Oxygen-defective Co3O4 for pseudo-capacitive lithium storage

Zhang, Jie; Jiang, Heng; Zeng, Yibo; Zhang, Ying

doi:10.1016/j.jpowsour.2019.227026

Cited by 49 publications

(19 citation statements)

References 67 publications

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“…The large peak width is due to the formation of a nanocrystalline Co 0 phase after the full conversion. Thus, Figure a indicates the two-step lithiation in Co 3 O 4 nanosheets, consistent with a previous report: Co 3 O 4 + 2Li + + 2e – → 3CoO + Li 2 O; CoO + 2Li + + 2e – → Co + Li 2 O. In contrast, Co 3 O 4 nanoarrays show a negligible trace of the CoO phase throughout the discharging process (Figure b).…”

Section: Resultssupporting

confidence: 90%

“…The large peak width is due to the formation of a nanocrystalline Co 0 phase after the full conversion. Thus, Figure 5a indicates the two-step lithiation in Co 3 O 4 nanosheets, consistent with a previous report: 18…”

Section: Effects Of Nanostructures On Lithiation Reaction Pathways Of...supporting

confidence: 91%

“…However, the detailed process of the conversion reaction in Co 3 O 4 remains controversial in the literature. Guo et al 18 found that a CoO phase forms as an intermediate phase during the conversion from Co 3 O 4 to Co 0 using ex situ X-ray diffractometry (XRD) on a Co 3 O 4 anode at different discharge states. Yuk et al 19 also revealed the CoO phase as the initial conversion product of Co 3 O 4 , followed by the formation of Co 0 using graphene liquid cell electron microscopy.…”

Section: Introductionmentioning

confidence: 99%

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Nanostructure-Mediated Phase Evolution in Lithiation/Delithiation of Co₃O₄

Guo

et al. 2021

ACS Appl. Mater. Interfaces

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Nanostructured transition-metal oxides have been under intensive investigation for their tantalizing potential as anodes of next-generation lithium-ion batteries (LIBs). However, the exact mechanism for nanostructures to influence the LIB performance remains largely elusive. In this work, we discover the nanostructure-mediated lithiation mechanism in Co3O4 anodes using ex situ transmission electron microscopy (TEM) and X-ray diffractometry: while Co3O4 nanosheets exhibit a typical two-step conversion reaction (from Co3O4 to CoO and then to Co0), Co3O4 nanoarrays can go through a direct conversion from Co3O4 to Co0 at a high discharge rate. Such nanostructure-dependent lithiation can be rationalized by the slow lithiation kinetics intrinsic to Co3O4 nanoarrays, which at a high discharge rate may cause local accumulation of lithium to initiate a one-step Co3O4-to-Co0 conversion. Combined with the larger volume change observed in Co3O4 nanoarrays, the slow lithiation kinetics can lead to inhomogeneous expansion with large stress developed at the reaction front, which can eventually cause structure failure and irreversible capacity loss, as explicitly observed by in situ TEM as well as galvanostatic discharge–charge measurement. Our observation resolves the nanostructure-dependent lithiation mechanism of Co3O4 and provides important insights into the interplay among lithiation kinetics, phase evolution, and lithium-storage performance, which can be translated into electrode design strategies for next-generation LIBs.

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Section: Resultssupporting

confidence: 90%

Section: Effects Of Nanostructures On Lithiation Reaction Pathways Of...supporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

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Nanostructure-Mediated Phase Evolution in Lithiation/Delithiation of Co₃O₄

Guo

et al. 2021

ACS Appl. Mater. Interfaces

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“…With the high utilization of metal oxides, the initial capacity of these oxygen-deficient electrodes can be increased. In addition, since the formation of OVs tends to occur at the surface of the electrodes, a high capacitive storage behavior is often observed, leading to enhanced rate performance [85,114]. Zhang et al [115] Moreover, 75% of the capacity of H-Nb 2 O 5 -10 was attributed to a capacitive process, and this ratio was further increased to 88% when the scan rate increased from 1 to 5 mV s −1 (Figure 10c).…”

Section: Increasing Active Sites To Store Ionsmentioning

confidence: 99%

The role of oxygen vacancies in metal oxides for rechargeable ion batteries

Wei

2021

Sci. China Chem.

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Rechargeable ion batteries are one of the most reliable energy storage technologies for the applications ranging from small portable devices and electric vehicles to renewable energy integration and large-scale stationary energy storage. In the roadmap of developing and understanding new electrode materials for rechargeable ion batteries, oxygen vacancies, known as defects in metal oxides, have shown a high impact on the final electrochemical performance of the oxides. The present review aims to summarise the synthesis methods and characterisation techniques of oxygen vacancies as well as some of the most recent and exciting progress made to understand the role of oxygen vacancies in the electrochemical performance of Li-, Na-, K-and Zn-ion batteries. This review discusses not only the role of oxygen vacancies directly in electrode materials and indirectly in the coating layers on electrode materials, but also the synergistic role of oxygen vacancies interplaying with other contributors such as carbonaceous materials, doping, amorphisation, structural transformation, nanostructuring and functional coating. Finally, perspectives are given to stimulate new ideas and open questions to facilitate the further development of oxygen deficient electrode materials in energy research landscape.

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“…Hence, the first three cycles in the CV curves of R‐MoO 3− x overlap with each other and retain their capacities during cycling (Figure 14f). Zhang et al [ 148 ] demonstrated oxygen‐deficient Co 3 O 4 with attractive stability and rate performance in an electrolyte of LiPF 6 dissolved in ethylene carbonate, dimethyl carbonate, and ethylmethyl carbonate.…”

Section: Applicationsmentioning

confidence: 99%

Oxygen‐Deficient Metal Oxides for Supercapacitive Energy Storage: From Theoretical Calculation to Structural Regulation and Utilization

Wan

Wang

et al. 2022

Adv Energy and Sustain Res

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Supercapacitors (SCs) have attracted considerable research interest because of their complementary role to dominated lithium-ion batteries (LIBs) for powering the electrified society. [1] In contrast to the bulk-involved reactions for energy storage in LIBs, SCs mainly store charges in the electric double layers (EDLs) via electrostatic adsorption where highly porous and conductive materials, for example, activated carbons, are needed. [2] This storage mechanism allows SCs to exhibit excellent rate capability, long cyclic life, and high safety; therefore, it is indispensable in many fields. [3] However, despite these advantages, the limited charge storage space within electrode materials considerably restricts the energy density of SCs. To overcome this limitation, tremendous efforts have been devoted to the search for electrode materials that employ alternative charge-storage mechanisms that can improve energy storage. [4] Some metal oxides (MOs) can afford extremely fast surface redox reactions which compare favorably with those of electrostatic charge adsorption at the EDLs. Although these processes are faradaic in nature, they show an excellent rate capability that is similar to that of the EDL charge storage in the porous carbon electrodes of current SCs. Then, these MOs are defined as pseudocapacitive materials, and they can improve the energy density of current SCs. [5] The theoretical capacitance of the MO-based electrodes can be calculated using Equation (1) [6] Cwhere n, F, M, and V represent the number of transferred electrons, Faraday constant (C mol À1 ), the molar mass of the MOs (g mol À1 ), and operating voltage window (V), respectively. The specific capacitance of the typical MO electrode materials is summarized in Table 1.The MOs should have suitable electronic structures, desired electrical conductivity, and sufficient active sites to facilitate surface redox reactions. To this end, tremendous progress has been realized via research efforts in recent decades. [7] Heteroatomdoping has been widely used to engineer electronic structures. [8] Zeng et al. [9] synthesized a Ti-doped Fe 2 O 3 @poly

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Oxygen-defective Co3O4 for pseudo-capacitive lithium storage

Cited by 49 publications

References 67 publications

Nanostructure-Mediated Phase Evolution in Lithiation/Delithiation of Co₃O₄

Nanostructure-Mediated Phase Evolution in Lithiation/Delithiation of Co₃O₄

The role of oxygen vacancies in metal oxides for rechargeable ion batteries

Oxygen‐Deficient Metal Oxides for Supercapacitive Energy Storage: From Theoretical Calculation to Structural Regulation and Utilization

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Oxygen-defective Co3O4 for pseudo-capacitive lithium storage

Cited by 49 publications

References 67 publications

Nanostructure-Mediated Phase Evolution in Lithiation/Delithiation of Co3O4

Nanostructure-Mediated Phase Evolution in Lithiation/Delithiation of Co3O4

The role of oxygen vacancies in metal oxides for rechargeable ion batteries

Oxygen‐Deficient Metal Oxides for Supercapacitive Energy Storage: From Theoretical Calculation to Structural Regulation and Utilization

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Product

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Nanostructure-Mediated Phase Evolution in Lithiation/Delithiation of Co₃O₄

Nanostructure-Mediated Phase Evolution in Lithiation/Delithiation of Co₃O₄