Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode

Boisse, Benoit Mortemard de; Liu, Guandong; Ma, Jiangtao; Nishimura, Shin Ichi; Chung, Sai Cheong; Kiuchi, Hisao; Harada, Yoshihisa; Kikkawa, Jun; Kobayashi, Yoshio; Okubo, Masashi; Yamada, Atsuo

doi:10.1038/ncomms11397

Cited by 259 publications

(260 citation statements)

References 46 publications

(68 reference statements)

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“…The pre-edge peak above 530 eV in sXAS O K-edge of LNRO (Fig. 4d) at the pristine and discharged states was more pronounced compared to that of LNMO, due to the different hybridization features between Ru-O 60 and Mn-O 28 . Additionally, the difference between the pristine and discharged LNRO samples is likely due to the formation of surface species, which is often different for materials with different surface reactivity.…”

Section: Resultsmentioning

confidence: 97%

Elucidating anionic oxygen activity in lithium-rich layered oxides

et al. 2018

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Recent research has explored combining conventional transition-metal redox with anionic lattice oxygen redox as a new and exciting direction to search for high-capacity lithium-ion cathodes. Here, we probe the poorly understood electrochemical activity of anionic oxygen from a material perspective by elucidating the effect of the transition metal on oxygen redox activity. We study two lithium-rich layered oxides, specifically lithium nickel metal oxides where metal is either manganese or ruthenium, which possess a similar structure and discharge characteristics, but exhibit distinctly different charge profiles. By combining X-ray spectroscopy with operando differential electrochemical mass spectrometry, we reveal completely different oxygen redox activity in each material, likely resulting from the different interaction between the lattice oxygen and transition metals. This work provides additional insights into the complex mechanism of oxygen redox and development of advanced high-capacity lithium-ion cathodes.

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Section: Resultsmentioning

confidence: 97%

Elucidating anionic oxygen activity in lithium-rich layered oxides

et al. 2018

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“…Previous XAS results 6,7,10,12–14,30–32 mainly utilized electron and fluorescence based detection modes (Fig. 2b), which are distorted by surface contributions, self-absorption, and peak broadening effects and show only a weak and broad feature at the same energy.…”

Section: Resultsmentioning

confidence: 99%

“…For example, Li-rich surface and near-surface regions often exhibit oxygen evolution and reconstruction during delithiation 24–28 , yet surface-sensitive X-ray photoelectron spectroscopy (XPS) is often used to infer the nature of bulk anion redox 5,9,11,29 . Likewise, correlations between spatially averaged X-ray absorption spectra (XAS) are often used to assess hybridization 6,7,10,12–14,30–32 , which assumes that redox chemistry occurs uniformly. The relatively subtle evolution in the spectra during anion redox, combined with their sensitivity to probing depth (a few nm for quantitative XPS and total-electron-yield (TEY) XAS) and detection mode (e.g., self-absorption distortions in fluorescence-yield (FY) XAS) has contributed to the conflicting proposed mechanisms for oxygen redox in certain materials and, consequently, explanations for its role in determining capacity and electrochemical stability 15,21,22,32,33 .…”

Section: Introductionmentioning

confidence: 99%

Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides

et al. 2017

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Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li1.17–xNi0.21Co0.08Mn0.54O2, these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by > 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.

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“…A recent work from Yamada and co-workers demonstrated the critical role of honeycomb-type cation ordering in Na 2 RuO 3 to trigger the oxygen redox process by evaluating the Na storage behaviors of two ordered and disordered polymorphs. [27] The ordered Na 2 RuO 3 with in-plan honeycomb ordering exhibited a capacity of 180 mA h g −1 based on a 1.3-electron reaction, while disordered Na 2 RuO 3 delivered only 135 mA h g −1 with a 1.0-electron reaction. The additional capacity delivered by the ordered Na 2 RuO 3 could be attributed to the formation of an ordered intermediate O1-phase NaRuO 3 .…”

Section: Layered Oxides With Anion Redox Couplementioning

confidence: 96%

Progress in High‐Voltage Cathode Materials for Rechargeable Sodium‐Ion Batteries

You

Manthiram

2017

Advanced Energy Materials

432

268

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potential (E° = −2.71 V vs standard hydrogen electrode (SHE) for Na + /Na, 0.3 V higher than that of Li + /Li).[5] Thus, rechargeable batteries based on sodium electrochemistry are considered as promising alternatives for grid-scale EES applications, which put specific requirements on the cost and sustainable resource supply of the battery. The component parts and the working principle for sodium-ion batteries (SIBs) are quite similar to those of LIBs, as shown in Figure 1. [6] Na + ions migrate between a positive electrode (cathode) and a negative electrode (anode) through an Na + electrolyte in between. Both electrodes are composed of intercalation compounds that allow reversible insertion and extraction of Na + ions. [7] Studies on Na + ions intercalation chemistry can be traced back to 1980s, [8] yet they did not attract much attention due to the LIBs, which held significant advantages in energy output and electrochemical stability over other rechargeable batteries and dominated the research/market for the next two decades. With the concern of potential shortage of Li resources, some concerted effort began to revisit the SIB technology and its key materials, especially after the year 2010. Al foil can be used as current collectors for the anode rather than Cu in SIBs because Na does not alloy with Al, which may help to further reduce the cost and increase the energy density. [9] Besides the cost advantages, SIBs also offer opportunities to obtain a faster kinetics with the electrochemical reaction; for example, it may enable a high Na + conductivity in bulk solid within a wide temperature range [10] and an easier charge transfer owing to less pronounced solvation. Such merits, according to the recent work, have led to surprisingly low polarization and high-rate capability (e.g., in Na 3 V 2 (PO 4 ) cathode materials), [11] making SIBs quite appealing for high-power applications. [12] Although SIBs present a less expensive raw materials compared with LIBs, it is worth noting that the higher energynormalized cost of prototype SIBs [13] demonstrates the importance to improve its energy density, which can be realized by increasing the output voltage or capacity. Given that the output voltage of an SIB is determined by the electrode potential difference between the positive and the negative electrodes and the positive electrode is the bottleneck for boosting the energy output of SIBs, major efforts have been devoted to develop advanced cathode materials with high output voltage and high capacity. [14] Prominent potential cathode candidates including Room-temperature rechargeable sodium-ion batteries are considered as a promising alternative technology for grid and other storage applications due to their competitive cost benefit and sustainable resource supply, triumphing other battery systems on the market. To facilitate the practical realization of the sodium-ion technology, the energy density of sodium-ion batteries needs to be boosted to the level of current commercial Li-ion batteries. An effective approach...

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Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode

Cited by 259 publications

References 46 publications

Elucidating anionic oxygen activity in lithium-rich layered oxides

Elucidating anionic oxygen activity in lithium-rich layered oxides

Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides

Progress in High‐Voltage Cathode Materials for Rechargeable Sodium‐Ion Batteries

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