Enhancing the Electrochemical Performance and Structural Stability of Ni-Rich Layered Cathode Materials via Dual-Site Doping

Chu, Mihai; Huang, Zhongyuan; Zhang, Taolve; Wang, Rui; Shao, Tielei; Wang, Chaoqi; Zhu, Weiming; He, Lunhua; Chen, Jie; Zhao, Wenguang; Xiao, Yinguo

doi:10.1021/acsami.1c00755

Cited by 58 publications

(35 citation statements)

References 46 publications

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“…Figure a corresponds to the in situ XRD of the first charging process. The (003) and (101) Bragg peaks around the 2θ region show a continuous hexagonal change upon charging, which is similar to that of other Ni-rich positive electrodes, that is H1 → M → H2 → H3. , Generally, the shift of the (003) reflection can be used to reflect the change of lattice parameters along the c -axis, and the shift of the (101) peak can be used to reflect the change of lattice parameters along the a -axis. When lithium ions are extracted, the (101) peak continues to shift monotonically to the right, indicating that the a -axis has suffered from continuous contraction along with the extraction of lithium ions, as shown in Figure b.…”

Section: Results and Discussionmentioning

confidence: 52%

Understanding of the Irreversible Phase Transition and Zr-Doped Modification Strategy for a Nickel-Rich Cathode under a High Voltage

Chen

et al. 2022

ACS Sustainable Chem. Eng.

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Increasing the nickel content and broadening the voltage window are important means for LiNi x Co y Mn 1−x−y O 2 layered cathodes with low cost and high energy density, but these nickel-rich cathodes often suffer from structural instability and unsatisfactory cyclic performance. The systematic and detailed degradation mechanism especially under a high voltage is still unclear, which hinders the further development of nickel-rich cathodes. Our results show that due to the migration of high valence nickel ions to lithium sites, especially upon the deep removal of Li + ions, the nickel-rich cathode undergoes an irreversible phase transformation from a layered structure to a spinel or even rocksalt phase. Such irreversible phase transitions within a wide voltage window would cause insufficient lithium utilization and voltage decay, finally deteriorating the electrochemical performance of nickel-rich cathodes. In a narrow voltage range of 3.0−4.3 V, the capacity retention of the Ni-rich cathode is 93.4%, and the voltage fading is only 40 mV after 250 cycles. However, the cathode only exhibits a capacity retention of 77.4% with a significant voltage decay over 180 mV, as the voltage range further extends to 3.0−4.6 V. Furthermore, various characterizations and electrochemical performances demonstrate that the strengthened metal−oxygen bonds in the transition layer can produce stable structures and suppress phase transitions, thereby displaying superior electrochemical performance in the widened voltage window. As a result, the cycling retention of a Zr-doped cathode reaches 84.5%, and the voltage decay is only 50 mV after 250 cycles at 3.0−4.6 V, which exhibits excellent long-term cycle performance. These insights provide guidance for understanding the electrochemical mechanism and the design of high-voltage cathode materials.

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Section: Results and Discussionmentioning

confidence: 52%

Understanding of the Irreversible Phase Transition and Zr-Doped Modification Strategy for a Nickel-Rich Cathode under a High Voltage

Chen

et al. 2022

ACS Sustainable Chem. Eng.

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“…Moreover, the stronger Nb–O bond stabilizes the stability of the lattice oxygen structure and inhibits the breakage of the Ni–O bond, thus inhibiting the migration of Ni 2+ to the Li layer during cycling and reducing the cation disorder. The smaller ion radius of transition metals Ni 3+ (0.56 Å), Co 3+ (0.55 Å), and Al 3+ (0.53 Å) relative to the dopant ion Nb 5+ (0.64 Å) and the conversion of Ni 3+ to Ni 2+ with a larger radius together contribute to the increased cell volume of NCA, thus enlarging the transition metal layer spacing …”

Section: Resultsmentioning

confidence: 99%

Enhancing Surface and Crystal Stability of the Ni-High NCA Cathode for High-Energy and Durable Lithium-Ion Batteries

Zhu

et al. 2022

Ind. Eng. Chem. Res.

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The promising LiNi 0.92 Co 0.05 Al 0.03 O 2 (NCA) cathode materials have become attractive recently for high-energy-density lithium-ion batteries (LIBs), but they suffer from severe capacity fade due to structure degradation and interface instability. Herein, a dual-modification strategy of Nb doping and Li 4 SiO 4 coating is employed to consolidate the surface and crystal stability of NCA. The Nb doping could suppress the anisotropic volume change and alleviate the generation of microcracks. Also, the Li 4 SiO 4 coating layer effectively accelerates the Li-ion transfer and protects the NCA surface from electrolyte attack. These advantages make the dual-modified NCA exhibit a high specific capacity of 199.2 mA h g −1 at 1 C with a capacity retention of 93.3% after 100 cycles. It delivers a high capacity of 160.0 mA h g −1 at 10 C, much higher than the pristine NCA (138.2 mA h g −1 ). The structure−performance relationship has been discussed. This work may provide guidance to modify Ni-high cathode materials for enhancing the high-energy and cyclic performance of LIBs.

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“…These 0D defects are either generated in the material synthesis process because of thermodynamic and kinetic limitations or generated during the battery cycling process. During the material synthesis process, atoms of similar sizes can exchange their positions, e.g., Li and Ni position exchange has been widely observed in layered oxide materials. − In addition to the intrinsic antisite defects, various atoms can also exchange their sites during the electrochemical cycling process, e.g., Ni goes to the Li site under a high delithiation state, leading to more antisite defects in battery materials. Moreover, under a high state of charge or thermal abuse condition, the oxygen ions may not be stable and can escape from the lattice in the form of oxygen gas .…”

Section: Origin Of Chemomechanical Degradationmentioning

confidence: 99%

Chemomechanics of Rechargeable Batteries: Status, Theories, and Perspectives

Vasconcelos

et al. 2022

Chem. Rev.

109

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Chemomechanics is an old subject, yet its importance has been revived in rechargeable batteries where the mechanical energy and damage associated with redox reactions can significantly affect both the thermodynamics and rates of key electrochemical processes. Thanks to the push for clean energy and advances in characterization capabilities, significant research efforts in the last two decades have brought about a leap forward in understanding the intricate chemomechanical interactions regulating battery performance. Going forward, it is necessary to consolidate scattered ideas in the literature into a structured framework for future efforts across multidisciplinary fields. This review sets out to distill and structure what the authors consider to be significant recent developments on the study of chemomechanics of rechargeable batteries in a concise and accessible format to the audiences of different backgrounds in electrochemistry, materials, and mechanics. Importantly, we review the significance of chemomechanics in the context of battery performance, as well as its mechanistic understanding by combining electrochemical, materials, and mechanical perspectives. We discuss the coupling between the elements of electrochemistry and mechanics, key experimental and modeling tools from the small to large scales, and design considerations. Lastly, we provide our perspective on ongoing challenges and opportunities ranging from quantifying mechanical degradation in batteries to manufacturing battery materials and developing cyclic protocols to improve the mechanical resilience.

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Enhancing the Electrochemical Performance and Structural Stability of Ni-Rich Layered Cathode Materials via Dual-Site Doping

Cited by 58 publications

References 46 publications

Understanding of the Irreversible Phase Transition and Zr-Doped Modification Strategy for a Nickel-Rich Cathode under a High Voltage

Understanding of the Irreversible Phase Transition and Zr-Doped Modification Strategy for a Nickel-Rich Cathode under a High Voltage

Enhancing Surface and Crystal Stability of the Ni-High NCA Cathode for High-Energy and Durable Lithium-Ion Batteries

Chemomechanics of Rechargeable Batteries: Status, Theories, and Perspectives

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