Nanoscale surface modification to suppress capacity fade of Ni-Rich layered oxide material at high cut-off voltage

Fan, Peng; Zhang, Lixuan; Yang, Guangchang; Li, Yahao; Pan, Qichang; Liu, Yu; Hu, Sun; Zheng, Fenghua; Wang, Hongqiang; Li, Qingyu

doi:10.1016/j.cej.2022.138911

Cited by 19 publications

(7 citation statements)

References 63 publications

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“…The lattice constant “ c ” for both cathode materials initially increased and then abruptly decreased at the end of charging, but the sample 1%Nb-NM91 had a greatly suppressed lattice contraction of 2.29% compared to NM91 with a contraction of 3.39% (Figure d). As a result, the lattice volume change of 1%Nb-NM91 was significantly smaller than that of NM91 (2.35 vs 5.34%) (Figure e), suggesting the greatly improved structural stability upon Nb doping. − …”

Section: Resultsmentioning

confidence: 97%

Structural Reinforcement through High-Valence Nb Doping to Boost the Cycling Stability of Co-Free and Ni-Rich LiNi_0.9Mn_0.1O₂ Cathode Materials

Hu,

Ma,

et al. 2023

Energy Fuels

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As an important Co-free and Ni-rich layered oxide, LiNi 0.9 Mn 0.1 O 2 (NM91) has garnered significant interest as a promising cathode material for lithium-ion batteries. Despite its attractively high specific capacity, the intrinsic structural instability poses a great challenge to its electrochemical performances, especially cycling performance. In this work, we circumvent the structural instability issue of NM91 through high-valence Nb doping. Our findings reveal that high-valence Nb 5+ dopants were successfully incorporated into the lattice of LiNi 0.9 Mn 0.1 O 2 , functioning as interlayer pillars that reinforce the structure and mitigate the detrimental H2 → H3 phase transition. This results in greatly improved cycling stability and rate capability of the cathode. The discharge capacities of 1%Nb-NM91 reached 211.8 mA h g −1 at 0.1 C and 159.3 mA h g −1 at 5 C, with a retention rate of 95.6% after 100 cycles at 0.5 C, even superior to the previously reported lower Ni content counterparts, including LiNi 0.8 Co 0.15 Al 0.05 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , and so forth. This study demonstrates that highvalence Nb doping is a promising strategy to overcome the structural instability issue in LiNi 0.9 Mn 0.1 O 2 and underscores the potential of Co-free Ni-rich layered oxides as cathode materials for lithium-ion batteries.

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Section: Resultsmentioning

confidence: 97%

Structural Reinforcement through High-Valence Nb Doping to Boost the Cycling Stability of Co-Free and Ni-Rich LiNi_0.9Mn_0.1O₂ Cathode Materials

Hu,

Ma,

et al. 2023

Energy Fuels

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“…Note that SC90@LSTP-10 exhibits an outstanding discharge capacity of 192.6 mAh g –1 with a reversible capacity retention of 95.6% after 100 cycles at 0.5C (Figure S6a), while the pristine SC90@LSTP-0 cathode maintains only 147.4 mAh g –1 after 100 cycles, corresponding to 72.1% capacity retention at a capacity of 0.5 C (Figure S6b). Higher requirements of the operating voltage of Ni-rich cathodes are put forward to obtain higher energy density LIBs; however, the surface and bulk of single-crystal Ni-rich cathodes are more vulnerable to undergo irreversible structure deterioration at a high cutoff voltage. , To evaluate whether the LSTP protective coating is still effective under a high cutoff voltage, the cycle performance of SC90@LSTP-0 and SC90@LSTP-10 was examined at 2.8–4.5 V. Inspiringly, SC90@LSTP-10 still sustains a desirable specific capacity of 196.6 mAh g –1 after 100 cycles (Figure d and Figure S6c), which retains 87.3% capacity retention. In contrast, the specific capacity of SC90@LSTP-0 leads to a rapid attenuation after 100 cycles (Figure S6d), displaying a lower capacity retention of 63.2%.…”

Section: Resultsmentioning

confidence: 99%

Construction of Planar Gliding Restriction Buffer and Kinetic Self-Accelerator Stabilizing Single-Crystalline LiNi_0.9Co_0.05Mn_0.05O₂ Cathode

Tan

et al. 2023

ACS Appl. Mater. Interfaces

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The single-crystalline Ni-rich cathode has aroused much attention for extenuating the cycling and safety crises in comparison to the polycrystalline cathode. However, planar gliding and kinetic hindrance hinder its chemo-mechanical properties with cycling, which induce delamination cracking and damage the mechanical integrity in single crystals. Herein, a robust Li2.64(Sc0.9Ti0.1)2(PO4)3 (LSTP) ion/electron conductive network was constructed to decorate single-crystal LiNi0.9Co0.05Mn0.05O2 (SC90) particles. Via physicochemical characterizations and theoretical calculations, this LSTP coating that evenly grows on the SC90 particle with good lattice matching and strong bonding effectively restricts the anisotropic lattice collapse along the c-axis and the cation mixing activity of SC90, thus suppressing planar gliding and delamination cracking during repeated high-voltage lithiation/delithiation processes. Moreover, such a 3D LSTP network can also facilitate the lithium-ion transport and prevent the electrolyte’s corrosion, lightening the kinetic hindrance and triggering the surface phase transformation. Combined with the Li metal anode, the LSTP-modified SC90 cell exhibits a desirable capacity retention of 90.5% at 5 C after 300 cycles and stabilizes the operation at 4.3/4.5 V. Our results provide surface modification engineering to mitigate planar gliding and kinetic hindrance of the single-crystalline ultra-high Ni-rich cathode, which inspires peers to design other layered cathode materials.

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“…The O1s spectrum in Figure 4c includes peaks corresponding to oxygen vacancies (532.5 eV), oxygen impurities (531.7 eV), and lattice oxygen (529.1 eV). [ 45 ] Se–LNO has a lower percentage of lattice oxygen than LNO at 529.1 eV due to the shielding of the lattice oxygen signal by the Se coating layer. The C 1s spectrum consists of peaks corresponding to CO 3 2− (289.8 eV), CO (288.8 eV), CO (285.5 eV), and CC (284.8 eV).…”

Section: Resultsmentioning

confidence: 99%

Cobalt‐Free LiNiO₂ with a Selenium Coating as a High‐Energy Layered Cathode Material for Lithium‐Ion Batteries

et al. 2023

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Nanoscale surface modification to suppress capacity fade of Ni-Rich layered oxide material at high cut-off voltage

Cited by 19 publications

References 63 publications

Structural Reinforcement through High-Valence Nb Doping to Boost the Cycling Stability of Co-Free and Ni-Rich LiNi_0.9Mn_0.1O₂ Cathode Materials

Structural Reinforcement through High-Valence Nb Doping to Boost the Cycling Stability of Co-Free and Ni-Rich LiNi_0.9Mn_0.1O₂ Cathode Materials

Construction of Planar Gliding Restriction Buffer and Kinetic Self-Accelerator Stabilizing Single-Crystalline LiNi_0.9Co_0.05Mn_0.05O₂ Cathode

Cobalt‐Free LiNiO₂ with a Selenium Coating as a High‐Energy Layered Cathode Material for Lithium‐Ion Batteries

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Nanoscale surface modification to suppress capacity fade of Ni-Rich layered oxide material at high cut-off voltage

Cited by 19 publications

References 63 publications

Structural Reinforcement through High-Valence Nb Doping to Boost the Cycling Stability of Co-Free and Ni-Rich LiNi0.9Mn0.1O2 Cathode Materials

Structural Reinforcement through High-Valence Nb Doping to Boost the Cycling Stability of Co-Free and Ni-Rich LiNi0.9Mn0.1O2 Cathode Materials

Construction of Planar Gliding Restriction Buffer and Kinetic Self-Accelerator Stabilizing Single-Crystalline LiNi0.9Co0.05Mn0.05O2 Cathode

Cobalt‐Free LiNiO2 with a Selenium Coating as a High‐Energy Layered Cathode Material for Lithium‐Ion Batteries

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Structural Reinforcement through High-Valence Nb Doping to Boost the Cycling Stability of Co-Free and Ni-Rich LiNi_0.9Mn_0.1O₂ Cathode Materials

Structural Reinforcement through High-Valence Nb Doping to Boost the Cycling Stability of Co-Free and Ni-Rich LiNi_0.9Mn_0.1O₂ Cathode Materials

Construction of Planar Gliding Restriction Buffer and Kinetic Self-Accelerator Stabilizing Single-Crystalline LiNi_0.9Co_0.05Mn_0.05O₂ Cathode

Cobalt‐Free LiNiO₂ with a Selenium Coating as a High‐Energy Layered Cathode Material for Lithium‐Ion Batteries