Oxygen Vacancy Diffusion and Condensation in Lithium‐Ion Battery Cathode Materials

Lee, Sanghan; Jin, Wooyoung; Kim, Su Hwan; Joo, Se Hun; Nam, Gyutae; Oh, Pilgun; Kim, Young-Ki; Kwak, Sang Kyu; Cho, Jaephil

doi:10.1002/anie.201904469

Cited by 125 publications

(74 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[3,34,35] As we all know, surface coating is a popular and effective strategy to alleviate the side reactions between cathode and electrolyte. [3,[36][37][38][39] Namely, the electrochemical performance of this single-crystal Ni-rich cathode may have a room for further improvement, if the surface modification is conducted.…”

Section: Resultsmentioning

confidence: 99%

Highly‐Dispersed Submicrometer Single‐Crystal Nickel‐Rich Layered Cathode: Spray Synthesis and Accelerated Lithium‐Ion Transport

Leng

Wang

Peng

et al. 2021

Small

View full text Add to dashboard Cite

For conventional polycrystalline Ni‐rich cathode material consisting of numerous primary particles in disordered orientation, the crystal anisotropy in charge/discharge process results in the poor rate capability and rapid capacity degradation. In this work, highly‐dispersed submicron single‐crystal LiNi0.8Co0.15Al0.05O2 (SC‐NCA) cathode is efficiently prepared by spray pyrolysis (SP) technique followed by a simple solid‐state lithiation reaction. Porous Ni0.8Co0.15Al0.05Ox precursor prepared via SP exhibits high chemical activity for lithiation reaction, enabling the fabrication of single‐crystal cathode at a relatively low temperature. In this way, the contradiction between high crystallinity and cation disordering is well balanced. The resulted optimized SC‐NCA shows polyhedral single‐crystal morphology with moderate grain size (≈1 μm), which are beneficial to shortening the Li+ diffusion path and improving the structural stability. As cathode for lithium ion batteries, SC‐NCA delivers a high discharge capacity of 202 and 140 mAh g−1 at 0.1 and 10 C, respectively, and maintains superior capacity retention of 161 mAh g−1 after 200 cycles at 1C. No micro‐crack is observed in the cycled SC‐NCA particles, indicating such single‐crystal morphology can greatly relieve the anisotropic micro‐strain. This effective, continuous and adaptable strategy for preparing single‐crystal Ni‐rich cathode without any additive may accelerate their practical application.

show abstract

Section: Resultsmentioning

confidence: 99%

Highly‐Dispersed Submicrometer Single‐Crystal Nickel‐Rich Layered Cathode: Spray Synthesis and Accelerated Lithium‐Ion Transport

Leng

Wang

Peng

et al. 2021

Small

View full text Add to dashboard Cite

show abstract

“…Lee et al suggested that the directional cracking through the TEM and STEM, the migration of oxygen vacancy in the bulk has a preference of facet. [25] The STEM results from Yan et al also support that the spinel phase and oxygen loss behavior in the bulk. [23] Furthermore, the enhanced ABF (eABF) imaging by 4D STEM reported by Ahmed et al sheds light on the better observation of light elements such as oxygen.…”

Section: Spectroscopic Techniques To Probe the Oxygen Redox Related Phenomenonmentioning

confidence: 86%

“…Figure25. Concentration gradient in coating: a) Representation of nickel-rich core for high capacity covered by a manganese-rich shell; the shell comprises crystallites with a columnar or slab-like morphology, with lithium diffusion direction radiating from particle center as indicated by the blue arrows; b) transmission electron microscopy (TEM) images of the columnar/slab-like crystallites comprising the manganese-rich shell; Reproduced with permission.…”

mentioning

confidence: 99%

Utilizing Oxygen Redox in Layered Cathode Materials from Multiscale Perspective

Lee

Lau

Yang

et al. 2021

Advanced Energy Materials

View full text Add to dashboard Cite

In high‐capacity layered oxide cathode materials, utilization of lattice oxygen as a redox center is considered to be one of the most promising approaches to overcome the capacity limitation set by conventional transition metal redox centers. However, rapid material degradation is often associated with oxygen oxidation, leading to formidable challenges in utilizing oxygen redox. Further mechanistic understanding of the oxygen activities thus becomes critical to better control oxygen redox reactions. This review summarizes recent advances for investigating oxygen redox reactions in cathode materials from a multiscale perspective, i.e., from the atomistic level to the microstructure regime. First the mechanistic aspects of oxygen redox and the consequences of this reaction on various electrode degradation pathways during battery operation (e.g., oxygen loss, transition metal migration, irreversible phase transition), relating structural changes at the crystallographic scale to those at the macro scale, are discussed. Then recent developments based on atomic and microstructure modifications that are promising for improving the reversibility of oxygen redox reaction or mitigating the harmful processes arising from oxidation of the oxygen centers under high operating voltage are recounted. The analysis is concluded with a commentary on further research directions toward optimizing the oxygen activity for high‐capacity charge storage.

show abstract

“…Previous research on oxygen vacancies focused on catalysis [22][23][24][25][26]. Only a few studies analyzed the effect of oxygen vacancies on lithium storage [27]. These limited studies suggest that the introduction of oxygen vacancies can improve electrical conductivity and increase active site, which is beneficial to enhancing lithium storage remarkably [28][29][30][31].…”

Section: Introductionmentioning

confidence: 99%

Oxygen vacancy-expedited ion diffusivity in transition-metal oxides for high-performance lithium-ion batteries

Wang

Liu

et al. 2022

Sci. China Mater.

View full text Add to dashboard Cite

Rapid capacity decay and inferior kinetics are the vital issues of anodes in the conversion reaction for lithium-ion batteries. Vacancy engineering can efficiently modulate the intrinsic properties of transition-metal oxide (TMO)-based electrode materials, but the effect of oxygen vacancies on electrode performance remains unclear. Herein, abundant oxygen vacancies are in situ introduced into the lattice of different TMOs (e.g., Co 3 O 4 , Fe 2 O 3 , and NiO) via a facile hydrothermal treatment combined with calcination. Taking Co 3 O 4 as a typical example, results prove that the oxygen vacancies in Co 3 O 4−x effectively accelerate charge transfer at the interface and significantly increase electrical conductivity and pseudocapacitance contribution. The Li-ion diffusion coefficient of Co 3 O 4−x is remarkably improved by two orders of magnitude compared with that of Co 3 O 4 . Theoretical calculations reveal that Co 3 O 4−x has a lower Li-insertion energy barrier and more density of states around the Fermi level than Co 3 O 4 , which is favorable for ion and electron transport. Therefore, TMOs with rich vacancies exhibit superior cycling performance and enhanced rate capability over their counterparts. This strategy regulating the reaction kinetics would provide inspiration for designing other TMObased electrodes for energy applications.

show abstract

Oxygen Vacancy Diffusion and Condensation in Lithium‐Ion Battery Cathode Materials

Cited by 125 publications

References 41 publications

Highly‐Dispersed Submicrometer Single‐Crystal Nickel‐Rich Layered Cathode: Spray Synthesis and Accelerated Lithium‐Ion Transport

Highly‐Dispersed Submicrometer Single‐Crystal Nickel‐Rich Layered Cathode: Spray Synthesis and Accelerated Lithium‐Ion Transport

Utilizing Oxygen Redox in Layered Cathode Materials from Multiscale Perspective

Oxygen vacancy-expedited ion diffusivity in transition-metal oxides for high-performance lithium-ion batteries

Contact Info

Product

Resources

About