Revisiting the charge compensation mechanisms in LiNi0.8Co0.2−yAlyO2 systems

Lebens-Higgins, Zachary W.; Faenza, Nicholas V.; Radin, Maxwell D.; Líu, Hao; Sallis, Shawn; Rana, Jatinkumar; Vinckevičiūtė, Julija; Reeves, Philip J.; Zuba, Mateusz; Badway, F.; Pereira, Nathalie; Chapman, Karena W.; Lee, Tien‐Lin; Wu, Tianpin; Grey, Clare P.; Melot, Brent C.; Ven, Anton Van der; Amatucci, Glenn G.; Yang, Wanli; Piper, Louis F. J.

doi:10.1039/c9mh00765b

Cited by 72 publications

(97 citation statements)

References 78 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These results further strengthen the reductive coupling scenario about the important role of TM-O interaction in oxygen redox systems, which is critical for the ultimate understanding of the mechanism of lattice oxygen redox reactions, something remains a grand challenge in the field and require further intensive studies. Another finding from our mRIXS results is the reversible lattice oxygen redox in such a conventional layered LiNiO 2 , which has very few direct experimental evidences, 32,36,[52][53][54] although the overall contribution is relatively small in the mRIXS maps were collected in the ultra-high efficiency iRIXS endstation at Beamline 8.0.1 at the Advanced Light Sources (ALS). 57 Sample surface was mounted 45° to the incident beam, and the outgoing photon direction along the RIXS spectrograph is 90° with other technical details available in our previous report.…”

Section: The Redox Chemistry Of Linio 2 Is Seemingly Straightforwardmentioning

confidence: 99%

Unraveling the Cationic and Anionic Redox Reactions in a Conventional Layered Oxide Cathode

et al. 2019

Self Cite

View full text Add to dashboard Cite

The increasing interest in high energy and high capacity batteries triggers the demand of clarifying the reaction mechanism in battery cathodes during high potential operations. This is critical for further improving the performance of commercially viable Ni rich compounds, however, the mechanism often involves both transition metal and oxygen activities that remain elusive. Here we report a comprehensive study of the both the

show abstract

Section: The Redox Chemistry Of Linio 2 Is Seemingly Straightforwardmentioning

confidence: 99%

Unraveling the Cationic and Anionic Redox Reactions in a Conventional Layered Oxide Cathode

et al. 2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…However, later studies clarified that Li2IrO3 does not have ORR unless doped with Sn, and voltage hysteresis unfortunately gets strong while ORR emerges in the Sn doped Li2IrO3 systems. 18 Secondly, very recent reports have revealed that non-Li-rich conventional layered compounds display ORR at high voltages too [19][20][21] . These findings benefit from recent advances of O-K highefficiency mapping of resonant inelastic X-ray scattering (mRIXS), which could reliably detect the lattice (non-released) ORR in battery electrodes at charged states.…”

Section: Toc Graphicsmentioning

confidence: 99%

“…22 Other conventional Naion materials were also found to feature strong ORR, 23,24 but the Mg dopants are highly ionic and actually mimic the chemical environment to oxygen as alkali metals, i.e., the case alike Li-rich compounds. Anyway, although all these non-alkali-rich compounds with ORR display generally improved voltage hysteresis behaviors compared with Li-rich compounds, the ORR itself takes place at high voltages, which always leads to strong voltage hysteresis and highly irreversible reactions [19][20][21] .…”

Section: Toc Graphicsmentioning

confidence: 99%

Negligible voltage hysteresis with strong anionic redox in conventional battery electrode

et al. 2020

Self Cite

View full text Add to dashboard Cite

“…With these merits, XAFS has been extensively applied for NRLO research. [ 75 ] Generally, the experimental setup and cell design from the above in situ/operando XRD test can also be applied to in‐place and real‐time XAFS measurements.…”

Section: Multiscale Characterizations Of Nrlo Degradationmentioning

confidence: 99%

“…[ 81 ] Besides sXAS, the resonant inelastic X‐ray scattering (RIXS) becomes popular recently to detect the anionic oxygen redox in batteries due to its good chemical sensitivity. [ 75,84 ] The RIXS fingerprint of oxygen redox is a sharp feature at approximately 523.8 eV emission energy. [ 75,84 ] The principle and application of RIXS in detecting oxygen redox can be found in another review.…”

Section: Multiscale Characterizations Of Nrlo Degradationmentioning

confidence: 99%

Probing and Resolving the Heterogeneous Degradation of Nickel‐Rich Layered Oxide Cathodes across Multi‐Length Scales

et al. 2020

View full text Add to dashboard Cite

though new energy storage devices such as lithium-sulfur batteries [2] and lithium-air batteries [3] have shown great promise due to large theoretical capacity, lithium ion batteries (LIBs) are still dominating in portable electronic devices, prevailing in electric vehicles, and gradually entering grid-energy storage markets. [4] The unsatisfactory energy density of cathodes is widely recognized as the critical bottleneck for higher-performance LIBs. [5] Among various cathodes, Ni-rich layered lithium transition-metal oxides possessing a larger reversible capacity (>180 mAh g −1) than LiCoO 2 (140 mAh g −1), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (160 mAh g −1), LiMn 2 O 4 (120 mAh g −1), and LiFePO 4 (160 mAh g −1), are regarded as one of the most promising cathodes for the next-generation LIBs. [6] In 2016, American electric vehicle company Tesla launched Model 3 with LiNi 0.85 Co 0.10 Al 0.05 O 2 as the cathode for its electric vehicle battery, a testament to the huge potential of Ni-rich layered oxides (NRLOs) (Scheme 1). NRLO cathodes generally consist of two main categories-LiNi 1−x−y Co x Mn y O 2 (NMC) and LiNi 1−x−y Co x Al y O 2 (NCA). The evolution from LiCoO 2 /LiNiO 2 / LiMnO 2 to LiNi 1−x−y Co x Mn y O 2 has been introduced in previous reviews. [7] Briefly, synthesizing LiCoO 2 with the low-defect density was relatively accessible due to the large difference in ionic radius between Li + and Co 3+ , but the irreversible structural change takes place when more than half a fraction of Li + is extracted from its lattice, restricting the capacity. Stoichiometric LiNiO 2 is difficult to prepare due to the instability of trivalent Ni at high temperatures, and the cation mixing between Li and Ni weakens the cycling stability of LiNiO 2. [8] Synthesis of the layered LiMnO 2 phase is not straightforward either, and the capacity fades rapidly because the structural transformation from layered to spinel phase is inevitable upon cycling. [9] LiNi 1−x−y Co x Mn y O 2 combines the strengths of nickel (high capacity), cobalt (good rate capability), and manganese (benign stability). [7] The redox couples of Ni 2+ /Ni 3+ /Ni 4+ and Co 3+ /Co 4+ contribute to the majority of the capacity. The existence of cobalt suppresses the cation mixing during the synthesis of stoichiometric compounds, while manganese helps stabilize the Ni-rich layered oxides (NRLO) are widely considered among the most promising cathode materials for high energy-density lithium ion batteries. However, the high proportion of Ni content accelerates the cycling degradation that restricts their large-scale applications. The origins of degradation are indeed heterogeneous and thus there are tremendous efforts devoted to understanding the underlying mechanisms at multi-length scales spanning atom/lattice, particle, porous electrode, solid-electrolyte interface, and cell levels and mitigating the degradation of the NRLO. This review combines various advanced in situ/ex situ analysis techniques developed for resolving NRLO degradation at multi-length scales and aims...

show abstract

Revisiting the charge compensation mechanisms in LiNi_0.8Co_0.2−yAl_yO₂ systems

Abstract: The emergence of oxidized oxygen RIXS features at high voltages for Ni-rich layered oxide cathodes.

Cited by 72 publications

References 78 publications

Unraveling the Cationic and Anionic Redox Reactions in a Conventional Layered Oxide Cathode

Unraveling the Cationic and Anionic Redox Reactions in a Conventional Layered Oxide Cathode

Negligible voltage hysteresis with strong anionic redox in conventional battery electrode

Probing and Resolving the Heterogeneous Degradation of Nickel‐Rich Layered Oxide Cathodes across Multi‐Length Scales

Contact Info

Product

Resources

About