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Origin of structural degradation in Li-rich layered oxide cathode

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Abstract

Li- and Mn-rich (LMR) cathode materials that utilize both cation and anion redox can yield substantial increases in battery energy density1,2,3. However, although voltage decay issues cause continuous energy loss and impede commercialization, the prerequisite driving force for this phenomenon remains a mystery3,4,5,6 Here, with in situ nanoscale sensitive coherent X-ray diffraction imaging techniques, we reveal that nanostrain and lattice displacement accumulate continuously during operation of the cell. Evidence shows that this effect is the driving force for both structure degradation and oxygen loss, which trigger the well-known rapid voltage decay in LMR cathodes. By carrying out micro- to macro-length characterizations that span atomic structure, the primary particle, multiparticle and electrode levels, we demonstrate that the heterogeneous nature of LMR cathodes inevitably causes pernicious phase displacement/strain, which cannot be eliminated by conventional doping or coating methods. We therefore propose mesostructural design as a strategy to mitigate lattice displacement and inhomogeneous electrochemical/structural evolutions, thereby achieving stable voltage and capacity profiles. These findings highlight the significance of lattice strain/displacement in causing voltage decay and will inspire a wave of efforts to unlock the potential of the broad-scale commercialization of LMR cathode materials.

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Fig. 1: Electrochemical profile and initial structure of the LMR cathodes.
Fig. 2: Strain evolution of the LMR primary particle and its relationship with oxygen release.
Fig. 3: Multiscale X-ray diffraction techniques used to investigate the structure evolution of the LMR cathode.
Fig. 4: Visible observation from atomic-level TEM, 3D electron diffraction and chemical state analysis from EELS.
Fig. 5: Schematic of the correlation of strain generation and O release as well as transition metal migration.

Data availability

The data that support the findings of this study are available from the corresponding authors upon request.

References

  1. Li, M. et al. Cationic and anionic redox in lithium-ion based batteries. Chem. Soc. Rev. 49, 1688–1705 (2020).

    CAS  PubMed  Article  Google Scholar 

  2. Hu, E. et al. Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release. Nat. Energy 3, 690–698 (2018).

    ADS  CAS  Article  Google Scholar 

  3. Assat, G. & Tarascon, J.-M. Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries. Nat. Energy 3, 373–386 (2018).

    ADS  CAS  Article  Google Scholar 

  4. Sathiya, M. et al. Reversible anionic redox chemistry in high-capacity layered-oxide electrodes. Nat. Mater. 12, 827–835 (2013).

    ADS  CAS  PubMed  Article  Google Scholar 

  5. Zheng, J. et al. Li‐and Mn‐rich cathode materials: challenges to commercialization. Adv. Energy Mater. 7, 1601284 (2017).

    Article  CAS  Google Scholar 

  6. Choi, J. W. & Aurbach, D. Promise and reality of post-lithium-ion batteries with high energy densities. Nat. Rev. Mater. 1, 16013 (2016).

    ADS  CAS  Article  Google Scholar 

  7. Sathiya, M. et al. Origin of voltage decay in high-capacity layered oxide electrodes. Nat. Mater. 14, 230–238 (2015).

    ADS  CAS  PubMed  Article  Google Scholar 

  8. 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).

    ADS  CAS  PubMed  Article  Google Scholar 

  9. Hong, J. et al. Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides. Nat. Mater. 18, 256–265 (2019).

    ADS  CAS  PubMed  Article  Google Scholar 

  10. Hu, S. et al. Insight of a phase compatible surface coating for long‐durable Li‐rich layered oxide cathode. Adv. Energy Mater. 9, 1901795 (2019).

    Article  CAS  Google Scholar 

  11. Shang, H. et al. Suppressing voltage decay of a lithium-rich cathode material by surface enrichment with atomic ruthenium. ACS Appl. Mater. Interfaces 10, 21349–21355 (2018).

    ADS  CAS  PubMed  Article  Google Scholar 

  12. Singer, A. et al. Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging. Nat. Energy 3, 641–647 (2018).

    ADS  CAS  Article  Google Scholar 

  13. Yan, P. et al. Injection of oxygen vacancies in the bulk lattice of layered cathodes. Nat. Nanotechnol. 14, 602–608 (2019).

    ADS  CAS  PubMed  Article  Google Scholar 

  14. Assat, G. et al. Fundamental interplay between anionic/cationic redox governing the kinetics and thermodynamics of lithium-rich cathodes. Nat. Commun. 8, 2219 (2017).

    ADS  PubMed  PubMed Central  Article  CAS  Google Scholar 

  15. 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).

    CAS  PubMed  Article  Google Scholar 

  16. Liu, T. et al. Understanding Co roles towards developing Co-free Ni-rich cathodes for rechargeable batteries. Nat. Energy 6, 277–286 (2021).

    ADS  CAS  Article  Google Scholar 

  17. Liu, T. et al. Correlation between manganese dissolution and dynamic phase stability in spinel-based lithium-ion battery. Nat. Commun. 10, 4721 (2019).

    ADS  PubMed  PubMed Central  Article  CAS  Google Scholar 

  18. Xu, C. et al. Bulk fatigue induced by surface reconstruction in layered Ni-rich cathodes for Li-ion batteries. Nat. Mater. 20, 84–92 (2021).

    ADS  CAS  PubMed  Article  Google Scholar 

  19. Xu, Z. et al. Charge distribution guided by grain crystallographic orientations in polycrystalline battery materials. Nat. Commun. 11, 83 (2020).

    ADS  CAS  PubMed  PubMed Central  Article  Google Scholar 

  20. Ulvestad, A. et al. Topological defect dynamics in operando battery nanoparticles. Science 348, 1344–1347 (2015).

    ADS  CAS  PubMed  Article  Google Scholar 

  21. Zhang, F. et al. Surface regulation enables high stability of single-crystal lithium-ion cathodes at high voltage. Nat. Commun. 11, 3050 (2020).

    ADS  CAS  PubMed  PubMed Central  Article  Google Scholar 

  22. Bi, Y. et al. Reversible planar gliding and microcracking in a single-crystalline Ni-rich cathode. Science 370, 1313–1317 (2020).

    ADS  CAS  PubMed  Article  Google Scholar 

  23. Qian, G. et al. Understanding the mesoscale degradation in nickel-rich cathode materials through machine-learning-revealed strain–redox decoupling. ACS Energy Lett. 6, 687–693 (2021).

    CAS  Article  Google Scholar 

  24. Robinson, I. & Harder, R. Coherent X-ray diffraction imaging of strain at the nanoscale. Nat. Mater. 8, 291–298 (2009).

    ADS  CAS  PubMed  Article  Google Scholar 

  25. Yoon, W.-S. et al. Local structure and cation ordering in O3 lithium nickel manganese oxides with stoichiometry Li[NixMn(2−x)/3Li(1−2x)/3]O2: NMR studies and first principles calculations. Electrochem. Solid-State Lett. 7, A167–A171 (2004).

    CAS  Article  Google Scholar 

  26. Yu, H. et al. Direct atomic‐resolution observation of two phases in the Li1.2Mn0.567Ni0.166Co0.067O2 cathode material for lithium‐ion batteries. Angew. Chem. Int. Ed. Engl. 52, 5969–5973 (2013).

    CAS  PubMed  Article  Google Scholar 

  27. Leifer, N. et al. Linking structure to performance of Li1.2Mn0.54Ni0.13Co0.13O2 (Li and Mn rich NMC) cathode materials synthesized by different methods. Phys. Chem. Chem. Phys. 22, 9098–9109 (2020).

    CAS  PubMed  Article  Google Scholar 

  28. Lin, F. et al. Synchrotron X-ray analytical techniques for studying materials electrochemistry in rechargeable batteries. Chem. Rev. 117, 13123–13186 (2017).

    CAS  PubMed  Article  Google Scholar 

  29. Xu, Z. et al. Charging reactions promoted by geometrically necessary dislocations in battery materials revealed by in situ single‐particle synchrotron measurements. Adv. Mater. 32, 2003417 (2020).

    CAS  Article  Google Scholar 

  30. Jha, S. K., Charalambous, H., Okasinski, J. S. & Tsakalakos, T. Using in operando diffraction to relate lattice strain with degradation mechanism in a NMC battery. J. Mater. Sci. 54, 2358–2370 (2019).

    ADS  CAS  Article  Google Scholar 

  31. Qiu, B. et al. Metastability and reversibility of anionic redox-based cathode for high-energy rechargeable batteries. Cell Rep. Phys. Sci. 1, 100028 (2020).

    Article  Google Scholar 

  32. Li, W., Erickson, E. M. & Manthiram, A. High-nickel layered oxide cathodes for lithium-based automotive batteries. Nat. Energy 5, 26–34 (2021).

    ADS  Article  CAS  Google Scholar 

  33. Zhao, S., Yan, K., Zhang, J., Sun, B. & Wang, G. Reaction mechanisms of layered lithium-rich cathode materials for high-energy lithium-ion batteries. Angew. Chem. Int. Ed. Engl. 60, 2208–2220 (2021).

    CAS  PubMed  Article  Google Scholar 

  34. Strehle, B. et al. The role of oxygen release from Li-and Mn-rich layered oxides during the first cycles investigated by on-line electrochemical mass spectrometry. J. Electrochem. Soc. 164, A400–A406 (2017).

    CAS  Article  Google Scholar 

  35. Nakayama, K., Ishikawa, R., Kobayashi, S., Shibata, N. & Ikuhara, Y. Dislocation and oxygen-release driven delithiation in Li2MnO3. Nat. Commun. 11, 4452 (2020).

    ADS  CAS  PubMed  PubMed Central  Article  Google Scholar 

  36. Rana, J. et al. Structural changes in Li2MnO3 cathode material for Li‐ion batteries. Adv. Energy Mater. 4, 1300998 (2014).

    Article  CAS  Google Scholar 

  37. Xiao, R., Li, H. & Chen, L. Density functional investigation on Li2MnO3. Chem. Mater. 24, 4242–4251 (2012).

    CAS  Article  Google Scholar 

  38. Chen, H. & Islam, M. S. Lithium extraction mechanism in Li-rich Li2MnO3 involving oxygen hole formation and dimerization. Chem. Mater. 28, 6656–6663 (2016).

    CAS  Article  Google Scholar 

  39. Li, L., Xie, Y., Maxey, E. & Harder, R. Methods for operando coherent X-ray diffraction of battery materials at the Advanced Photon Source. J. Synchrotron Radiat. 26, 220–229 (2019).

    CAS  PubMed  Article  Google Scholar 

  40. Robinson, I., Vartanyants, I., Williams, G., Pfeifer, M. & Pitney, J. Reconstruction of the shapes of gold nanocrystals using coherent X-ray diffraction. Phys. Rev. Lett. 87, 195505 (2001).

    ADS  CAS  PubMed  Article  Google Scholar 

  41. Maiti, S. et al. Understanding the role of alumina (Al2O3), pentalithium aluminate (Li5AlO4), and pentasodium aluminate (Na5AlO4) coatings on the Li and Mn-rich NCM cathode material 0.33Li2MnO3·0.67Li (Ni0.4Co0.2Mn0.4)O2 for enhanced electrochemical performance. Adv. Funct. Mater. 31, 2008083 (2021).

    CAS  Article  Google Scholar 

  42. Li, J. et al. Structural origin of the high-voltage instability of lithium cobalt oxide. Nat. Nanotechnol. 16, 599–605 (2021).

    ADS  CAS  PubMed  Article  Google Scholar 

  43. Eum, D. et al. Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes. Nat. Mater. 19, 419–427 (2020).

    ADS  CAS  PubMed  Article  Google Scholar 

  44. House, R. A. et al. First-cycle voltage hysteresis in Li-rich 3d cathodes associated with molecular O2 trapped in the bulk. Nat. Energy 5, 777–785 (2020).

    ADS  CAS  Article  Google Scholar 

  45. Csernica, P. M. et al. Persistent and partially mobile oxygen vacancies in Li-rich layered oxides. Nat. Energy 642–652(2021).

  46. Liu, H. et al. Unraveling the rapid performance decay of layered high-energy cathodes: from nanoscale degradation to drastic bulk evolution. ACS Nano 12, 2708–2718 (2018).

    CAS  PubMed  Article  Google Scholar 

  47. Boulineau, A., Simonin, L., Colin, J. F., Bourbon, C. & Patoux, S. First evidence of manganese-nickel segregation and densification upon cycling in Li-rich layered oxides for lithium batteries. Nano Lett. 13, 3857–3863 (2013).

    ADS  CAS  PubMed  Article  Google Scholar 

  48. Teufl, T., Strehle, B., Müller, P., Gasteiger, H. A. & Mendez, M. A. Oxygen release and surface degradation of Li- and Mn-rich layered oxides in variation of the Li2MnO3 content. J. Electrochem. Soc. 165, A2718–A2731 (2018).

    CAS  Article  Google Scholar 

  49. Chen, Z., Li, J. & Zeng, X. C. Unraveling oxygen evolution in Li-rich oxides: a unified modeling of the intermediate peroxo/superoxo-like dimers. J. Am. Chem. Soc. 141, 10751–10759 (2019).

    CAS  PubMed  Article  Google Scholar 

  50. Wan, W., Sun, J., Su, J., Hovmöller, S. & Zou, X. Three-dimensional rotation electron diffraction: software RED for automated data collection and data processing. J. Appl. Crystallogr. 46, 1863–1873 (2013).

    CAS  PubMed  PubMed Central  Article  Google Scholar 

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Acknowledgements

We gratefully acknowledge support from the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. This work was also supported by the Clean Vehicles, US–China Clean Energy Research Centre (CERC-CVC2) under US DOE EERE Vehicle Technologies Office. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under contract number DE-AC02-06CH11357. This research was also supported by the National Key R&D Program of China (2016YFB0700600), Soft Science Research Project of Guangdong Province (no. 2017B030301013) and the Shenzhen Science and Technology Research Grants (no. ZDSYS201707281026184). This research used resources of the Advanced Photon Source (11-ID-C, 9BM and 34-ID-C), a US DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. Work at Brookhaven National Laboratory was supported by the DOE, Office of Science, Office of Basic Energy Sciences, under contract no. DE-SC0012704. Electron microscopy was carried out at the Center for Nanoscale Materials, an Office of Science user facility, supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357.

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Authors and Affiliations

Authors

Contributions

T.L., J. Liu, L.L., J. Lu, F.P. and K.A. conceived the idea and designed the experiments. T.L., J. Liu, R.Q. and S.X. synthesized all the materials and conducted electrochemical measurements. J. Liu, L.Y., T.Z., Y.X., W.Z. and J.W. carried out the TEM, EELS and 3D-rED measurements. T.L., A.D., T.W., L.W. and Y.R. performed ex situ synchrotron HEXRD and XAS. T.L., L.L, J.D., W.C., R.H. and I.R. performed in situ BCDI, CMCD and data analysis. S.L., J.Z. and F.P. conducted DFT calculation. T.L., J. Liu, J. Lu, F.P. and K.A. wrote the manuscript and all authors edited the manuscript.

Corresponding authors

Correspondence to Jun Lu, Feng Pan or Khalil Amine.

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Nature thanks Doron Aurbach and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data figures and tables

Extended Data Fig. 1 The morphology, particle distribution, surface area and composition of the LMR cathode.

a, b The SEM image of the LMR powder. The particle size ranges from 200–600 nm. c The particle size distribution of the as-prepared LMR cathode. The mean particle size of LMR cathode is around 583 nm. d The nitrogen adsorption/desorption isotherm of LMR. e The corresponding BET plot of LMR. The nitrogen adsorption/desorption isotherm and the corresponding BET plot of the as-prepared LMR cathode indicate that its specific surface area is calculated to be 2.804 m2 g−1. f SEM-EDS results of the pristine LMR cathode. The actual chemical composition complies well with the design (Mn : Co : Ni = 4 : 1 : 1).

Extended Data Fig. 2 The electrochemical properties of the LMR cathode.

a, b The first charge/discharge curve and corresponding dQ/dV curve of LMR cathode. The first charge profile exhibits two distinct electrochemical stages at different voltage ranges. Stage 1 corresponds to the Li+ extraction (de-lithiation) from LiTMO2 domains with concomitant oxidation of Ni2+ and Co3+. Stage 2 corresponds to the activation of Li2MnO3 domains, further Li+ extraction and at this stage oxygen is oxidized (at high potentials) to per-oxo species: (2O2− ↔ [O2]2− + 2e). c, d The galvanostatic intermittent titration technique (GITT) test of the first charge. The Li-ion diffusion coefficient keeps stable in stage 1 but dramatically decreases after the activation of Li2MnO3 domains (stage 2).

Extended Data Fig. 3 The morphology, particle distribution, surface area and in situ DEMS of the Li2MnO3 cathode.

a The SEM image of the as-prepared Li2MnO3 powder. The as-prepared Li2MnO3 exhibits a single-particle morphology with average particle size of 100–200 nm. b The nitrogen adsorption/desorption isotherm of the as-prepared Li2MnO3 powder. c The corresponding BET plot of the as-prepared Li2MnO3 powder. The specific surface area of Li2MnO3 is calculated to be 3.1106 m2 g−1. d The particle size distribution of the as-prepared Li2MnO3 powder. e In situ DEMS for the first charge of Li2MnO3. The signal of O2 evolution is not detected until 20% delithiation of Li2MnO3.

Extended Data Fig. 4 The ex situ and in situ XRD and ex situ XAS of the LMR cathode.

a The ex situ XRD patterns of the first charge/discharge for the LMR cathode. The superlattice evolution of the LMR cathode can be observed in the 2 theta range of 1.5–1.8°. The obvious lattice parameter changes can be observed from ex situ XRD pattern, particularly in the 2 theta range of 3.0–6.0°. b The in situ XRD patterns of the as-prepared LMR cathode during the first charge/discharge in the voltage range of 2.0–4.8 V using a current rate of C/10 (1C = 250 mA g-1). The obvious lattice parameter changes can be observed from in situ XRD patterns, particularly in the 2 theta range of 1.3–1.5°. Generally, the structure evolution observed in in situ XRD is completely consistent with that in ex situ XRD (Figure 3c). c-e Ex situ Mn K-edge EXAFS spectra of the samples at pristine, 4.5V and 4.8V and the corresponding fitting results. Detailed fitting results are shown in Extended Data Table 2.

Extended Data Fig. 5 Visible lattice displacement observations using TEM of the LMR charged to 4.47 V.

High magnification TEM image of the LMR charged to 4.47 V. Although the layered structure is maintained, lattices in the marked areas are deformed significantly.

Extended Data Fig. 6 Visible structural observations of the LMR charged to 4.5 V.

a High magnification TEM image of the LMR charged to 4.5 V. b The enlarged image of the selected area in Extended Data Fig. 6a. c The corresponding Fourier pattern of the select area of Extended Data Fig. 6a. d, e, f and g The simulated patterns of standard electron diffractions for layer [210], spinel [112], and Li2MnO3 [100]/[110]. h, i and j TEM images of the LMR cathode charged to 4.5 V. The lattice displacements are highlighted with yellow marks. k, l and m The corresponding FFT images of Extended Data Fig. 6h, i and j. Obvious lattice displacements are observed in the different particles and the corresponding FFT images confirm the existence of spinel phase at 4.5 V, which is highly consistent with Fig. 4g results.

Extended Data Fig. 7 The SAED images captured at different rotation angles from −40 to 36º.

These SAED images in Extended Data Fig. 7 are used for 3D-rED reconstruction present in Fig. 4e–f.

Extended Data Fig. 8 Lattice displacement and structure changes observed from 3D-rED and SAED.

a, b The reciprocal lattice viewed along the a* axis of the LMR cathode at 4.5 V. c The selected area electron diffraction (SAED) image of the sample charged to 4.5 V. In addition to the typical layered structure and weak Li2MnO3 reflection, the reflection that corresponds to the spinel lattice can be also observed. d, e, f and g The simulated patterns of standard electron diffractions for Layer [210], spinel [112], and Li2MnO3 [100]/[110].

Extended Data Fig. 9 Visible structural observations and chemical state changes of the LMR charged to 4.8 V.

a, b Low and High magnification TEM image of the LMR charged to 4.8 V. A clear reconstruction surface layer with the spinel phase can be visualized. c Electron energy loss spectroscopy line scans of the O K-edge, Mn L-edge, Co & Ni L-edge for the LMR charged to 4.8 V along the direction from surface to bulk. The intensity of O-K edge pre-peaks substantially reduces from the interior to the exterior and almost disappears near the surface. Concurrently, Mn L-edge shows left shift near the surface. d Electron energy loss spectroscopy line scans of the O K-edge, Mn L-edge, Co & Ni L-edge for the LMR charged to 4.8 V along the surface fringe. The O-K line-scan parallel to the surface confirms that the oxygen release uniformly occurs in the entire particle surface as the disappeared O pre-peak.

Extended Data Fig. 10 Structure and electrochemical properties of O2 phase-based LMR.

a The XRD pattern of as-prepared LixNi0.13Mn0.54Co0.13O2. The diffraction peaks belonging to an O2 phase with P63mc symmetry are indexed by blue marks, while some tiny peaks belonging to O3 phase with R-3m symmetry are indexed by red marks. b High-resolution TEM image showing the atomic arrangements of O2 phase LMR. The Li2MnO3-like domain is rarely observed in the O2-type LMR, which suggests that the Li@Mn6 structural motifs in the O2 type LMR cathode are dispersed in the TM layer instead of being aggregated to form a Li2MnO3-like domain. c The charge/discharge profiles of O2 phase-based LMR cathode. The cells were activated at C/10 within first 3 cycles and then cycled at C/3. The smooth charging behaviour with no apparently differentiated voltage plateaus indicates effectively suppressed differential electrochemical activities. d The voltage stability of the O2 type LMR cathode during cycles presents in the plot of average (mean) voltage profiles vs cycle number.

Extended Data Table 1 Lattice parameters obtained by the two-phase structure model refinement of pristine LMR cathode
Extended Data Table 2 Structural parameters of the samples obtained by fitting the EXAFS data

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Liu, T., Liu, J., Li, L. et al. Origin of structural degradation in Li-rich layered oxide cathode. Nature 606, 305–312 (2022). https://doi.org/10.1038/s41586-022-04689-y

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