Engineering of cobalt-free Ni-rich cathode material by dual-element modification to enable 4.5 V-class high-energy-density lithium-ion batteries

Lv, Yao; Huang, Shan; Lu, Sirong; Jia, Tianqi; Liu, Yanru; Ding, Wenbo; Yu, Xiaoliang; Kang, Feiyu; Zhang, Jiujun; Cao, Yidan

doi:10.1016/j.cej.2022.140652

Cited by 18 publications

(13 citation statements)

References 64 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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“…The Li x PO y F z signal implies the decomposition of the lithium salt. 43 The presence of a LiF signal is closely associated with the side reaction between the surface residual LiOH and HF generated by the decomposition of the lithium salt. For the C 1s spectra, as shown in Figure 5c, the intensities of C�O, C−O, and OCO 2 peaks are significantly lower in AT-NCM as compared to those in P-NCM, indicating that the degree of decomposition of the electrolyte was reduced after introducing Al/Ta.…”

Section: Structure and Interfacial Stability After Cyclingmentioning

confidence: 99%

Structure and Charge Regulation Strategy Enabling Superior Cycling Stability of Ni-Rich Cathode Materials

Zeng,

Fan,

Zheng

et al. 2024

ACS Appl. Mater. Interfaces

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Ni-rich layered oxides LiNi x Co y Mn 1−x−y O 2 (NCMs, x > 0.8) are the most promising cathode candidates for Li-ion batteries because of their superior specific capacity and cost affordability. Unfortunately, NCMs suffer from a series of formidable challenges such as structural instability and incompatibility with commonly used electrolytes, which seriously hamper their practical applications on a large scale. Herein, the Al/Ta codoping modification strategy is proposed to improve the performance of the LiNi 0.83 Co 0.1 Mn 0.07 O 2 cathode, and the asprepared Al/Ta-modified LiNi 0.83 Co 0.1 Mn 0.07 O 2 delivers exceptional cycling stability with a capacity retention of 97.4% after 150 cycles at 1C and an excellent rate performance with a high capacity of 143.2 mAh g −1 even at 3C. Based on the experimental study, it is found that the structural stability of NCM is strengthened due to the regulated coordination of oxygen by introducing a robust Ta−O covalent bond, which prevents the layered structure from collapsing. Moreover, the reconstructed rock-salt-like surface is capable of effectively inhibiting interfacial side reactions as well as the overgrowth of the cathode−electrolyte interface. Theoretically, the energy of Li/Ni mixing is significantly increased with the introduction of Al and Ta elements in Al/Ta codoped NCM, leading to inhibited adverse phase transition during cycling. A feasible pathway for designing and developing advanced Ni-rich cathode materials for Li-ion batteries is provided in this work.

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“…1,2,11,3−10 Recent literature has reported that NM cathode material would exhibit higher thermal stability than NCM; however, it suffers from poor rate capacity and larger Li/Ni cation disorder as a result of magnetic resistance between Ni 2+ /Ni 3+ and Mn 4+ . 12−14 Tailoring the formation of single-crystal, 15,16 coating microstructures, 17−19 and doping high-valence elements involving Zr 4+ , 20 Sn 4+ , 21 Ta 5+ , 22−24 Nb 5+ , 22 W 6+ , 25−27 and Mo 6+28−30 have been adopted to restrain Li/Ni mixing and the lattice parameter changes in the H2−H3 phase transition of the NM cathode, to improve the structural stability. In addition, the Keggin structure metal oxide cluster PMo 12 O 40 3− , with ionic conductivity and electronic transferability, has been studied in the LIB field.…”

Section: Introductionmentioning

confidence: 99%

“…Tailoring the formation of single-crystal, , coating microstructures, − and doping high-valence elements involving Zr 4+ , Sn 4+ , Ta 5+ , − Nb 5+ , W 6+ , − and Mo 6+ − have been adopted to restrain Li/Ni mixing and the lattice parameter changes in the H2–H3 phase transition of the NM cathode, to improve the structural stability. In addition, the Keggin structure metal oxide cluster PMo 12 O 40 3– , with ionic conductivity and electronic transferability, has been studied in the LIB field.…”

Section: Introductionmentioning

confidence: 99%

Ion-Exchanged Phosphomolybdic Acid Interfacial Modification Enhances the Electrochemical Performance of LiNi_0.9Mn_0.1O₂

Zhou,

Zhang,

Zhai

et al. 2023

Energy Fuels

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With the Keggin structure PMo 12 O 40 3− of phosphomolybdic acid (PMA) taken into account, the interfacial physicochemical property of PMA was adjusted through Li-ion exchange, and then Liexchanged PMA was adopted to modify the cathode material LiNi 0.9 Mn 0.1 O 2 (NM91) via the solid-phase method, aiming at improving the rate performance and cycling stability of the cathode. The optimal ion-exchanged PMA (PMA-e2)-modified NM91 (named 91PMA-e2) shows an initial discharge capacity of 216.6 mAh g −1 at 0.1 C and a capacity retention of 84.8% after 100 cycles (1 C and 2.8−4.5 V) as well as the best rate performance, which is superior to those of pristine NM91. With characterization by X-ray diffraction (XRD), X-ray photoelectron spectroscopy, high-resolution transmission electron microscope, in situ XRD measurements, etc., it indicates that PMA-e2 modification can reduce the Li/Ni mixing degree but enlarge the thickness of the lithium layer (T LiOd 6 ) and facilitate Li + diffusion. The results suggest that the Keggin structure of PMA as well as the acidity property and priority adsorption toward water molecules are associated with the Li-ion exchange degree. In combination with the depth-profiling XPS measurement of the spent samples experienced in 300 cycles, it illustrates that spent 91PMA-e2 possesses higher amounts of LiF and Ni 3+ but a lower amount of Li x PO y F z , which are due to the coating layer generated from the Keggin structure of PMA-e2. Such a Keggin structure has the capacity to trap trace amounts of water and inhibit the hydrolysis reaction of PF 5 , consequently maintaining the stable structure of the cathode and achieving superior cycling retention.

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Engineering of cobalt-free Ni-rich cathode material by dual-element modification to enable 4.5 V-class high-energy-density lithium-ion batteries

Cited by 18 publications

References 64 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

Structure and Charge Regulation Strategy Enabling Superior Cycling Stability of Ni-Rich Cathode Materials

Ion-Exchanged Phosphomolybdic Acid Interfacial Modification Enhances the Electrochemical Performance of LiNi_0.9Mn_0.1O₂

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Engineering of cobalt-free Ni-rich cathode material by dual-element modification to enable 4.5 V-class high-energy-density lithium-ion batteries

Cited by 18 publications

References 64 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

Structure and Charge Regulation Strategy Enabling Superior Cycling Stability of Ni-Rich Cathode Materials

Ion-Exchanged Phosphomolybdic Acid Interfacial Modification Enhances the Electrochemical Performance of LiNi0.9Mn0.1O2

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Product

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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

Ion-Exchanged Phosphomolybdic Acid Interfacial Modification Enhances the Electrochemical Performance of LiNi_0.9Mn_0.1O₂