Elucidating and Mitigating High‐Voltage Degradation Cascades in Cobalt‐Free LiNiO<sub>2</sub> Lithium‐Ion Battery Cathodes (Adv. Mater. 3/2022)

Park, Kyu‐Young; Zhu, Yizhou; Torres‐Castanedo, Carlos G.; Jung, Hee Joon; Luu, Norman S.; Kahvecioğlu, Özgenur; Yoo, Yiseul; Seo, Jung-Woo; Downing, Julia R.; Lim, Hyeon‐Sook; Bedzyk, Michael J.; Wolverton, Christopher; Hersam, Mark C.

doi:10.1002/adma.202270026

Cited by 16 publications

(20 citation statements)

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“…It is generally considered that performance deteriorations in ultrahigh-Ni cathodes are tightly associated with the intergranular cracks that originate from the randomly oriented primary grains within secondary particles, which are primarily induced by the build-up of anisotropic mechanical strain due to the dramatic lattice shrinkage of the c -axis from H2 to H3 phase transitions. − This further results in detrimental electrode pulverization and electric isolation. What is worse, intergranular cracks will provide more channels for the facile electrolyte permeation into the particle interior, which exacerbates the interfacial side reactions between electrode (containing large amounts of unstable Ni 4+ ) and electrolyte at the fully charged state, further expediting the surface degradations and impedance growth during prolonged cycling. , Various approaches have been made to circumvent these issues for the performance enhancement of ultrahigh-Ni cathodes.…”

Section: Introductionmentioning

confidence: 99%

Multiscale Crystal Field Effect for High-Performance Ultrahigh-Ni Layered Cathode

Chen

Gao

et al. 2023

ACS Nano

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Further popularization of ultrahigh-Ni layered cathodes for high-energy lithium-ion batteries (LIBs) is hampered by their grievous structural and interfacial degeneration upon cycling. Herein, by leveraging the strong electronegativity and low solubility properties of Sb element, a multifunctional modification that couples atomic/microstructural reconstruction with interfacial shielding is well designed to improve the LiNi 0.94 Co 0.04 Al 0.02 O 2 (NCA) cathode by combining Sb 5+ doping and Li 7 SbO 6 coating. Notably, a robust O framework is established by regulating local O coordination owing to the incorporation of a strong Sb−O covalence bond, leading to the inhibited lattice O evolution at high voltage, as revealed by synchrotron X-ray absorption spectroscopy. Moreover, the radially aligned primary particles with (003) crystallographic texture and refined/elongated sizes are achieved by the pinning of Sb on grain boundaries and are confirmed by scanning transmission electron microscopy, resulting in the fast Li + diffusion and mitigated particle cracking. Additionally, in situ construction of the Li 7 SbO 6 ionic conductive layer on grain boundaries can effectively boost interfacial stability and Li + kinetics. As a result, the optimal Sb-modified NCA delivers a high capacity retention of 94.6% after 200 cycles at 1 C and a good rate capacity of 183.9 mAh g −1 at 10 C, which is expected to be applied to next-generation advanced LIBs.

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Section: Introductionmentioning

confidence: 99%

Multiscale Crystal Field Effect for High-Performance Ultrahigh-Ni Layered Cathode

Chen

Gao

et al. 2023

ACS Nano

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“…This approach, however, leads to a more rapid capacity fade during charge/discharge cycling. [ 7–10 ] Therefore, a thorough understanding of the degradation mechanism of Ni‐rich cathode upon high‐voltage cycling is of great importance for the development of high‐energy‐density LIBs.…”

Section: Introductionmentioning

confidence: 99%

High‐Voltage Induced Surface and Intragranular Structural Evolution of Ni‐Rich Layered Cathode

Liu

Xie

et al. 2022

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Layered Ni‐rich lithium transition metal oxides are promising cathode materials for high‐energy‐density lithium‐ion batteries. These cathodes, however, suffer from rapid performance decay under high‐voltage operation. In this work, the electrochemical properties and structural evolution of the LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode upon high‐voltage cycling are investigated. The results show that the NMC811 cathode not only experiences surface evolution with the formation of Li‐deficient rock‐salt layers, but also suffers from drastic intragranular structural changes inside bulk grains after high‐voltage cycling. Direct evidence for the formation of transition‐metal/Li disordering domains with uneven Li content and lattice plane distortion at the internal grains of 4.6 V‐cycled NMC811 are provided with their atomic ordering and spatial distribution clearly resolved. The complex intragranular structural changes impede Li+ diffusion inside bulk material, resulting in kinetic limitation and capacity loss. The results demonstrate that the high‐voltage cycling would induce severe structural degradation at the grain interior of the cathode material beyond surface evolution, which contributes significantly to the rapid performance decay of the NMC811 cathode. The findings provide new insights for developing effective countermeasures to mitigate this degradation pathway.

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“…Figure 4e exhibits the cycling stability conducted at 1 C between 2.7 and 4.5 V, in which the accelerated capacity fading is noticed for both electrodes compared with the voltage range of 2.7–4.3 V, which may be attributed to the irreversible lattice oxygen loss and aggravated electrode/electrolyte interface side reaction at high‐voltage. [ 13 ] Notably, an outstanding capacity retention of 93.1% coupled with a slight voltage drop of 0.124 V is achieved for SrZr‐NCM after 200 cycles, which are still much better than those of NCM (69.5% and 0.514 V, respectively), as confirmed in Figure 4e and Figure S20, Supporting Information, further confirming the reinforced structure/interface stability after Sr/Zr modification. The cycling performances at a high temperature of 55 °C demonstrated that both electrodes suffer severe capacity fading, as shown in Figure 4f, only 68.0% and 93.4% of the initial capacity are retained after 100 cycles for NCM and SrZr‐NCM, respectively.…”

Section: Resultsmentioning

confidence: 56%

Enabling Structure/Interface Regulation for High Performance Ni‐Rich Cathodes

Ni,

Chen,

Guo

et al. 2023

Adv Funct Materials

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Further commercialization of Ni‐rich layered cathodes is hindered by severe structure/interface degradation and kinetic hindrance that occur during electrochemical operation, which leads to safety risks and reduced range in electric vehicles (EVs). Herein, by selecting elements with different solubility properties, a multifunctional strategy that synchronously fabricates perovskite‐type SrZrO3 coating and Sr/Zr co‐doping is employed to strengthen the structure/interface stability and the Li+ transport mobility of LiNi0.85Co0.10Mn0.05O2 (NCM). Perovskite‐type SrZrO3 protective layers formed on the particle surface can substantially mitigate the unexpected interfacial side reactions and surface phase transitions. In addition, a robust crystal framework is constructed by optimizing local O coordination through the introduction of strong Zr−O bonds. Notably, Li+ diffusion kinetics is effectively improved due to expanded cell parameters and O‐Li‐O slab spacing with the incorporation of large‐diameter Sr pillar ions, as revealed by X‐ray diffraction. As a result, the Sr/Zr‐modified NCM achieves a remarkable capacity retention of 99.4% after 200 cycles at 1 C, and a high rate capacity of 168.9 mAh g−1 at 10 C. This work opens new avenues to develop high‐performance NCM cathodes with high energy and high power for EVs with long calendar life.

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Elucidating and Mitigating High‐Voltage Degradation Cascades in Cobalt‐Free LiNiO₂ Lithium‐Ion Battery Cathodes (Adv. Mater. 3/2022)

Cited by 16 publications

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Multiscale Crystal Field Effect for High-Performance Ultrahigh-Ni Layered Cathode

Multiscale Crystal Field Effect for High-Performance Ultrahigh-Ni Layered Cathode

High‐Voltage Induced Surface and Intragranular Structural Evolution of Ni‐Rich Layered Cathode

Enabling Structure/Interface Regulation for High Performance Ni‐Rich Cathodes

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Elucidating and Mitigating High‐Voltage Degradation Cascades in Cobalt‐Free LiNiO2 Lithium‐Ion Battery Cathodes (Adv. Mater. 3/2022)

Cited by 16 publications

References 0 publications

Multiscale Crystal Field Effect for High-Performance Ultrahigh-Ni Layered Cathode

Multiscale Crystal Field Effect for High-Performance Ultrahigh-Ni Layered Cathode

High‐Voltage Induced Surface and Intragranular Structural Evolution of Ni‐Rich Layered Cathode

Enabling Structure/Interface Regulation for High Performance Ni‐Rich Cathodes

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Product

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Elucidating and Mitigating High‐Voltage Degradation Cascades in Cobalt‐Free LiNiO₂ Lithium‐Ion Battery Cathodes (Adv. Mater. 3/2022)