Multiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfide

Britto, Sylvia; Leskes, Michal; Hua, Xiao; Hébert, Claire-Alice; Shin, Hyeon Suk; Clarke, Simon J.; Borkiewicz, Olaf J.; Chapman, Karena W.; Seshadri, Ram; Cho, Jaephil; Grey, Clare P.

doi:10.1021/jacs.5b03395

Cited by 141 publications

(200 citation statements)

References 59 publications

(128 reference statements)

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“…As a member of the TMSs, VS 4 has a unique chain‐like structure linked by van der Waals forces and a large interchain distance of 0.58 nm, which facilitates sodium‐ion transport . In addition, owing to its high sulfur content, VS 4 provides a large theoretical capacity based on a conversion reaction . Despite such anticipated advantages, the development of VS 4 for SIBs has remained slow to date.…”

Section: Introductionmentioning

confidence: 99%

VS₄ Nanoparticles Anchored on Graphene Sheets as a High‐Rate and Stable Electrode Material for Sodium Ion Batteries

Pang

Zhao

et al. 2018

ChemSusChem

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The size and conductivity of the electrode materials play a significant role in the kinetics of sodium-ion batteries. Various characterizations reveal that size-controllable VS nanoparticles can be successfully anchored on the surface of graphene sheets (GSs) by a simple cationic-surfactant-assisted hydrothermal method. When used as an electrode material for sodium-ion batteries, these VS @GS nanocomposites show large specific capacity (349.1 mAh g after 100 cycles), excellent long-term stability (84 % capacity retention after 1200 cycles), and high rate capability (188.1 mAh g at 4000 mA g ). A large proportion of the capacity was contributed by capacitive processes. This remarkable electrochemical performance was attributed to synergistic interactions between nanosized VS particles and a highly conductive graphene network, which provided short diffusion pathways for Na ions and large contact areas between the electrolyte and electrode, resulting in considerably improved electrochemical kinetic properties.

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Section: Introductionmentioning

confidence: 99%

VS₄ Nanoparticles Anchored on Graphene Sheets as a High‐Rate and Stable Electrode Material for Sodium Ion Batteries

Pang

Zhao

et al. 2018

ChemSusChem

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“…24 More recently, transition metal tri-and tetrasulfide materials have been studied for their more complex chemistries as electrodes in conversion reactions involving both redox-active cationic and anionic species. [25][26][27] For example, upon lithiation of VS 4 , the vanadium species is oxidized from V +4 (VS 4 ) to V +5 (Li 3 VS 4 ) then to a mixture of both valences (Li 3+x VS 4 ) before reduction to V 0 (Li 2 S + V). 27 This was concomitant with a reduction of the sulfur species from S 2− 2 to S 2− .…”

Section: Introductionmentioning

confidence: 99%

“…[25][26][27] For example, upon lithiation of VS 4 , the vanadium species is oxidized from V +4 (VS 4 ) to V +5 (Li 3 VS 4 ) then to a mixture of both valences (Li 3+x VS 4 ) before reduction to V 0 (Li 2 S + V). 27 This was concomitant with a reduction of the sulfur species from S 2− 2 to S 2− . Despite initial high gravimetric capacities, retention remains a challenge with transitional metal sulfide electrodes.…”

Section: Introductionmentioning

confidence: 99%

Molybdenum Polysulfide Chalcogels as High-Capacity, Anion-Redox-Driven Electrode Materials for Li-Ion Batteries

Subrahmanyam²,

et al. 2016

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Sulfur cathodes in conversion reaction batteries offer high gravimetric capacity but suffer from parasitic polysulfide shuttling. We demonstrate here that transition metal chalcogels of approximate formula MoS 3.4 achieve high gravimetric capacity close to 600 mAh g −1 (close to 1000 mAh g −1 on a sulfur-basis), as electrode materials for lithium-ion batteries. Transition metal chalcogels are amorphous, and comprise polysulfide chains connected by inorganic linkers. The linkers appear to act as a "glue" in the electrode to prevent polysulfide shuttling. The Mo chalcogels function as electrodes in carbonate-as well as ether-based electrolytes, which further provides evidence for polysulfide solubility not being a limiting issue. We employ X-ray spectroscopy and operando pair distribution function techniques to elucidate the structural evolution of the electrode. Raman and X-ray photoelectron spectroscopy track the chemical moieties that arise during the anion-redox-driven processes. We find the redox state of Mo remains unchanged across the electrochemical cycling and correspondingly, the redox

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“…9,10 Conversion materials are of interest because the full oxidation state of the transition metal can be utilized, enabling high theoretical capacities. The electrochemical activity of alternative anode materials is often evaluated in composite electrodes at low potentials, close to that of Li/Li + , to demonstrate charge storage at viable anode potentials.…”

mentioning

confidence: 99%

Reversible Capacity of Conductive Carbon Additives at Low Potentials: Caveats for Testing Alternative Anode Materials for Li-Ion Batteries

See

Lumley

Stucky

et al. 2016

J. Electrochem. Soc.

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The electrochemical performance of alternative anode materials for Li-ion batteries is often measured using composite electrodes consisting of active material and conductive carbon additives. Cycling of these composite electrodes at low voltages demonstrates charge storage at the operating potentials of viable anodes, however, the conductive carbon additive is also able to store charge in the low potential regime. The contribution of the conductive carbon additives to the observed capacity is often neglected when interpreting the electrochemical performance of electrodes. To provide a reference for the contribution of the carbons to the observed capacity, we report the charge storage behavior of two common conductive carbon additives Super P and Ketjenblack as a function of voltage, rate, and electrolyte composition. Both carbons exhibit substantial capacities after 100 cycles, up to 150 mAh g −1 , when cycled to 10 mV. The capacity is dependent on the discharge cutoff voltage and cycling rate with some dependence on electrolyte composition. The first few cycles are dominated by the formation of the SEI followed by a fade to a steady, reversible capacity thereafter. Neglecting the capacity of the carbon additive can lead to significant errors in the estimation of charge storage capabilities of the active material. The investigation of alternative anode materials for Li batteries is driven by the need for sustainable materials exhibiting high, reversible capacity at low voltages that outperform the current ubiquitous anode chemistry provided by Li intercalated graphite. Although the Li-ion battery is currently capacity limited by the cathode, next-generation cathodes such as elemental S 8 , for example, have high theoretical capacities, up to five times higher than the conventional lithiated graphite anode. Due to this capacity mismatch, Li-S cells rely on the use of unsafe Li metal anodes that add significant challenges to the already complicated cathode chemistry to achieve high energy densities.Systems evaluated as high capacity anodes include elemental electrode materials such as Si, 1,2 and conversion materials including transition metal oxides, 3-5 fluorides, 6,7 hydrides, 8 and sulfides. 9,10 Conversion materials are of interest because the full oxidation state of the transition metal can be utilized, enabling high theoretical capacities. The electrochemical activity of alternative anode materials is often evaluated in composite electrodes at low potentials, close to that of Li/Li + , to demonstrate charge storage at viable anode potentials. The composite electrodes contain varying percentages of conductive carbon and polymeric binder in addition to the active material, as shown schematically in Figure 1, in order to enhance the conductivity and mechanical stability of the electrode.11 The capacity of the electrode is usually dominated by the charge storage behavior of the active material. However, the charge storage abilities of the slurry could arise from a combination of the capacity of all three compon...

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Multiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfide

Cited by 141 publications

References 59 publications

VS₄ Nanoparticles Anchored on Graphene Sheets as a High‐Rate and Stable Electrode Material for Sodium Ion Batteries

VS₄ Nanoparticles Anchored on Graphene Sheets as a High‐Rate and Stable Electrode Material for Sodium Ion Batteries

Molybdenum Polysulfide Chalcogels as High-Capacity, Anion-Redox-Driven Electrode Materials for Li-Ion Batteries

Reversible Capacity of Conductive Carbon Additives at Low Potentials: Caveats for Testing Alternative Anode Materials for Li-Ion Batteries

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Multiple Redox Modes in the Reversible Lithiation of High-Capacity, Peierls-Distorted Vanadium Sulfide

Cited by 141 publications

References 59 publications

VS4 Nanoparticles Anchored on Graphene Sheets as a High‐Rate and Stable Electrode Material for Sodium Ion Batteries

VS4 Nanoparticles Anchored on Graphene Sheets as a High‐Rate and Stable Electrode Material for Sodium Ion Batteries

Molybdenum Polysulfide Chalcogels as High-Capacity, Anion-Redox-Driven Electrode Materials for Li-Ion Batteries

Reversible Capacity of Conductive Carbon Additives at Low Potentials: Caveats for Testing Alternative Anode Materials for Li-Ion Batteries

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Product

Resources

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VS₄ Nanoparticles Anchored on Graphene Sheets as a High‐Rate and Stable Electrode Material for Sodium Ion Batteries

VS₄ Nanoparticles Anchored on Graphene Sheets as a High‐Rate and Stable Electrode Material for Sodium Ion Batteries