Microstrain screening towards defect-less layered transition metal oxide cathodes | Nature Nanotechnology
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Microstrain screening towards defect-less layered transition metal oxide cathodes | Nature Nanotechnology

Oct 24, 2024

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Microstrain and the associated surface-to-bulk propagation of structural defects are known to be major roadblocks to developing high-energy and long-life batteries. However, the origin and effects of microstrain during the synthesis of battery materials remain largely unknown. Here we perform microstrain screening during real-time and realistic synthesis of sodium layered oxide cathodes. Evidence gathered from multiscale in situ synchrotron X-ray diffraction and microscopy characterization collectively reveals that the spatial distribution of transition metals within individual precursor particles strongly governs the nanoscale phase transformation, local charge heterogeneity and accumulation of microstrain during synthesis. This unexpected dominance of transition metals results in a counterintuitive outward propagation of defect nucleation and growth. These insights direct a more rational synthesis route to reduce the microstrain and crystallographic defects within the bulk lattice, leading to significantly improved structural stability. The present work on microstrain screening represents a critical step towards synthesis-by-design of defect-less battery materials.

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Research at Argonne National Laboratory was funded by the US Department of Energy (DOE), Vehicle Technologies Office. Support from T. Duong of the US DOE’s Office of Vehicle Technologies Program is gratefully acknowledged. Use of the Advanced Photon Source and the Center for Nanoscale Materials, both Office of Science user facilities at Argonne National Laboratory, was supported by the US DOE, Office of Science and Office of Basic Energy Sciences, under contract number DE-AC02-06CH11357. This research used resources of the Argonne Leadership Computing Facility, a US DOE Office of Science user facility at Argonne National Laboratory and is based on research supported by the US DOE Office of Science–Advanced Scientific Computing Research Program, under contract number DE-AC02-06CH11357. This research used beamline 18-ID of the National Synchrotron Light Source II, a US DOE Office of Science user facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract number DE-SC0012704.

These authors contributed equally: Wenhua Zuo, Jihyeon Gim, Tianyi Li.

Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA

Wenhua Zuo, Jihyeon Gim, Yibo Gao, Shiyuan Zhou, Chen Zhao, Xin Jia, Zhenzhen Yang, Gui-Liang Xu & Khalil Amine

X-ray Sciences Division, Advanced Photon Source, Argonne National Laboratory, Lemont, IL, USA

Tianyi Li & Wenqian Xu

Centre for Nanoscale Materials, Argonne National Laboratory, Lemont, IL, USA

Dewen Hou & Yuzi Liu

National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY, USA

Xianghui Xiao

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G.-L.X., W.Z. and K.A. conceived the idea and designed the experiments. G.-L.X. and K.A. initiated and supervised the project. J.G. synthesized the precursors. W.Z., Y.G. and X.J. synthesized the cathode materials. W.Z. carried out the SEM, EDS and electrochemical tests. W.Z. performed TXM characterization and analysis under supervision of X.X. W.Z., T.L. and C.Z. carried out in situ and ex situ SXRD measurements and analysis with the assistance of W.X. Z.Y. and W.Z. carried out argon ion milling. Z.Y. conducted XPS measurements. W.Z., S.Z. and Y.L. performed FIB measurements. D.H. and Y.L. contributed TEM measurements. G.-L.X. and W.Z. wrote the paper with input from all authors. All authors discussed the results, co-wrote and commented on the paper.

Correspondence to Xianghui Xiao, Gui-Liang Xu or Khalil Amine.

The authors declare no competing interests.

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

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The XRD patterns of core–shell and conventional Ni0.80Mn0.10Co0.10(OH)2 precursors demonstrate excellent crystallization with hexagonal \(P\bar{3}m1\) space group and no obvious impurities. X-ray wavelength is 1.5406 Å.

(a-b) SXRD identification and structural evolution of (a) conventional and (b) core–shell Ni0.80Mn0.10Co0.10(OH)2-NaOH mixtures during calcination. (c) Structural illustration of NaOH·H2O, α-NaOH, β-NaOH, and γ-NaOH phases. The heating process began at room temperature (28 °C) with a mixture of Ni0.80Mn0.10Co0.10(OH)2 precursor and α-NaOH. At the very start of heating, a small part of α-NaOH hydrates, leading to the formation of NaOH·H2O phase; this hydration occurs due to exposure to ambient atmosphere when mounting the sample in quartz tubes. As the temperature rises to 56 °C, NaOH·H2O undergoes dehydration, transforming back to α-NaOH. In addition to being consumed during chemical reactions between NaOH and TM(OH)2, the α-NaOH undergoes a transition to β-NaOH at 226°C, followed by a transition to γ-NaOH at 274 °C, and ultimately liquefies at 293 °C. The cubic γ-NaOH is rarely reported due to the transition temperature from β-NaOH to γ-NaOH approaching or even exceeding the melting point of NaOH. Here, the distinct appearance of γ-NaOH might be attributed to the influence of transition metal cations on the thermodynamic equilibrium. Having a melted Na source is kinetically more favourable to accelerate the solid-state reactions; thus, NaOH is preferred over other Na sources that have a much higher melting point, such as Na2O2 (460 °C), Na2CO3 (851 °C), and Na2O (900 °C). NaOH underwent same phase transformations at similar temperatures for both conventional and core–shell samples.

(a-b) TEM images of core–shell NaNMC811 grain at 250 °C. Labelled regions in (b) are highlighted in (c) and (d) images. The high-resolution TEM images of a primary granule (b-d) show that the sodium insertion process exhibits a nucleation and growth pattern through a needle-like texture. This process initiated at the grain edges and advanced toward the inner grain areas (from region c to region d). Moreover, an intermediate nanosized rock-salt structure was observed during the transition from hydroxide to O-type phases (d), accompanied by other structural defects, such as edge dislocation and lattice disorder. These observations indicate a structure with high microstrain, leading to the development of intragranular cracks. The scale bars in (c) and (d) are 5 nm and 10 nm, respectively.

Sodiation/lithiation mechanisms of layered oxide cathodes illustrated (a) without and (b) with the spatial distribution of transition metal during solid-state synthesis. Here we present a comprehensive comparison of two distinct lithiation/sodiation mechanisms encountered by layered oxide cathodes based on a Ni-rich compound during the solid-state synthesis. The first is the topotactic lithiation/sodiation mechanism, depicted in (a). This mechanism represents an ideal scenario where lithium/sodium ions progressively diffuse from the surface to the interior of particles. Upon the phase transformation of the hydroxide precursor to layered oxide structures, the Ni cations transition from a divalent state (Ni2+(OH)2) to a high valence state (NaxNi3+/4+O2, 0 < x < 1.0), before reducing to a trivalent upon further insertion of sodium ions. That is, inward surface-to-bulk propagation will be observed. At O2-deficient calcination conditions, hydroxide precursors decompose into rock-salt NiO phase. The transition from NiO to a layered oxide poses a higher energy barrier compared to that from Ni(OH)2, resulting in a more sluggish sodiation process. A second sodiation mechanism is specific to particles with core–shell chemical distribution (b). Owing to the inhomogeneous dominance of transition metal (Ni in this case), the inserted sodium ions tend to accumulate in the inner Ni-rich core, leading to a scenario where the inner layers exhibit a lower valence state of Ni ions and a Na-rich phase, in contrast to the higher Ni valence state and Na-less phase in the outer layers. This inhomogeneity in the lithiation/sodiation process, whether arising from chemical inhomogeneity or the variance in topotactic/decomposition reactions, results in an observation of outward propagation of sodiation and the consequent defect generation.

(a) F1s and (b) C1s XPS spectra of the cycled core–shell NaNMC811-T440-R1 (1°C min-1) and core–shell NaNMC811-T440-R5 (5°C min-1) cathodes.

In situ heating SXRD patterns of the (a) desodiated core–shell NaNMC811-T440-R5 cathode (3.9 V charged state) and (b) desodiated core–shell NaNMC811-T440-R1 cathode (3.9 V charged state).

Supplementary Figs. 1–15.

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Zuo, W., Gim, J., Li, T. et al. Microstrain screening towards defect-less layered transition metal oxide cathodes. Nat. Nanotechnol. (2024). https://doi.org/10.1038/s41565-024-01734-x

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Received: 26 February 2024

Accepted: 28 June 2024

Published: 20 August 2024

DOI: https://doi.org/10.1038/s41565-024-01734-x

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