Role of Residual Li and Oxygen Vacancies in Ni-rich Cathode Materials

Li, Lingjun; Chen, Jiaxin; Huang, He; Liu, Tan; Song, Liubin; Wu, Hong‐Hui; Wang, Chu; Zhao, Zixiang; Yi, Hongling; Duan, Junfei; Dong, Ting

doi:10.1021/acsami.1c06550

Cited by 64 publications

(35 citation statements)

References 54 publications

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“…In Figure d, the O 1s peaks (531.2 eV) are related to carbonates from the electrolyte decomposition, which corresponds to the CO bond in the C 1s spectrum (Figure S8 of the Supporting Information), and the peak at 530.2 eV is assigned to metal–oxygen (M–O). , In the XPS spectra of 1.0% V-NCM@ZVO, the reinforced M–O bonding and reduced CO bonding show a less interfacial parasitic reaction as a result of stable lattice oxygen contributing to the strong V–O bonds and robust ZVO protective layer. For the F 1s spectra (Figure e), LiF (684.3 eV) and Li x PO y F z (685.4 eV) are derived from interface side reactions, ,− which are consistent with the P–O–F bonds in P 2p spectra (Figure S9 of the Supporting Information). The peak intensity of LiF and Li x PO y F z in 1.0% V-NCM@ZVO is lower than that of NCM83, indicating a more stable interface.…”

Section: Resultssupporting

confidence: 64%

In Situ Co-modification Strategy for Achieving High-Capacity and Durable Ni-Rich Cathodes for High-Temperature Li-Ion Batteries

et al. 2022

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Operating Li-ion batteries in a harsh environment will greatly degrade the cyclic performance and safety of Ni-rich layered cathodes, which challenges the current modification approaches to form a more stable interface with the electrolyte and a robust crystal structure. Herein, we demonstrate the surface engineering enabling V-doped and ZrV 2 O 7 -coated Ni-rich layered cathodes (V-NCM@ZVO), where stoichiometric ZVO generates on the surface of oxides and tailorable V subsequently diffuses into the bulk phase during high-temperature lithiation. The introduction of high-energy V−O bonds vastly refrains the lattice oxygen escape, and meantime, ionic conductive and electrochemically inert ZVO ensures a robust interphase on the Ni-rich cathode, greatly enhancing the thermal stability. At 55 °C, the modified cathode displays a high reversible capacity of 220.3 mAh g −1 at 0.2 C and 183.0 mAh g −1 at 10 C. More impressively, the assembled V-NCM@ZVO//graphite pouch-type cell exhibits a capacity retention of 90.2% at 1 C after 400 cycles at 55 °C. This work exhibits a feasible modification strategy to strengthen the surface and crystal stability in parallel of Ni-rich cathodes to meet high-temperature Li-ion batteries.

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Section: Resultssupporting

confidence: 64%

In Situ Co-modification Strategy for Achieving High-Capacity and Durable Ni-Rich Cathodes for High-Temperature Li-Ion Batteries

et al. 2022

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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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“…Lithium-ion batteries (LIBs) have been widely used in various energy storage devices due to their high specific capacity, long cycle life, no memory effect, and environmental friendliness. − The performance of the battery is mainly limited by the cathode material, so the development of high-capacity cathode materials has become the focus of researchers. − Compared with traditional lithium cobaltate (LiCoO 2 , LCO), spinel lithium manganate (LiMn 2 O 4 , LMO) has the advantages of low cost, high safety, and environmental friendliness and is one of the most competitive cathode materials of LIBs. , Different from precious metal resources such as nickel and cobalt, manganese resources are rich in reserves. Electrolytic manganese dioxide (EMD) is the product of anodic oxidation of divalent manganese, with low price and abundant output.…”

Section: Introductionmentioning

confidence: 99%

Effect of Co³⁺ Doping on Crystal Structure and Electrochemical Properties of Spinel LiMn₂O₄ Cathode Material

Luo

Wang

et al. 2022

Energy Fuels

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To inhibit the influence of structural distortion caused by the Jahn–Teller effect on LiMn2O4 (LMO), the spinel LMO doped with cobalt ions is prepared by a simple solid-state calcining method. The effects of different cobalt doping amounts on the structure and electrochemical properties of LMO are investigated. The XRD refinement results show that Co3+ successfully enters the lattice of LMO, and its spinel structure is not changed. Due to the smaller radius of Co3+ and the larger bond energy, the unit cell of the LMO material shrinks, and the spinel structure is more stable. The initial capacity of the material decreases with the increase of Co doping content, but the cycle performance is significantly improved. Impressively, when Co doped at x = 0.04, the initial discharge specific capacity of the LMO-0.04 sample is 115.5 mAh·g–1 at 0.1C, and the capacity retention rate is still 81.04% after 500 cycles. The cycle times are much higher than that of the pure LMO sample. Additionally, the diffusion coefficient of Li+ calculated by the Randles–Sevcik equation shows that the doping of Co3+ significantly improves the mobility of Li+ compared with pure LMO. Hence, Co3+ doping can effectively inhibit the structural distortion caused by the Jahn–Teller effect and improve the electrochemical performance of LMO.

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Role of Residual Li and Oxygen Vacancies in Ni-rich Cathode Materials

Cited by 64 publications

References 54 publications

In Situ Co-modification Strategy for Achieving High-Capacity and Durable Ni-Rich Cathodes for High-Temperature Li-Ion Batteries

In Situ Co-modification Strategy for Achieving High-Capacity and Durable Ni-Rich Cathodes for High-Temperature Li-Ion Batteries

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

Effect of Co³⁺ Doping on Crystal Structure and Electrochemical Properties of Spinel LiMn₂O₄ Cathode Material

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Role of Residual Li and Oxygen Vacancies in Ni-rich Cathode Materials

Cited by 64 publications

References 54 publications

In Situ Co-modification Strategy for Achieving High-Capacity and Durable Ni-Rich Cathodes for High-Temperature Li-Ion Batteries

In Situ Co-modification Strategy for Achieving High-Capacity and Durable Ni-Rich Cathodes for High-Temperature Li-Ion Batteries

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

Effect of Co3+ Doping on Crystal Structure and Electrochemical Properties of Spinel LiMn2O4 Cathode Material

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Effect of Co³⁺ Doping on Crystal Structure and Electrochemical Properties of Spinel LiMn₂O₄ Cathode Material