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In situ multiscale probing of the synthesis of a Ni-rich layered oxide cathode reveals reaction heterogeneity driven by competing kinetic pathways

Abstract

Nickel-rich layered oxides are envisaged as key near-future cathode materials for high-energy lithium-ion batteries. However, their practical application has been hindered by their inferior cycle stability, which originates from chemo-mechanical failures. Here we probe the solid-state synthesis of LiNi0.6Co0.2Mn0.2O2 in real time to better understand the structural and/or morphological changes during phase evolution. Multi-length-scale observations—using aberration-corrected transmission electron microscopy, in situ heating transmission electron microscopy and in situ X-ray diffraction—reveal that the overall synthesis is governed by the kinetic competition between the intrinsic thermal decomposition of the precursor at the core and the topotactic lithiation near the interface, which results in spatially heterogeneous intermediates. The thermal decomposition leads to the formation of intergranular voids and intragranular nanopores that are detrimental to cycling stability. Furthermore, we demonstrate that promoting topotactic lithiation during synthesis can mitigate the generation of defective structures and effectively suppress the chemo-mechanical failures.

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Fig. 1: Topotactic lithiation into layered TM(OH)2 precursor at low temperature.
Fig. 2: Heterogeneous phase evolution at low-temperature intermediate by kinetic competition.
Fig. 3: Effect of heterogeneity on the final products of layered oxides.
Fig. 4: Electrochemical properties of NCM layered oxide with two-step calcination.
Fig. 5: Proposed mechanism of reaction heterogeneity during synthesis of nickel-rich layered oxides.

Data availability

All the data supporting the findings of this study are available within the article and its Supplementary Information and also from the corresponding authors upon reasonable request. Source data are provided with this paper.

Code availability

The code for calculation of particle average TEM intensity is available at https://github.com/parkhayoungg/Parklab_nchem_NCM_code.

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Acknowledgements

This work was supported by the Institute of Basic Science (IBS-R006-A2 and IBS-R006-D1) and by the Defense Challengeable Future Technology Program of the Agency for Defense Development, Republic of Korea (contract no. UC190025RD); financially supported by SK Innovation; and supported by a National Research Foundation of Korea grant funded by the Korean government’s Ministry of Science and ICT (no. 2021R1C1C2012688). K.K. acknowledges support from Samsung SDI. Hayoung Park, S.K., J.K. and J.P. acknowledge National Research Foundation of Korea grants, funded by the Korean government’s Ministry of Science and ICT (no. NRF-2017R1A5A1015365, no. NRF-2021M3H4A1A02045962 and no. NRF-2020R1A2C2101871). Hayoung Park, Y.J. and J.P. acknowledge support by the Samsung Research Funding & Incubation Center of Samsung Electronics under project no. SRFC-MA2002-03 for the development of the in situ TEM method. K.S. acknowledges the work at the Korea Institute of Materials Science by the Fundamental Research Program of the Korea Institute of Materials Science (grant no. PNK8450).

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Hyeokjun Park, Hayoung Park, J.P. and K.K. conceived the original idea and designed the research project. Hyeokjun Park and Hayoung Park carried out the synthesis and the structural and electrochemical characterizations of the materials; participated in all experiments and relevant analyses; and led the project direction. K.S. conducted the in situ heating environment TEM imaging experiments. S.H.S. and H.K. performed the in situ heating X-ray diffraction measurements and provided constructive advice on the analysis of the diffraction results. S.K. conducted the focused ion beam preparation and the high-resolution TEM and high-resolution STEM imaging experiments. K.-H.K., D.E., Y.J., J.K. and W.M.S. offered valuable comments and discussion on the experimental design and analyses. Hyeokjun Park, Hayoung Park, J.P. and K.K. wrote the manuscript with the help of the other authors. The manuscript reflects the contributions of all authors. J.P. and K.K. supervised all aspects of the research.

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Correspondence to Jungwon Park or Kisuk Kang.

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Nature Chemistry thanks Jianming Bai, Helmut Ehrenberg, Kerstin Volz and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Ex situ XRD pattern of the mixture of transition-metal hydroxide and lithium hydroxide with heating.

The ex situ samples were collected at different temperatures following the heating profiles of the conventional synthesis of NCM622. Note that the TM(OH)2 is a CdI2-type layered structure in the \(P{\bar 3}m1\) space group whose main Bragg reflection appears near 19.5°.

Source data

Extended Data Fig. 2 In situ XRD pattern of the mixture of transition-metal hydroxide and lithium carbonate.

(a) In situ XRD pattern at given equilibrated temperature for calcinations of precursor for layered oxide. (b) Phase and structural evolution during the synthesis. The phase fraction of Li2CO3 might be overestimated at the certain temperature region near 250 °C because of the decrease in the overall crystallinity of mixed transition metal compounds that undergo the decomposition. Nevertheless, the phase analysis result clearly verifies the distinct synthetic mechanism with the usage of Li2CO3 by which thermal dehydration of NCM hydroxide precursor is preceded into the oxide phase, followed by synthetic reaction with Li2CO3 at a much higher temperature, resulting in slow formation of layered oxide structures.

Source data

Extended Data Fig. 3 Cross-sectional SEM and TEM images of transition-metal hydroxide mixture with lithium hydroxide heated ex situ at 500 °C.

(a) Cross-sectional SEM image. TEM images and SAED pattern of primary particles at the (b) core and (c) shell region, as marked in (a). The radial heterogeneity was alleviated to some extent, which agrees with the results of the negative intensity difference at higher temperature (> 340 °C) in Fig. 2f. The SAED patterns on the sample also indicate that both the core and surface regions of the particle evolved to the lithium-containing layered oxide. This result suggests that the continuous inward supply of lithium through the interface could induce the full lithiation within the secondary particle at this temperature, although the path toward the layered structure formation differs for the shell and core regions.

Extended Data Fig. 4 EELS line scan results of nanopore in transition-metal hydroxide heated at 500 °C.

(a) STEM image of nanopore within primary particle, (b) EELS Mn L-edge, Co L-edge, and Ni L-edge in corresponding area. The oxidation state of the transition metal in the nanopore was slightly more reduced, corresponding to the typical transition-metal states in the rock-salt phase.

Source data

Extended Data Fig. 5 TG analysis results for mixture of transition-metal hydroxide and lithium hydroxide.

(a) TG curve with different holding times at 200 °C to 6 h with a heating rate of 5 °C min−1. (b) Column graph showing the percentage of weight loss from lithiation and dehydration of transition-metal hydroxide as a function of holding time. Each weight loss is derived from the value measured at 200–225 °C (before 225 °C) and 225–300 °C (after 225 °C) for lithiation and dehydration, respectively. The temperature of 225 °C corresponds to the local minimum point between the two peaks in the TG curve. We set the maximum of the temperature range for thermal dehydration to 300 °C, beyond which negligible thermal activity is observed in the TG curve for the mixture of transition-metal hydroxide and lithium hydroxide. The inversely proportional relationship of the weight loss for the two events indicates that it is reasonable that as much synthetic lithiation as possible occurs. The amount of remaining transition-metal hydroxide precursor that can be thermally decomposed is reduced.

Source data

Extended Data Fig. 6 Electrochemical properties of NCM electrodes at different rates.

(a) Capacity retention at 1 C. (b) Rate capability and capacity retention at 0.1 C.

Source data

Supplementary information

Supplementary Information

Supplementary Figs. 1–10, Tables 1 and 2, and Notes 1–4.

Supplementary Video 1

In situ TEM snapshots during heating of transition-metal hydroxide and lithium hydroxide from 150 °C to 350 °C.

Supplementary Data 1

Source data for the supplementary figures.

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Source Data Fig. 2

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Source Data Fig. 4

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Source Data Extended Data Fig. 1

Source data for Extended Data Fig. 1.

Source Data Extended Data Fig. 2

Source data for Extended Data Fig. 2.

Source Data Extended Data Fig. 4

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Park, H., Park, H., Song, K. et al. In situ multiscale probing of the synthesis of a Ni-rich layered oxide cathode reveals reaction heterogeneity driven by competing kinetic pathways. Nat. Chem. 14, 614–622 (2022). https://doi.org/10.1038/s41557-022-00915-2

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