Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles with Operando X-ray Absorption Spectroscopy

Nowack, Lea V.; Grolimund, Daniel; Samson, Vallerie Ann; Marone, Federica; Wood, Vanessa

doi:10.1038/srep21479

Cited by 51 publications

(40 citation statements)

References 47 publications

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“…The propagation of redox reactions governs the electrochemical properties of battery materials and their critical performance metrics in practical cells [3][4][5] . The recent research progress, especially aided by advanced analytical techniques 6 , has revealed that incomplete and heterogeneous redox reactions prevail in many electrode materials, such as olivine phosphates [7][8][9][10][11][12][13][14] , layered oxides [15][16][17][18][19][20] , spinel oxides 21,22 , and conversion materials 23,24 . Advanced highcapacity cathode materials for lithium (Li) ion and sodium (Na) ion batteries are mostly polycrystalline materials that exhibit complex charge distribution (the valence state distribution of the redox-active cations) due to the presence of numerous constituting grains and grain boundaries.…”

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confidence: 99%

Charge distribution guided by grain crystallographic orientations in polycrystalline battery materials

et al. 2020

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Architecting grain crystallographic orientation can modulate charge distribution and chemomechanical properties for enhancing the performance of polycrystalline battery materials. However, probing the interplay between charge distribution, grain crystallographic orientation, and performance remains a daunting challenge. Herein, we elucidate the spatially resolved charge distribution in lithium layered oxides with different grain crystallographic arrangements and establish a model to quantify their charge distributions. While the holistic "surface-to-bulk" charge distribution prevails in polycrystalline particles, the crystallographic orientation-guided redox reaction governs the charge distribution in the local charged nanodomains. Compared to the randomly oriented grains, the radially aligned grains exhibit a lower cell polarization and higher capacity retention upon battery cycling. The radially aligned grains create less tortuous lithium ion pathways, thus improving the charge homogeneity as statistically quantified from over 20 million nanodomains in polycrystalline particles. This study provides an improved understanding of the charge distribution and chemomechanical properties of polycrystalline battery materials.

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Charge distribution guided by grain crystallographic orientations in polycrystalline battery materials

et al. 2020

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“…However, these studies are handicapped by the stringent sample requirements (thickness of <100 nm, for example), high-vacuum environment and the limitation in sample size. In recent years, hard X-ray full-field transition microscopy imaging combined with X-ray absorption near-edge structure (FF-TXM-XANES) was introduced as a revolutionarily new approach for visualizing electrochemically driven solid-state phase transformation18192021. The brightness and the energy tunability of synchrotron-based hard X-ray enable nanoscale spatial resolution at ∼30 nm along with high chemical and elemental sensitivities in a large field-of-view (FOV; 30 × 30 μm).…”

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Phase transformation mechanism in lithium manganese nickel oxide revealed by single-crystal hard X-ray microscopy

et al. 2017

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Understanding the reaction pathway and kinetics of solid-state phase transformation is critical in designing advanced electrode materials with better performance and stability. Despite the first-order phase transition with a large lattice mismatch between the involved phases, spinel LiMn1.5Ni0.5O4 is capable of fast rate even at large particle size, presenting an enigma yet to be understood. The present study uses advanced two-dimensional and three-dimensional nano-tomography on a series of well-formed LixMn1.5Ni0.5O4 (0≤x≤1) crystals to visualize the mesoscale phase distribution, as a function of Li content at the sub-particle level. Inhomogeneity along with the coexistence of Li-rich and Li-poor phases are broadly observed on partially delithiated crystals, providing direct evidence for a concurrent nucleation and growth process instead of a shrinking-core or a particle-by-particle process. Superior kinetics of (100) facets at the vertices of truncated octahedral particles promote preferential delithiation, whereas the observation of strain-induced cracking suggests mechanical degradation in the material.

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“…Inhomogeneous behavior in lithium battery electrodes has been the subject of many recent articles . The presence of these heterogeneities has been revealed by both in situ and ex situ techniques, which include conventional X‐ray diffraction (XRD), energy dispersive X‐ray diffraction, X‐ray tomography, X‐ray absorption spectroscopy, transmission X‐ray microscopy, and transmission electron microscopy . Another technique, Raman spectroscopy, offers an opportunity to probe local structure in a manner that complements data obtained by the X‐ray and electron beam techniques.…”

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Composition and Impedance Heterogeneity in Oxide Electrode Cross‐Sections Detected by Raman Spectroscopy

Gilbert

Maroni

Cui

et al. 2018

Adv Materials Inter

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the upper cutoff voltage (UCV) for cycling is increased. [4][5][6][7][8] The capacity fade in these cells mainly results from immobilization of Li + ions in the solid electrolyte interphase (SEI) of the graphite electrode; this immobilization is accelerated by the dissolution of TM ions from the positive electrode that deposit in the negative electrode SEI. [9,10] Cell impedance rise on aging arises mainly at the positive electrode. Contributing factors include the build-up of electrolyte decomposition products in the electrode, [11] crystal reconstruction at the oxide-particle surfaces, [12,13] increased separation of primary particles within the secondary particle agglomerates, [14,15] and intragranular cracking within the primary particles. [16] An interesting finding from our studies is the significant scatter in electrochemical performance data observed for cells cycled at a C/1 rate to an UCV > 4.3 V. [8] We attributed this nonuniform behavior to the fracture of sintered boundaries between the submicrometer-size primary particles, which occurs in an unpredictable and relatively random manner. Such "intergranular cracking" was also reported recently by Liu et al. [17] who obtained transmission X-ray tomograms on LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) oxide electrodes cycled in operando to a UCV = 4.5 V. These authors described heterogeneities in the oxide behavior noting the presence of "active" and "sluggish" populations in cells that displayed ≈20% capacity fade. This observation points to an impedance inhomogeneity within the oxide particle population that develops on extended cycling, wherein the active and sluggish particles can be described as having low impedance and high impedance, respectively.Inhomogeneous behavior in lithium battery electrodes has been the subject of many recent articles. [18][19][20][21][22][23][24][25][26] The presence of these heterogeneities has been revealed by both in situ and ex situ techniques, which include conventional X-ray diffraction (XRD), [17,19] energy dispersive X-ray diffraction, [20] X-ray tomography, [21] X-ray absorption spectroscopy, [22] transmission X-ray microscopy, [23] and transmission electron microscopy. [24][25][26] Another technique, Raman spectroscopy, offers an opportunity to probe local structure in a manner that complements data obtained by the X-ray and electron beam techniques. Whereas the latter techniques provide average information from all particles within the path of the X-ray or electron beam, Raman Lithium-bearing layered transition metal oxides are the materials of choice for positive electrodes in high energy lithium-ion cells being developed for electric vehicle applications. During electrochemical cycling, the loss of mobile lithium-ions due to undesirable side reactions and an increase in cell resistance leads to a decline in the energy and power performance of the cells. This performance loss is often nonuniform across multiple cells, especially for those cycled at high voltages or high C-rates. This nonuniformity results from inhomoge...

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Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles with Operando X-ray Absorption Spectroscopy

Cited by 51 publications

References 47 publications

Charge distribution guided by grain crystallographic orientations in polycrystalline battery materials

Charge distribution guided by grain crystallographic orientations in polycrystalline battery materials

Phase transformation mechanism in lithium manganese nickel oxide revealed by single-crystal hard X-ray microscopy

Composition and Impedance Heterogeneity in Oxide Electrode Cross‐Sections Detected by Raman Spectroscopy

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