Padding molybdenum net with Graphite/MoO3 composite as a multi-functional interlayer enabling high-performance lithium-sulfur batteries

Yue, Xin‐Yang; Li, Xun‐Lu; Meng, Jingke; Wu, Xiaojing; Zhou, Yong‐Ning

doi:10.1016/j.jpowsour.2018.07.017

Cited by 42 publications

(18 citation statements)

References 30 publications

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“…Scanning electron microscopy (SEM) images present more details. The top surface of the electrode is flat and dense under high magnification (Figure d; Figure S5, Supporting Information), while the back side of MLF electrode (Figure e) shows the cross‐linked Mo skeleton partially embedded in Li metal, which has good mechanical property and high electronic conductivity as the supporting matrix . Figure f displays the cross‐sectional SEM image of MLF electrode.…”

Section: Resultsmentioning

confidence: 99%

“…[40] By using this method, a certain amount of Li metal was successfully stored into the MLF electrode by controlling the melting time (≈10 s). [41] Figure 1f displays the cross-sectional SEM image of MLF electrode. The electrochemical test ( Figure S3, Supporting Information) shows that the complete Li stripping capacity of MLF electrode before potential mutation is about 30 mAh cm −2 .…”

Section: Characterization Of the Mlf Electrodementioning

confidence: 99%

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“Top‐Down” Li Deposition Pathway Enabled by an Asymmetric Design for Li Composite Electrode

Yue

Bao

et al. 2019

Advanced Energy Materials

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safety issue due to dendrite growth during the repeated Li stripping/plating process. [7][8][9] On one hand, the surface defects of the bare Li serve as the active sites to increase the local current density, leading to uneven Li deposition. [10] On the other hand, the "hostless" feature of Li metal results in huge volume change during cycling, causing unstable solid electrolyte interphase (SEI). [11] As a result, the fresh Li exposure created by SEI fracturing consumes electrolyte continuously, leading to low coulombic efficiency. [12] As such, the Li dendrites develop in an uncontrolled fashion that can eventually pierce the separator and cause short circuit. Moreover, the fractures of dendrites during repeated Li deposition/stripping result in "dead" Li sections composed of isolated Li fragments surrounded by e −insulating SEI. [13,14] The "dead" Li with high impedance leads to poor kinetics and shortened lifespan of the battery. [15] In order to inhibit Li dendrite growth and build stable SEI layers, considerable efforts have been made. One approach is the coating of an artificial SEI with high mechanical strength onto the electrode surface. [16][17][18][19] However, because of the volume change of Li metal, the structural integrity of the protective layers is hard to be maintained during prolonged running. In order to remit the volume change, great efforts have been made to design porous frameworks to accommodate Li. [20][21][22][23][24][25][26] A series of host frameworks have been reported, such as 3D CoO/Ni foam skeleton, [27] coralloid carbon fiber scaffolds, [28] lithiophilic Cu-Ni core-shell nanowire network, [29] and 3D carbon fiber framework. [30] The host frameworks can not only accommodate the volume change of Li during cycling, but also reduce the local current density. [31][32][33][34] More importantly, the porous structure of these frameworks can suppress the dendrite formation by changing Li plating/ stripping behavior. [35][36][37] It should be noted that most of the reported composited electrodes possess symmetric structure for their two sides, especially for the electrodes fabricated by thermal infusion method. [38] However, as the anode for the battery, the two sides of the electrode are in different environments: one side contacts with the separator, while the other side faces the current collector. The requirements and functions for the two sides are thus quite different. [39] The side facing the separator should be facile for Li-ion transportation.Designing Li composite electrodes with host frameworks for accommodating Li metal has been considered to be an effective approach to suppress Li dendrites. Herein, an asymmetric design of a Mo net/Li metal film (MLF) composite electrode is developed by an inverted thermal infusion method. The asymmetric MLF electrode has a dense oxide passivated layer on the top side, a porous Mo net matrix on the back side, and active Li layer in between. The back side has a larger specific area and higher electric field than the top side, which contacts with ...

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Section: Resultsmentioning

confidence: 99%

Section: Characterization Of the Mlf Electrodementioning

confidence: 99%

“Top‐Down” Li Deposition Pathway Enabled by an Asymmetric Design for Li Composite Electrode

Yue

Bao

et al. 2019

Advanced Energy Materials

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“…Over the past decades, massive efforts like encapsulating S 8 in conductive matrix, protective coating layers, and inducing interlayer between cathode and separator, have been made to manipulate this deficiency, aiming to lighten shuttling and migration of Li 2 S n during long‐term cycling and to improve the electrode kinetics. 2D materials with large specific area, such as graphene oxides (GOs), MnO 2 , Co 4 N, MXene, provide numerous anchoring sites and have been successfully employed as cathode hosts to suppress shuttling and migration of Li 2 S n in the Li–S batteries. Usually, heteroatoms doping is a general modification technique to further increase the polarity of 2D materials to adsorb Li 2 S n , giving birth to nitrogen‐doped graphene, nitrogen‐doped MXene, cobalt‐doped porous carbon, molybdenum‐doped MoO 3 , etc.…”

Section: Introductionmentioning

confidence: 99%

Tin Intercalated Ultrathin MoO₃ Nanoribbons for Advanced Lithium–Sulfur Batteries

Yang

Xiao

et al. 2018

Advanced Energy Materials

136

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batteries is greatly limited by the highly insulating nature of S 8 /Li 2 S 2-x (x ≤ 1) and the dissolution of intermediate lithium polysulfides (Li 2 S n , 4 ≤ n ≤ 8) during charge/discharge process. [7][8][9] Over the past decades, massive efforts like encapsulating S 8 in conductive matrix, [10][11][12][13] protective coating layers, [14][15][16] and inducing interlayer between cathode and separator, [17][18][19] have been made to manipulate this deficiency, aiming to lighten shuttling and migration of Li 2 S n during long-term cycling and to improve the electrode kinetics. 2D materials with large specific area, such as graphene oxides (GOs), [20][21][22][23][24] MnO 2 , [25] Co 4 N, [26] MXene, [27] provide numerous anchoring sites and have been successfully employed as cathode hosts to suppress shuttling and migration of Li 2 S n in the Li-S batteries. Usually, heteroatoms doping is a general modification technique to further increase the polarity of 2D materials to adsorb Li 2 S n , giving birth to nitrogen-doped graphene, [28] nitrogen-doped MXene, [29] cobalt-doped porous carbon, [30] molybdenum-doped MoO 3 , [31] etc. However, the doping amount is very limited, which seriously restricts the improvement of their electrochemical performance. Comparing with the traditional doping strategy, intercalation can induce more heteroatoms in their van der Waals gap with good uniformity and change the properties of 2D materials more significantly. [32] For example, in our previous study, we proved that the n-type semiconducting SnS 2 can turn to a p-type semiconductor or metal after intercalation of different transition metal atoms. [33] Besides the electrical properties, the electrochemical properties of 2D materials might also be tuned effectively by this intercalation strategy.Here, ultrathin 2D layered α-MoO 3 nanoribbons with thickness of ≈10 nm have been synthesized and selected as the host. The strong polarity of MoO 3 together with its high specific surface area provides numerous active sites to bind sulfur species effectively, thus suppressing the "shuttle effect" obviously. Intercalation of metal tin (Sn) into van der Waals gap was further used to enhance the intrinsic conductivity of MoO 3 and improve the binding energy with sulfur species. Transmission electron microscopy (TEM) proved that Sn was inserted into the van der Waals gap of MoO 3 uniformly. First-principles calculations further certify that binding energy as large as 3.01 eV Heteroatom doping strategies have been widely developed to engineer the conductivity and polarity of 2D materials to improve their performance as the host for sulfur cathode in lithium-sulfur batteries. However, further improvement is limited by the inhomogeneity and the small amount of the doping atoms. An intercalation method to improve the conductivity and polarity of 2D-layered α-MoO 3 nanoribbons is developed here, thus, resulting in much improved electrochemical performance as sulfur host with better rate and cycle performance. The first principle calculations show t...

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“…As shown in Figure h, the Mo 3d spectrum can be deconvoluted into four peaks. The first two peaks located at 228.8 and 231.9 eV are assigned to the Mo–Mo bond for metallic Mo (Mo 0 ). , The other two peaks at 233.0 and 236.1 eV suggest the presence of MoO x species, which probably results from the oxidation of metallic Mo in air . After loading with LPS solution in the CNT/Mo composite, negative shifts for the peaks of MoO x species are observed in the high-resolution XPS Mo 3d spectra (Figure j), which suggests the electrons transfer from the electronegative S atoms of LPS species to the electropositive Mo atoms of MoO x species.…”

Section: Resultsmentioning

confidence: 52%

Enhanced Chemical Immobilization and Catalytic Conversion of Polysulfide Intermediates Using Metallic Mo Nanoclusters for High-Performance Li–S Batteries

Wang

et al. 2019

ACS Nano

128

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Rechargeable lithium–sulfur batteries have attracted tremendous scientific attention owing to their high energy density. However, their practical application is greatly hindered by the notorious shuttling of soluble lithium polysulfide (LPS) intermediates with sluggish redox reactions and uncontrolled precipitation behavior. Herein, we report a semiliquid cathode composed of an active LPS solution/carbon nanofiber (CNF) composite layer, capped with a carbon nanotube (CNT) thin film decorated with metallic Mo nanoclusters that regulate the electrochemical redox reactions of LPS. The trace amount (0.05 mg cm–2) of metallic Mo on the CNT film provides sufficient capturing centers for the chemical immobilization of LPS. Together with physical blocking of LPS by the compact CNT film, free diffusion of LPS is significantly restrained and the self-discharge behavior of the Li–S cell is thus effectively suppressed. Importantly, the metallic Mo nanoclusters enable fast catalytic conversion of LPS and regular deposition of lithium sulfide. As a result, the engineered cathode exhibits a high active sulfur utilization (1401 mAh g–1 at 0.1 C), stable cycling (500 cycles at 1 C with 0.06% decay per cycle), high rate performance (694 mAh g–1 at 5 C), and low self-discharge rate (3% after 72 h of rest). Moreover, a high reversible areal capacity of 4.75 mAh cm–2 is maintained after 100 cycles at 0.2 C for a cathode with a high sulfur loading of 7.64 mg cm–2. This work provides significant insight into the structural and materials design of an advanced sulfur-based cathode that effectively regulates the electrochemical reactions of sulfur species in high-energy Li–S batteries.

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Padding molybdenum net with Graphite/MoO3 composite as a multi-functional interlayer enabling high-performance lithium-sulfur batteries

Cited by 42 publications

References 30 publications

“Top‐Down” Li Deposition Pathway Enabled by an Asymmetric Design for Li Composite Electrode

“Top‐Down” Li Deposition Pathway Enabled by an Asymmetric Design for Li Composite Electrode

Tin Intercalated Ultrathin MoO₃ Nanoribbons for Advanced Lithium–Sulfur Batteries

Enhanced Chemical Immobilization and Catalytic Conversion of Polysulfide Intermediates Using Metallic Mo Nanoclusters for High-Performance Li–S Batteries

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Padding molybdenum net with Graphite/MoO3 composite as a multi-functional interlayer enabling high-performance lithium-sulfur batteries

Cited by 42 publications

References 30 publications

“Top‐Down” Li Deposition Pathway Enabled by an Asymmetric Design for Li Composite Electrode

“Top‐Down” Li Deposition Pathway Enabled by an Asymmetric Design for Li Composite Electrode

Tin Intercalated Ultrathin MoO3 Nanoribbons for Advanced Lithium–Sulfur Batteries

Enhanced Chemical Immobilization and Catalytic Conversion of Polysulfide Intermediates Using Metallic Mo Nanoclusters for High-Performance Li–S Batteries

Contact Info

Product

Resources

About

Tin Intercalated Ultrathin MoO₃ Nanoribbons for Advanced Lithium–Sulfur Batteries