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Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries

Nature Energy volume 1, Article number: 15004 (2016) Cite this article

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Abstract

In technologically important LiNi1−x−yMnxCoyO2 cathode materials, surface reconstruction from a layered to a rock-salt structure is commonly observed under a variety of operating conditions, particularly in Ni-rich compositions. This phenomenon contributes to poor high-voltage cycling performance, impeding attempts to improve the energy density by widening the potential window at which these electrodes operate. Here, using advanced nano-tomography and transmission electron microscopy techniques, we show that hierarchically structured LiNi0.4Mn0.4Co0.2O2 spherical particles, made by a simple spray pyrolysis method, exhibit local elemental segregation such that surfaces are Ni-poor and Mn-rich. The tailored surfaces result in superior resistance to surface reconstruction compared with those of conventional LiNi0.4Mn0.4Co0.2O2, as shown by soft X-ray absorption spectroscopy experiments. The improved high-voltage cycling behaviour exhibited by cells containing these cathodes demonstrates the importance of controlling LiNi1−x−yMnxCoyO2 surface chemistry for successful development of high-energy lithium ion batteries.

The development of lithium ion battery technologies has spurred major breakthroughs in portable electronics, power tools, electric vehicles, and grid energy storage. In a lithium ion cell, the energy and power delivery is achieved by shuttling lithium ions between positive and negative electrodes, where the active materials undergo redox reactions using electrons from an external circuit within certain voltage windows. So far, cathode materials have received considerable attention because they are considered to be a primary determinant for increasing cell energy and power densities1,2,3,4. One way to increase the practical discharge capacities of cathode materials is to increase the upper voltage limit during charge, provided that the electrolytic solution can withstand this increase in cell potential. Side reactions and thermodynamic instability of cathode materials at high voltages (high degree of lithium removal), however, have handicapped this approach. To achieve a stable cycling performance for cathode materials, it is important to maintain desirable crystal and electronic structures that allow for efficient transport of electrons and ions for the redox reactions at transition metal sites5,6. Numerous studies, in particular those using electronic and structural diagnostic techniques (for example, core-level spectroscopy, electron microscopy), have shown that undesirable phase transformations occur in cathodes that can lead to failure in batteries cycled to high voltages7,8,9,10,11,12,13,14. In particular, surface reconstruction (surface transition metal reduction) from a layered structure to a mixed spinel/rock-salt structure is related to the high-voltage failure of stoichiometric layered cathode materials, that is, R 3 ̄ m LiNi1−x−yMnxCoyO2 (NMC; refs 7,10,11). In other cathode materials, such as lithium–manganese-rich layered NMCs (also known as LMR-NMCs or xLi2MnO3⋅ (1 − x) LiMO2, where M = Mn, Ni, Co and so on), LixNi0.8Co0.15Al0.05O2 and high-voltage spinel LiNi0.5Mn1.5O4, surface reconstruction is also a factor in the poor Coulombic efficiency, and fast capacity fading that is observed8,9,15,16,17 as well as transition metal dissolution and complexation18. Our previous density functional theory calculations indicated that, in NMC materials, the thermodynamic driving force to form rock-salt structures increases as a function of the degree of deintercalation11,19. Furthermore, it has been shown that cathode–electrolyte side reactions (for example, simply by exposing NMC materials to LiPF6-based organic electrolytic solutions) also contribute to the surface reconstruction12.

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Figure 1: Elemental mapping and association calculation using transmission X-ray tomography.
Figure 2: 3D elemental association maps generated using transmission X-ray tomography.
Figure 3: Characterization of the NMC-442 materials synthesized by spray pyrolysis.
Figure 4: Electronic and compositional characterization using EELS.
Figure 5: Battery cycling performance of lithium half-cells containing the NMC-442 materials.
Figure 6: Surface chemistry of NMC materials before and after electrochemical cycling.
Figure 7: 3D elemental association mapping and elemental distribution of co-precipitated NMC particles.

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Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy under Contract No. DE-AC02-05CH11231. This research used the Hitachi dedicated STEM of the Center for Functional Nanomaterials, which is a US Department of Energy Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704. The synchrotron X-ray portions of this research were carried out at the Stanford Synchrotron Radiation Lightsource, a Directorate of SLAC National Accelerator Laboratory and an Office of Science User Facility operated for the US Department of Energy Office of Science by Stanford University. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. F.L. acknowledges J. Xu and C. Tian for valuable discussion. Y.Liu thanks D. Van Campen for valuable discussions and his engineering support for experiments at beamline 6-2C of SSRL. F.L., D.N. and T.-C.W. would like to thank J.-S. Lee and G. Kerr for their assistance at SSRL. This document was prepared as an account of work sponsored by the United States Government. While this document is believed to contain correct information, neither the United States Government nor any agency thereof, nor the Regents of the University of California, nor any of their employees, makes any warranty, express or implied, or assumes any legal responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by its trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favouring by the United States Government or any agency thereof, or the Regents of the University of California. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof or the Regents of the University of California.

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  1. Tsu-Chien Weng

    Present address: † Present address: Center for High Pressure Science & Technology Advanced Research, Shanghai 201203, China.,

Authors and Affiliations

  1. Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    Feng Lin, Yuyi Li, Matthew K. Quan, Lei Cheng & Marca M. Doeff

  2. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA

    Dennis Nordlund, Tsu-Chien Weng & Yijin Liu

  3. Department of Materials Science and Engineering, University of California, Berkeley, California 94720, USA

    Lei Cheng

  4. Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, USA

    Huolin L. Xin

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Contributions

F.L., Y.Liu, H.L.X. and M.M.D. participated in conceiving and designing the experiments. F.L. performed the materials syntheses, electrochemical measurements and characterization, and wrote the paper with assistance from M.M.D., Y.Liu and H.L.X. F.L., Y.Liu, D.N. and T.-C.W. designed and performed synchrotron experiments. Y.Liu analysed the TXM tomography data. H.L.X. performed STEM–EELS experiments and co-analysed the data with F.L. Y.Li and M.K.Q. participated in developing materials syntheses. L.C. participated in the data analysis and discussion. M.M.D. supervised the project. All authors participated in discussions and know the implications of the work.

Corresponding authors

Correspondence to Yijin Liu, Huolin L. Xin or Marca M. Doeff.

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Supplementary information

Supplementary Information

Supplementary Figures 1–3. (PDF 516 kb)

Supplementary Video 1

3D chemical distribution of particles collected directly after spray pyrolysis, before annealing. The particle surfaces are first shown from different angles then the colour-coded distribution of each element is shown as slices, to reveal the interior. (MOV 3207 kb)

Supplementary Video 2

3D chemical distribution of particles collected after annealing. The particle surfaces are first shown from different angles then the colour-coded distribution of each element is shown as slices, to reveal the interior. (MOV 5852 kb)

Supplementary Video 3

3D chemical associations for an annealed particle. The initial views show the surfaces of the particle from different viewpoints and later views show slices from the interior, also from different vantages. The colour keys are the same as in Figure 2: Mn is blue, Co is red, Ni is green, Mn/Co is purple, Mn/Ni is cyan, Co/Ni is yellow and Mn/Co/Ni is white. (MOV 9752 kb)

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Lin, F., Nordlund, D., Li, Y. et al. Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries. Nat Energy 1, 15004 (2016). https://doi.org/10.1038/nenergy.2015.4

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