Monitoring the Formation of Nickel-Poor and Nickel-Rich Oxide Cathode Materials for Lithium-Ion Batteries with Synchrotron Radiation

Ying, Bixian; Fitzpatrick, Jack; Teng, Zhenjie; Chen, Tianxiang; Lo, Tsz Woon Benedict; Siozios, Vassilios; Murray, Claire; Brand, Helen E. A.; Day, Sarah; Tang, Chiu C.; Weatherup, Robert S.; Merz, Michael; Nagel, Peter; Schuppler, S.; Winter, Martin; Kleiner, Karin

doi:10.1021/acs.chemmater.2c02639

Cited by 18 publications

(12 citation statements)

References 60 publications

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“…As is commonly reported in the literature, the presence of Mn in the structure necessitates higher annealing temperatures to form a pure layered phase (Liu et al, 2022;McCalla & Dahn, 2013). Previous studies have also shown that the reaction pathway and observed intermediate phases differ markedly for various cathode-material compositions despite targeting the same final layered structure (Ying et al, 2023;Duffiet et al, 2022;Hua et al, 2019). Qualitatively, the in situ diffraction data collected from the Mn-containing mixtures look very similar to the LNO data shown earlier in Fig.…”

Section: Resultssupporting

confidence: 83%

In situ neutron diffraction to investigate the solid-state synthesis of Ni-rich cathode materials

Goonetilleke¹,

Suard²,

Bergner³

et al. 2023

J Appl Crystallogr

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Studying chemical reactions in real time can provide unparalleled insight into the evolution of intermediate species and can provide guidance to optimize the reaction conditions. For solid-state synthesis reactions, powder diffraction has been demonstrated as an effective tool for resolving the structural evolution taking place upon heating. The synthesis of layered Ni-rich transition-metal oxides at a large scale (grams to kilograms) is highly relevant as these materials are commonly employed as cathodes for Li-ion batteries. In this work, in situ neutron diffraction was used to monitor the reaction mechanism during the high-temperature synthesis of Ni-rich cathode materials with a varying ratio of Ni:Mn from industrially relevant hydroxide precursors. Rietveld refinement was further used to model the observed phase evolution during synthesis and compare the behaviour of the materials as a function of temperature. The results presented herein confirm the suitability of in situ neutron diffraction to investigate the synthesis of batches of several grams of electrode materials with well-controlled stoichiometry. Furthermore, monitoring the structural evolution of the mixtures with varying Ni:Mn content in real time reveals a delayed onset of lithiation as the Mn content is increased, necessitating the use of higher annealing temperatures to achieve layering.

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Section: Resultssupporting

confidence: 83%

In situ neutron diffraction to investigate the solid-state synthesis of Ni-rich cathode materials

Goonetilleke¹,

Suard²,

Bergner³

et al. 2023

J Appl Crystallogr

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“…Li 2 CO 3 or LiOH) in air or O 2 . [18][19][20][21] A further advantage of mixed metal hydroxide or carbonate precursors are their open structure, which enables rapid lithiation kinetics during this heating step, thus minimizing the heating time and thereby also minimizing the amount of lithium lost during the heating step by evaporation. Despite these advantages, co-precipitation is a complex method that involves many process steps.…”

mentioning

confidence: 99%

Quantitative Measurement of Compositional Inhomogeneity in NMC Cathodes by X-ray Diffraction

Tahmasebi,

Obrovac

2023

J. Electrochem. Soc.

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A novel X-ray diffraction (XRD) analysis technique is described for quantitatively measuring compositional inhomogeneity in Li[NixMnyCoz]O2 (NMC) cathode materials and NMC precursors. Single-phase rock salt precursors with varying degrees of compositional inhomogeneity were prepared by grinding mixtures of Ni, Mn, and Co oxides for different times and then heating. These precursors were then heated with lithium to form cathode materials. A modified Williamson-Hall analysis was used to measure the degree of compositional inhomogeneity in the precursors and the final NMC materials. This analysis showed that precursors made with low grinding times had higher compositional inhomogeneity and that this compositional inhomogeneity was amplified in the final NMC, leading to interlayer mixing and poor electrochemical performance. Higher precursor grinding times lead to more compositionally homogeneous NMC, while even higher compositional homogeneity was achieved by NMC made from conventional hydroxide precursors, with correspondingly improved electrochemical performance. The ability described here to measure the degree of compositional homogeneity in NMC precursors and NMC cathode materials by simple XRD measurements presents a powerful tool for the research and development of NMC and other cathode materials.

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“…The synthesis of the lithium transition metal oxides, poor nickel (NCM111, LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) and rich nickel (NCM811, LiNi 0.8 Co 0.1 Mn 0.1 O 2 ), was studied by in situ SR XRD. [116] These two layered cathode materials have been developed of two completely different reaction mechanisms. The NCM811 will appear a rock salt type intermediate phase driven by high Ni content at ≈325 • C, and the structure transforms a rhombohedral structure because of a sufficient amount of lithium ions and lowering steric constraints during the 2 h holding step at 500 • C, while NCM111 only shows layered structure in the whole synthesis process (Figure 6D).…”

Section:  Xrd For Resolving Crystalline Structurementioning

confidence: 99%

Section: Application Examples Of Battery Structure Detectionmentioning

confidence: 99%

Recent advances in battery characterization using in situ XAFS, SAXS, XRD, and their combining techniques: From single scale to multiscale structure detection

Cheng,

Zhao,

Lai

et al. 2023

Exploration

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Revealing and clarifying the chemical reaction processes and mechanisms inside the batteries will bring a great help to the controllable preparation and performance modulation of batteries. Advanced characterization techniques based on synchrotron radiation (SR) have accelerated the development of various batteries over the past decade. In situ SR techniques have been widely used in the study of electrochemical reactions and mechanisms due to their excellent characteristics. Herein, the three most wide and important synchrotron radiation techniques used in battery research were systematically reviewed, namely X‐ray absorption fine structure (XAFS) spectroscopy, small‐angle X‐ray scattering (SAXS), and X‐ray diffraction (XRD). Special attention is paid to how these characterization techniques are used to understand the reaction mechanism of batteries and improve the practical characteristics of batteries. Moreover, the in situ combining techniques advance the acquisition of single scale structure information to the simultaneous characterization of multiscale structures, which will bring a new perspective to the research of batteries. Finally, the challenges and future opportunities of SR techniques for battery research are featured based on their current development.

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Monitoring the Formation of Nickel-Poor and Nickel-Rich Oxide Cathode Materials for Lithium-Ion Batteries with Synchrotron Radiation

Cited by 18 publications

References 60 publications

In situ neutron diffraction to investigate the solid-state synthesis of Ni-rich cathode materials

In situ neutron diffraction to investigate the solid-state synthesis of Ni-rich cathode materials

Quantitative Measurement of Compositional Inhomogeneity in NMC Cathodes by X-ray Diffraction

Recent advances in battery characterization using in situ XAFS, SAXS, XRD, and their combining techniques: From single scale to multiscale structure detection

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