Engineering Oxygen Vacancies in a Polysulfide‐Blocking Layer with Enhanced Catalytic Ability

Li, Zhaohuai; Zhou, Cheng; Hua, Junhui; Hong, Xufeng; Sun, Congli; Li, Haiwen; Xu, Xu; Mai, Liqiang

doi:10.1002/adma.201907444

Cited by 186 publications

(132 citation statements)

References 45 publications

(38 reference statements)

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“…[11,12] Firstly, the oxygen vacancies would act as electron donors (n-type defects) to augment the carrier concentration to facilitate the charge transfer process. [13,14] Secondly, the Li-ion diffusion process would be accelerated due to the local built-in electric field derived from the unbalanced charge distribution around the OVs [15] Thirdly, the oxygen vacancies could tailor the electronic structure of the active materials, elevating the electrical conductivity of metal oxide. [16] Finally, the presence of oxygen vacancies at the electrode/ electrolyte interface has a modification effect of surface thermodynamics to facilitate the phase transitions of the materials, thus preserving the integrity of the structure.…”

Section: Introductionmentioning

confidence: 99%

Tailoring Oxygen Vacancies in CoMoO₄ for Superior Lithium Storage

et al. 2020

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The application of transition-metal oxides in the energy storage field is hampered by its low electronic conductivity, sluggish Li + diffusion, and huge volume changes. The construction of oxygen vacancy defects can effectively modify the electronic structure of the active materials, accelerating the charge transfer process. Herein, the CoMoO 4 nanorods with different oxygen vacancy concentrations are synthesized through the facile calcination process under N 2 and Air atmospheres. The ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS) analysis and Density Functional Theory (DFT) calculation results confirm that the bandgap reduces along with the increment of the oxygen vacancy content. The CoMoO 4-N 2 with higher oxygen vacancy concentration exhibits more superior electrochemical performance than CoMoO 4-Air, which delivers an ultrahigh specific capacity (999 mA h g À 1 after 500 cycles at 0.5 A g À 1), remarkable rate capacity (477 mA h g À 1 at 9 A g À 1), and excellent cycling stability (650 mA h g À 1 after 1000 cycles at 2 A g À 1).

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Section: Introductionmentioning

confidence: 99%

Tailoring Oxygen Vacancies in CoMoO₄ for Superior Lithium Storage

et al. 2020

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“…[71] For instance, Mai et al have verified that the O vacancies in TiO 2 possess the high LiPSs adsorption ability, favorable catalytic ability, and superior ion/ electron conductivities based on the first-principle calculations and experiment operations. [72] By enhancing the binding energy of O vacancies-TiO 2 (OVs-TiO 2 ) to LiPSs, the O vacancies can increase the TiO polarity, improve the ionic conductivity, and facilitate the fast conversion of soluble long-chain LiPSs. Also, because O vacancies locate in the bandgap of metal oxides, the defective metal oxides can obtain electron holes at lower formation energy, which promotes the electron transport to enhance electrical conductivity.…”

Section: Sulfur Cathodementioning

confidence: 99%

“…For instance, Mai et al. have verified that the O vacancies in TiO 2 possess the high LiPSs adsorption ability, favorable catalytic ability, and superior ion/electron conductivities based on the first‐principle calculations and experiment operations [72] . By enhancing the binding energy of O vacancies‐TiO 2 (OVs‐TiO 2 ) to LiPSs, the O vacancies can increase the TiO 2 polarity, improve the ionic conductivity, and facilitate the fast conversion of soluble long‐chain LiPSs.…”

Section: Defective Materials On High‐capacity Li‐based Batteriesmentioning

confidence: 99%

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Function and Application of Defect Chemistry in High‐Capacity Electrode Materials for Li‐Based Batteries

Qiao

Lin

Yan

et al. 2020

Chemistry An Asian Journal

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Current commercial Li-based batteries are approaching their energy density limitation, yet still cannot satisfy the energy density demand of the high-end devices. Hence, it is critical to developing advanced electrode materials with high specific capacity. However, these electrode materials are facing challenges of severe structural degradation and fast capacity fading. Among various strategies, constructing defects in electrode materials holds great promise in addressing these issues. Herein, we summarize a series of significant defect engineering in the high-capacity electrode materials for Li-based batteries. The detailed retrospective on defects specification, function mechanism, and corresponding application achievements on these electrodes are discussed from the view of point, line, planar, volume defects. Defect engineering can not only stabilize the structure and enhance electric/ionic conductivity, but also act as active sites to improve the ionic storage and bonding ability of electrode materials to Li metal. We hope this review can spark more perspectives on evaluating high-energydensity Li-based batteries.

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“…[ 12,13 ] Tremendous efforts have been devoted to the design of advanced cathode host materials to mitigate the shuttle effect. [ 14,15 ] These designed cathode strategies include: employing porous carbon materials as the hosts; [ 7,16–19 ] coating the cathode materials with graphene, metal oxide, or conductive polymers; [ 20–24 ] and heteroatoms doping. [ 25–27 ] However, these cathode engineering would inevitably reduce the mass ratio of selenium by introducing additional components, leading to decreased energy density.…”

Section: Introductionmentioning

confidence: 99%

Interface Engineering of MXene Composite Separator for High‐Performance Li–Se and Na–Se Batteries

Zhang

Guo

Xiong

et al. 2020

Advanced Energy Materials

101

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However, the development of metal-Se batteries has been blocked by the severe shuttle effect of polyselenides, particularly in ether-based electrolyte, where the polyselenides diffuse across the separator and react with the metal anode. [12,13] Tremendous efforts have been devoted to the design of advanced cathode host materials to mitigate the shuttle effect. [14,15] These designed cathode strategies include: employing porous carbon materials as the hosts; [7,[16][17][18][19] coating the cathode materials with graphene, metal oxide, or conductive polymers; [20][21][22][23][24] and heteroatoms doping. [25][26][27] However, these cathode engineering would inevitably reduce the mass ratio of selenium by introducing additional components, leading to decreased energy density. [28] Recently, functional separators have been prepared to inhibit the shuttle effect in Se-or S-based batteries. [17,[29][30][31][32][33][34] For example, MXenes (M n+1 X n T x , where M = transition metal, X = carbon/nitrogen, n = 1, 2, and 3, and T x represents surface functional groups) modified separators have been proved to be effective in suppressing the shuttle effect due to their anisotropic shape and large 2D dimensions that increases the diffusion pathway of polysulfide/polyselenide species. [35][36][37] In addition, MXene shows strong adsorption to polysulfides due to the Lewis acid-base interaction between polysulfides and Ti sites, [38,39] which may also work for polyselenides. Nazar and co-workers have shown that the surface environment on MXene enhances such Lewis acid-base chemisorption via thiosulfate formation. [38] However, this enhanced adsorption undergoes a two-step process with sluggish kinetics. Although the shuttle effect can be mitigated, the battery showed slow redox reaction, especially under high current densities. In addition, the MXene nanosheets also suffer from restacking and poor electrolyte affinities due to the van der Waals (vdW) forces and rich hydrophilic surface groups (OH and F), respectively. [40,41] It is well known that the hydrophilic groups on MXene have low compatibility to organic electrolyte. [42] The inferior separator-electrolyte contact will lead to a poor solid-electrolyte interface (SEI) and slow electrolyte infiltration process. [43] Herein, we developed a novel self-assembled cetrimonium bromide (CTAB)/carbon nanotube (CNT)/Ti 3 C 2 T x MXene Selenium (Se), due to its high electronic conductivity and high energy density, has recently attracted considerable interest as a cathode material for rechargeable Li/Na batteries. However, the poor cycling stability originating from the severe shuttle effect of polyselenides hinders their practical applications. Herein, highly stable Li/Na-Se batteries are developed using ultrathin (≈270 nm, loading of 0.09 mg cm −2 ) cetrimonium bromide (CTAB)/carbon nanotube (CNT)/Ti 3 C 2 T x MXene hybrid modified polypropylene (PP) (CCNT/ MXene/PP) separators. The hybrid separator can immobilize the polyselenides via enhanced Lewis acid-base interactions betwee...

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Engineering Oxygen Vacancies in a Polysulfide‐Blocking Layer with Enhanced Catalytic Ability

Cited by 186 publications

References 45 publications

Tailoring Oxygen Vacancies in CoMoO₄ for Superior Lithium Storage

Tailoring Oxygen Vacancies in CoMoO₄ for Superior Lithium Storage

Function and Application of Defect Chemistry in High‐Capacity Electrode Materials for Li‐Based Batteries

Interface Engineering of MXene Composite Separator for High‐Performance Li–Se and Na–Se Batteries

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Engineering Oxygen Vacancies in a Polysulfide‐Blocking Layer with Enhanced Catalytic Ability

Cited by 186 publications

References 45 publications

Tailoring Oxygen Vacancies in CoMoO4 for Superior Lithium Storage

Tailoring Oxygen Vacancies in CoMoO4 for Superior Lithium Storage

Function and Application of Defect Chemistry in High‐Capacity Electrode Materials for Li‐Based Batteries

Interface Engineering of MXene Composite Separator for High‐Performance Li–Se and Na–Se Batteries

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Tailoring Oxygen Vacancies in CoMoO₄ for Superior Lithium Storage

Tailoring Oxygen Vacancies in CoMoO₄ for Superior Lithium Storage