The effect of oxygen vacancy and spinel phase integration on both anionic and cationic redox in Li-rich cathode materials

Li, Qingyuan; Ning, De; Zhou, Dong; An, Ke; Wong, Deniz; Zhang, Lijuan; Chen, Zhenhua; Schuck, Götz; Schulz, Christian; Xu, Zijian; Schumacher, G.; Liu, Xiangfeng

doi:10.1039/d0ta02517h

Cited by 119 publications

(89 citation statements)

References 71 publications

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“…The underlying fine structure could be revealed by the vibration near the elastic peak at 0.1–0.9 eV (Fig. 4f ) 26 , 38 . It is reported that the vibration frequency is closely related to the species of O–O dimer 26 .…”

Section: Resultsmentioning

confidence: 99%

Addressing voltage decay in Li-rich cathodes by broadening the gap between metallic and anionic bands

Zhang

Wong

et al. 2021

Nat Commun

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Oxygen release and irreversible cation migration are the main causes of voltage fade in Li-rich transition metal oxide cathode. But their correlation is not very clear and voltage decay is still a bottleneck. Herein, we modulate the oxygen anionic redox chemistry by constructing Li2ZrO3 slabs into Li2MnO3 domain in Li1.21Ni0.28Mn0.51O2, which induces the lattice strain, tunes the chemical environment for redox-active oxygen and enlarges the gap between metallic and anionic bands. This modulation expands the region in which lattice oxygen contributes capacity by oxidation to oxygen holes and relieves the charge transfer from anionic band to antibonding metal–oxygen band under a deep delithiation. This restrains cation reduction, metal–oxygen bond fracture, and the formation of localized O2 molecule, which fundamentally inhibits lattice oxygen escape and cation migration. The modulated cathode demonstrates a low voltage decay rate (0.45 millivolt per cycle) and a long cyclic stability.

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Section: Resultsmentioning

confidence: 99%

Addressing voltage decay in Li-rich cathodes by broadening the gap between metallic and anionic bands

Zhang

Wong

et al. 2021

Nat Commun

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“…LMNCA‐urea‐mic and LMNCA‐EG‐mic samples have slightly increased lattice parameters compared to LMNCA‐urea‐a and LMNCA‐EG‐a. The increase in lattice parameters is due to the reduction expansion mainly caused by the reduction of transition metal cation oxidation states and the corresponding increased cation radii of the reduced transition metals cations [37, 38]. The slight increase in the lattice parameters and unit cell volume for microwave irradiation LMNCA urea‐mic and LMNCA EG‐mic suggests better lithium diffusion in the structure.…”

Section: Resultsmentioning

confidence: 99%

“…The slight increase in the lattice parameters and unit cell volume for microwave irradiation LMNCA urea-mic and LMNCA EG-mic suggests better lithium diffusion in the structure. The small lattice contraction that maybe caused by oxygen vacancies has minor effect in the lattice parameters for nonstoichiometric compounds [37,39,40]. The I (003) /I (104) intensity ratio is usually used to characterized the degree of cation mixing in the Li layer formed by some Ni 2 + ions occupying Li + sites due to similar radii of Li + (0.76 Å) and Ni 2 + (0.69 Å) [41][42][43].…”

Section: Morphology and Structure Characterizationmentioning

confidence: 99%

Influence of Microwave Irradiation and Combustion Fuels on the Rate Capability and Cycle Performance of Li_1.2Mn_0.52Ni_0.13Co_0.13Al_0.02O₂ Layered Material

et al. 2020

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Commercialization of lithium-manganese rich oxides (LMR-NMC) cathodes for lithium-ion batteries is hindered by shortcomings such as severe capacity fade and poor rate capability. This work reveals the synergetic effect of the structure and morphology in reducing capacity fade and improving rate capability in Li 1.2 Mn 0.52 Ni 0.13 Co 0.13 Al 0.02 O 2 (LMNCA) cathode. The results show that the hybrid microwave irradiation-combustion synthesis results in smaller particles, increased lattice parameters, reduced transition metal oxidation states, and high Li-ion diffusion coefficients. These resulted in powders with reduced capacity fade and enhanced rate performance. LMNCA urea-mic exhibited the best electrochemical performance with a discharge capacity of 360 mAh/g and capacity retention of 88 % after 50 cycles at 0.1 C.

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“…Ni +2/+4 , Co +3/+4 , and Mn +3/+4 contribute a maximum of 170-180 mAh g -1 capacity, whereas the bulk oxygen redox accounts for the rest of the capacity. Several theories on oxygen redox are reported in the literature [80,81]. Whatever way it takes part in the charge-discharge mechanism, it also brings in several adverse side effects when oxygen gas is released from the surface.…”

Section: Lithiation-delithiation Mechanismmentioning

confidence: 99%

A Review on High-Capacity and High-Voltage Cathodes for Next-Generation Lithium-ion Batteries

Ghosh¹,

charjee²,

Bhowmik³

et al. 2021

JEPT

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lithium-ion battery (LIB) is at the forefront of energy research. Over four decades of research and development have led electric mobility to a reality. Numerous materials capable of storing lithium reversibly, either as an anode or as a cathode, are reported on a daily basis. But very few among them, such as LiCoO2, lithium nickel manganese cobalt oxide (Li-NMC) variants (LiNi0.33Mn0.33Co0.33O2, LiNi0.5Mn0.3Co0.2O2, LiNi0.6Mn0.2Co0.2O2, and LiNi0.8Mn0.1Co0.1O2), LiNi0.8Co0.15Al0.05O2, LiFePO4, graphite, and Li4Ti5O12 are successful at commercial scale. Future energy requirements demand a push in the energy density of LIBs to meet the criteria of electric aviation, power trains, stationary grids, etc. All these applications have different needs which cannot be satisfied by a particular set of materials. Therefore, various materials need to be utilized in widespread fields of battery applications in the near future. This review discusses potential cathode materials that show a capacity of ≥ 250 mAh g-1 (Li-rich oxides, conversion materials, etc.) or average voltage of ≥ 4 V vs. Li+/Li (polyanionic materials, spinel oxides, etc.). Failure mechanisms, challenges, and way-outs to overcome all the issues are put forward to determine commercial viability.

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The effect of oxygen vacancy and spinel phase integration on both anionic and cationic redox in Li-rich cathode materials

Abstract: The effect of oxygen vacancy and spinel phase integration on anionic and cationic redox in Li-rich cathode materials was unraveled.

Cited by 119 publications

References 71 publications

Addressing voltage decay in Li-rich cathodes by broadening the gap between metallic and anionic bands

Addressing voltage decay in Li-rich cathodes by broadening the gap between metallic and anionic bands

Influence of Microwave Irradiation and Combustion Fuels on the Rate Capability and Cycle Performance of Li_1.2Mn_0.52Ni_0.13Co_0.13Al_0.02O₂ Layered Material

A Review on High-Capacity and High-Voltage Cathodes for Next-Generation Lithium-ion Batteries

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The effect of oxygen vacancy and spinel phase integration on both anionic and cationic redox in Li-rich cathode materials

Abstract: The effect of oxygen vacancy and spinel phase integration on anionic and cationic redox in Li-rich cathode materials was unraveled.

Cited by 119 publications

References 71 publications

Addressing voltage decay in Li-rich cathodes by broadening the gap between metallic and anionic bands

Addressing voltage decay in Li-rich cathodes by broadening the gap between metallic and anionic bands

Influence of Microwave Irradiation and Combustion Fuels on the Rate Capability and Cycle Performance of Li1.2Mn0.52Ni0.13Co0.13Al0.02O2 Layered Material

A Review on High-Capacity and High-Voltage Cathodes for Next-Generation Lithium-ion Batteries

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Influence of Microwave Irradiation and Combustion Fuels on the Rate Capability and Cycle Performance of Li_1.2Mn_0.52Ni_0.13Co_0.13Al_0.02O₂ Layered Material