service (http://www.hpc.cam.ac.uk) funded by EPSRC Tier-2 capital grant EP/P020259/1, via the Advanced Materials for Alkali-ion Batteries (AMAiB) project. Synchrotron radiation experiments were performed at the i21 beamline, Diamond Light Source, Harwell, UK, with supporting data collected from the ADRESS beamline, Swiss Light Source, Villigen, Switzerland, and BL27SU, Spring8, Japan. We acknowledge technical and experimental support at the ADRESS beamline by T. Schmitt, D. McNally, X. Lu, L. Nue and M. Dantz and at the BL27SU beamline by K. Tsuruta. We thank N. Rees for help in collecting NMR spectra.
Author information
Authors and Affiliations
Contributions
R.A.H., U.M., M.R.R. and P.G.B. conceived the study. U.M. and R.A.H. carried out the materials synthesis, characterization and testing. R.A.H., U.M., J.W.S., M.R.R. and L.C.D. contributed to the measurement processing and interpretation of the spectroscopic data. M.A.P.-O. performed the DFT calculations. L.J. collected, processed and interpreted the NMR data. J.G.L. performed and interpreted the ADF-STEM measurements. R.A.H., A.N., A.W. and K.-J.Z. performed high-resolution RIXS and sXAS measurements. R.A.H. and P.G.B. wrote the manuscript with contributions and revisions from all authors.
Corresponding author
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.
Extended data figures and tables
Extended Data Fig. 1 Further structural characterization of pristine materials.
a, b, Neutron powder diffraction data for (a) Na0.75[Li0.25Mn0.75]O2 and (b) Na0.6[Li0.2Mn0.8]O2 refined using the P63/mmc space group, which excludes superstructure ordering. Rietveld refinement was performed with GSAS II software. Refinement parameters are given in the tables in the lower part of the figure, including the goodness of fit (G.O.F). Inductively coupled plasma (ICP) optical emission spectroscopy was used to confirm the chemical compositions.
Extended Data Fig. 2 Diffraction peaks arising from ribbon superstructure ordering in Na0.6[Li0.2Mn0.8]O2.
a, PXRD data for pristine Na0.6[Li0.2Mn0.8]O2 indexed using the P63/mmc space group which does not account for superstructure peaks arising from in-plane ordering in the TM layer. b, Superstructure region of PXRD compared with computer generated diffraction patterns. Model crystal structures were prepared with different alignments of ribbon ordered layers. The only structure to successfully match all the peaks is the P21/c space group. Structures are all viewed along the [010] direction.
Extended Data Fig. 3 Operando gas evolution analysis.
OEMS collected on Na0.6[Li0.2Mn0.8]O2 at 10 mA g−1 between 2 V and 4.5 V. No direct O2 loss is observed. Only a very small quantity of CO2 is released at 3.5–4.2 V, characteristic of alkali carbonate decomposition; a small amount is released at 4.5 V due to direct electrolyte oxidation. Overall, 0.005 moles of CO2 per mole of active material were detected during charge compared with 0.4 moles of charge stored per mole of active material. Even if all of this CO2 arose from O loss from the lattice, it would constitute only a minimal contribution (0.02 moles of charge stored per formula unit, f.u., or about 5%), to the charge capacity observed.
Extended Data Fig. 4 Manganese L-edge spectra and low-resolution RIXS for Na0.6[Li0.2Mn0.8]O2.
a, Electrochemical load curve for first cycle of Na0.6[Li0.2Mn0.8]O2 showing state of charge points selected for ex situ analysis. b, Manganese L-edge data collected in inverse partial fluorescence yield mode show that Na0.6[Li0.2Mn0.8]O2 remains unchanging at Mn4+ throughout the charge and discharge cycle. Standards shown below are MnO (+2), Mn2O3 (+3) and Li2MnO3 (+4). c, Low-resolution RIXS spectra collected at BL27SU, Spring8 synchrotron, Japan, at 531 eV excitation energy show a new feature at an emission energy of approximately 523 eV corresponding to new hole states formed on O and an increase in the elastic peak intensity (labelled with arrows). These new features disappear on discharge indicating O reduction, and the spectra are almost superimposable with those collected for the pristine material. The intensity of both features appears much less pronounced than the O redox features measured on honeycomb-ordered O-redox materials.
Extended Data Fig. 5 Two-phase evolution in Li environment in Na0.6[Li0.2Mn0.8]O2.
Ex situ 6Li MAS NMR spectra for Na0.6[Li0.2Mn0.8]O2 collected at different states of charge illustrate the two-phase nature of the charge–discharge plateau. Negligible change in the lithium environment is observed below the end of the plateau on discharge in the single-phase region. Arrows indicate the unique isotropic chemical shifts for Li.
Extended Data Fig. 6 Further electron microscopy imaging showing retention of ribbon and loss of honeycomb ordering.
a, b, ADF-STEM images showing further spatial investigation of the charged and discharged samples of (a) Na0.6[Li0.2Mn0.8]O2 with ribbon ordering and (b) Na0.75[Li0.25Mn0.75]O2 with honeycomb ordering. A further image showing Na0.6[Li0.2Mn0.8]O2 after 10 charge–discharge cycles is also included.
Extended Data Fig. 7 Energetic stability afforded by O2 formation and computed discharge voltage.
a, Energetics of possible configurations of desodiated structural models for Na0.0Li0.25Mn0.75O2. The models considered are: P2-type stacking with Li in the TM layer (P2/LiTM); O2-type stacking with Li in the TM layer (O2/LiTM); O2-type stacking with Li in the AM layer (O2/LiAL); and O2-type stacking with Li in the AM layer and with in-plane Mn disorder (O2/LiAL/Mndis). In the last case, various Mn disorder configurations were investigated corresponding to the different crosses. The lowest-energy structure is pictured (ab-plane) and possesses clusters of vacancies and Mn-bound O2 with an O–O bond length of 1.2 Å corresponding to molecular O2. For simplicity, the energies of the optimized models are plotted relative to the energy of the model P2/LiTM, the energy of which was set to zero. The yellow curve is a guide to the eye to indicate the models with the lowest total energies. b, Calculated lattice parameters for pristine, charged, and discharged Na0.75Li0.25Mn0.75O2. They are compared with experimental data. The deviation between theory and experiment is also reported. c, d, Structural models used to compute the change in energy and average voltage for Na0.75Li0.25Mn0.75O2 (c) and Na0.6Li0.2Mn0.8O2 (d) respectively. Discharge reactions and calculated voltages are given in (iii). Purple, Mn; green, Li; yellow, Na.
Extended Data Fig. 8 Ribbon ordering identified in P3-type Na0.6[Li0.2Mn0.8]O2.
PXRD data for P3-type Na0.6[Li0.2Mn0.6]O2 reproduced with permission from ref. 14. Below are calculated diffraction patterns for the P3 structure with and without ribbon ordering of Li and Mn in the TM layer. Vertical dotted lines show positions of superstructure peaks. The structure used for the calculation of the ribbon-ordered P3-type Na0.6Li0.2Mn0.6O2 diffraction pattern is shown to the right and possesses an offset arrangement of ordered layers.
Extended Data Fig. 9 Evolution of electrochemical behaviour over resting and cycling.
a, Electrochemical load curves for Na0.6[Li0.2Mn0.8]O2 electrodes charged to 4.5 V at a rate of 10 mA g−1, then rested at open circuit voltage (OCV) for varying amounts of time before discharge at 10 mA g−1. b, c, Electrochemical load curves for ribbon-ordered Na0.6[Li0.2Mn0.8]O2 and honeycomb-ordered Na0.75[Li0.25Mn0.75]O2 electrodes respectively, cycled between 2.0 V and 4.5 V at a rate of 10 mA g−1. First cycle blue.
Extended Data Fig. 10 Gradual loss of ribbon superstructure ordering from diffraction.
Ex situ PXRD patterns for Na0.6[Li0.2Mn0.8]O2 in the discharged state (2.0 V) after 1, 10 and 20 charge–discharge cycles (between 2.0 V and 4.5 V at 10 mA g−1). Peaks arising from the periodicity uniquely along the c-axis remain sharp upon cycling (indexed as 002 and 004 according to the P63/mmc space group without superstructure), whereas all other peaks, especially the 010 and 110, which are unique to ordering within the ab plane, broaden and reduce in intensity as the ribbon superstructure is lost on cycling.
Rights and permissions
About this article
Cite this article
House, R.A., Maitra, U., Pérez-Osorio, M.A. et al. Superstructure control of first-cycle voltage hysteresis in oxygen-redox cathodes. Nature 577, 502–508 (2020). https://doi.org/10.1038/s41586-019-1854-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41586-019-1854-3
This article is cited by
-
Sustainable layered cathode with suppressed phase transition for long-life sodium-ion batteries
Nature Sustainability (2024)
-
Trapped O2 and the origin of voltage fade in layered Li-rich cathodes
Nature Materials (2024)
-
Achieving a high-performance sodium-ion pouch cell by regulating intergrowth structures in a layered oxide cathode with anionic redox
Nature Energy (2024)
-
Structurally robust lithium-rich layered oxides for high-energy and long-lasting cathodes
Nature Communications (2024)
-
Ternary-phase layered cathodes toward ultra-stable and high-rate sodium ion storage
Rare Metals (2024)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.