Recent advance in structure regulation of high‐capacity Ni‐rich layered oxide cathodes

Qiu, Lang; Zhang, Mengke; Song, Yang; Xiao, Yao; Wu, Zhenguo; Xiang, Wei; Wang, Gongke; Sun, Yan; Zhang, Jun; Zhang, Bin; Guo, Xiaodong

doi:10.1002/eom2.12141

Cited by 43 publications

(29 citation statements)

References 151 publications

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“…Additionally, cathodes long time storage induces the loss of material surface oxygen, which makes TM ions migrate to the material surface, resulting in serious cation mixing. These intricate analysis unveil that TM/Li ions tend to migrate and induce structural reconstruction in layered structures with O vacancies, and points out that the following three aspects should be noted during the synthesis of layered cathodes with well-ordered structure and high stability: [33][34][35][36][37] (1) control the oxygen content in the synthesis process, fill oxygen vacancies in time, and reduce the migration of TM ions; (2) doping elements with strong metal-oxygen bond can improve the stability of the lattice oxygen; (3) maintain the stability of material interface to reduce oxygen loss, so as to inhibit TM ions segregation.…”

Section: Discussionmentioning

confidence: 99%

Structural Reconstruction Driven by Oxygen Vacancies in Layered Ni‐Rich Cathodes

Qiu

Song

Zhang

et al. 2022

Advanced Energy Materials

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However, the LiNi 1-x-y Co x Mn y O 2 (1 − x − y > 0.9) commercialization is hindered, because it suffers from serious structural instability in the long-term cycling due to the crack formation, structure degradation, and cathode-electrolyte interface film formation. [8][9][10] Notably, both the structure formation during calcination and the structure change during attenuation were directly related to the properties for NCM cathodes. [11,12] Currently, much efforts have been done on the structure evolution in the formation (high-temperature lithiation reaction) and degradation (charging/discharging) of NCM cathodes. For NCM formation, Wang and coworkers revealed that the structure change was actually a topological phase transformation process during the high-temperature lithiation of LiNi 0.77 Co 0.1 Mn 0.13 O 2 and involved multiple phase transformations. [1,[13][14][15] For NCM degradation, the loss of active elements, cation migration, and the lattice stress caused by Li + (de)intercalation led to the destruction of the layered structure and the sharp decay of performance during the charging/discharging. [16][17][18][19][20] Structure reconstruction induced by the migration ofLi, O, and transition metal (TM) ions plays a key role in the performance of Ni-based cathodes, yet their interactions are still poorly understood. This work investigates systematically the structure transformation of the high-temperature lithiation in air and oxygen rich atmosphere, charging process, and long-term storage. Structural and electrochemical characterization of Li-free/Li-containing phases (Ni 0.92 Co 0.04 Mn 0.04 (OH) 2 and Li x Ni 0.92 Co 0.04 Mn 0.04 O y ) and a series of detailed analyses provide an in-depth understanding of the structural reconstruction induced by the interaction of Li, O, and TM ions, i.e., the shift of Li/TM ions in the lattice leads to structural reconstruction via a layered structure with oxygen vacancies.

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Section: Discussionmentioning

confidence: 99%

Structural Reconstruction Driven by Oxygen Vacancies in Layered Ni‐Rich Cathodes

Qiu

Song

Zhang

et al. 2022

Advanced Energy Materials

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“…SPC is formed due to the large volume change during repeated H2-H3 phase transformation and is believed by some to be the main causes of capacity fade with high-Ni cathodes. 28,29 However, during the H2-H3 phase transformation, a large fraction of Ni 3+ ions become Ni 4+ ions that exhibit a strong reactivity towards the electrolyte. This makes the decoupling of EER and SPC complicated.…”

Section: Secondary Particle Cracking and Primary Particle Crackingmentioning

confidence: 99%

Degradation Pathways of Cobalt-free LiNiO2 Cathode in Lithium Batteries

Pan

Cui

et al. 2022

Preprint

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Electrode-electrolyte reactivity (EER) and particle cracking (PC) are considered two main causes of capacity fade in high-nickel layered oxide cathodes in lithium-based batteries. However, whether EER or PC is more critical remains debatable. Herein, the fundamental correlation between EER and PC is systematically investigated with LiNiO2 (LNO), the ultimate cobalt-free lithium layered oxide cathode. Specifically, EER is found more critical than secondary particle cracking (SPC) in determining the cycling stability of LNO; EER leads to primary particle cracking (PPC), but contrary to conventional wisdom, prevents SPC. Two surface degradation pathways are identified for cycled LNO under low and high EERs. A common blocking surface reconstruction layer (SRL) containing electrochemically-inactive Ni3O4 spinel and NiO rock-salt phases is formed on LNO at the charged state in an electrolyte with high EER; in contrast, an electrochemically-active SRL featuring regions of electron- and lithium-ion-conductive LiNi2O4 spinel phase is formed on LNO at the charged state in an electrolyte with low EER, even though bulk LiNi2O4 crystals are believed to be non-existent. These findings unveil the intrinsic degradation pathways of LNO cathode and are foreseen to provide new insights into the development of lithium-based batteries with minimized EER and maximized service life.

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“…The lithium-ion batteries (LIBs), first mass-marketed by Sony in 1990, are now widely used in electric vehicles (EVs) due to their advantages of high volumetric and gravimetric energy density. − However, the existing LIBs have not yet met the energy density required for EV applications, and the demand for researching a high-energy-density electrode material has increased significantly. Compared with the layered (LiCoO 2 ), spinel (LiNi 0.5 Mn 1.5 O 4 ), and olivine (LiFePO 4 and LiFe x Mn 1– x PO 4 ) materials, Ni-rich layered oxide cathodes (LiNi x Co y Mn z O 2 or LiNi x Co y Al z O 2, x + y + z = 1) have been considered as one of the most promising candidates for EVs because they can deliver a practical capacity over 200 mA h·g –1 , − thus meeting the requirements of the high endurance range of EVs.…”

Section: Introductionmentioning

confidence: 99%

Lattice Engineering to Refine Particles and Strengthen Bonds of the LiNi_0.9Co_0.05Mn_0.05O₂ Cathode toward Efficient Lithium Ion Storage

Tan

et al. 2022

ACS Sustainable Chem. Eng.

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Microstructural degradation of Ni-rich cathode materials is a major bottleneck limiting their widespread applications, originating from their microcracks due to lattice strain. Herein, a facile lattice engineering strategy (praseodymium substitution at octahedral 3b Ni sites) is constructed to greatly reduce the lattice strain of the LiNi0.9Co0.05Mn0.05O2 cathode. The relationship between the lattice strain and electrochemical performance is systematically examined to gain insights into the Pr activity-governing mechanisms. Furthermore, the experimental and DFT calculations reveal that praseodymium substitution not only reduces the lattice strain during the de-/lithiation and enhances the electronic activity near the Fermi level but also reduces local stress buildup by refining the primary particles to grow along the radial direction. The ameliorated LiNi0.9Co0.05Mn0.05O2 shows low lattice strain and achieves a record capacity retention of 92.3% after 100 cycles, higher than that of the original sample (capacity retention of 78.7%). Moreover, it still exhibits an ultrahigh capacity of 168 mA h·g–1 even at 10 C due to a lower Li+ migration energy barrier. This work deeply investigates the information on the bulk structure, electronic properties, and interaction mechanism between substitution cations and Ni-rich layered oxides, which provides a new insight into the design and construction of advanced high-capacity cathode materials.

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Recent advance in structure regulation of high‐capacity Ni‐rich layered oxide cathodes

Cited by 43 publications

References 151 publications

Structural Reconstruction Driven by Oxygen Vacancies in Layered Ni‐Rich Cathodes

Structural Reconstruction Driven by Oxygen Vacancies in Layered Ni‐Rich Cathodes

Degradation Pathways of Cobalt-free LiNiO2 Cathode in Lithium Batteries

Lattice Engineering to Refine Particles and Strengthen Bonds of the LiNi_0.9Co_0.05Mn_0.05O₂ Cathode toward Efficient Lithium Ion Storage

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Recent advance in structure regulation of high‐capacity Ni‐rich layered oxide cathodes

Cited by 43 publications

References 151 publications

Structural Reconstruction Driven by Oxygen Vacancies in Layered Ni‐Rich Cathodes

Structural Reconstruction Driven by Oxygen Vacancies in Layered Ni‐Rich Cathodes

Degradation Pathways of Cobalt-free LiNiO2 Cathode in Lithium Batteries

Lattice Engineering to Refine Particles and Strengthen Bonds of the LiNi0.9Co0.05Mn0.05O2 Cathode toward Efficient Lithium Ion Storage

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Lattice Engineering to Refine Particles and Strengthen Bonds of the LiNi_0.9Co_0.05Mn_0.05O₂ Cathode toward Efficient Lithium Ion Storage