In Operando X-ray Diffraction and Transmission X-ray Microscopy of Lithium Sulfur Batteries

Nelson, Johanna; Misra, Supriya; Yang, Yuan; Jackson, Ariel; Liu, Yijin; Wang, Hailiang; Dai, Hongjie; Andrews, Joy C.; Cui, Yi; Toney, Michael F.

doi:10.1021/ja2121926

Cited by 477 publications

(484 citation statements)

References 37 publications

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“…135 In situ NMR spectroscopy study also suggested that sulphur is reduced to soluble polysulfide species during the first discharge plateau concurrently with the formation of Li 2 S. 136 In situ XRD and transmission X-ray microscopy study suggests that crystalline Li 2 S is not formed at the end of discharge and most of the intermediate polysulfides are retained inside the cathode matrix. 137 While experimental result shows that the lithiation/delithiation for S 2-4 occurs as a solid-solid process if the micropores of carbon are small enough to prevent the penetration of the solvent molecules. 138 Direct evidence for these proposed mechanisms is difficult to obtain due to multistep reactions that are further complicated by the formation of a variety of transient species.…”

Section: Polysulphide-based Li-redox Flow Batteriesmentioning

confidence: 95%

A chemistry and material perspective on lithium redox flow batteries towards high-density electrical energy storage

et al. 2015

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Electrical energy storage system such as secondary batteries is the principle power source for portable electronics, electric vehicles and stationary energy storage. As an emerging battery technology, Li-redox flow batteries inherit the advantageous features of modular design of conventional redox flow batteries and high voltage and energy efficiency of Li-ion batteries, showing great promise as efficient electrical energy storage system in transportation, commercial, and residential applications. The chemistry of lithium redox flow batteries with aqueous or non-aqueous electrolyte enables widened electrochemical potential window thus may provide much greater energy density and efficiency than conventional redox flow batteries based on proton chemistry. This Review summarizes the design rationale, fundamentals and characterization of Li-redox flow batteries from a chemistry and material perspective, with particular emphasis on the new chemistries and materials. The latest advances and associated challenges/ opportunities are comprehensively discussed.

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Section: Polysulphide-based Li-redox Flow Batteriesmentioning

confidence: 95%

A chemistry and material perspective on lithium redox flow batteries towards high-density electrical energy storage

et al. 2015

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“…Some literature suggests that the transition from the high to the low discharge voltage plateau happens concurrently with the start of the formation of solid Li 2 S 2 and Li 2 S 6, 14. This stage contributes to the major portion of the capacity with a fixed voltage.…”

Section: Theoretical Capacity Fade Analysis Of Li–s Batteriesmentioning

confidence: 98%

Capacity Fade Analysis of Sulfur Cathodes in Lithium–Sulfur Batteries

2016

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Rechargeable lithium–sulfur (Li–S) batteries are receiving ever‐increasing attention due to their high theoretical energy density and inexpensive raw sulfur materials. However, their rapid capacity fade has been one of the key barriers for their further improvement. It is well accepted that the major degradation mechanisms of S‐cathodes include low electrical conductivity of S and sulfides, precipitation of nonconductive Li2S2 and Li2S, and poly‐shuttle effects. To determine these degradation factors, a comprehensive study of sulfur cathodes with different amounts of electrolytes is presented here. A survey of the fundamentals of Li–S chemistry with respect to capacity fade is first conducted; then, the parameters obtained through electrochemical performance and characterization are used to determine the key causes of capacity fade in Li–S batteries. It is confirmed that the formation and accumulation of nonconductive Li2S2/Li2S films on sulfur cathode surfaces are the major parameters contributing to the rapid capacity fade of Li–S batteries.

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“…Experimental details were described in our previous work. 24 COMSOL 3.4 was used for simulation. Figure 2 illustrates the morphology of both pristine and ballmilled Li 2 S particles.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

High-Capacity Micrometer-Sized Li₂S Particles as Cathode Materials for Advanced Rechargeable Lithium-Ion Batteries

Yang¹,

Zheng²,

et al. 2012

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Li 2 S is a high-capacity cathode material for lithium metal-free rechargeable batteries. It has a theoretical capacity of 1166 mAh/g, which is nearly 1 order of magnitude higher than traditional metal oxides/phosphates cathodes. However, Li 2 S is usually considered to be electrochemically inactive due to its high electronic resistivity and low lithiumion diffusivity. In this paper, we discover that a large potential barrier (∼1 V) exists at the beginning of charging for Li 2 S. By applying a higher voltage cutoff, this barrier can be overcome and Li 2 S becomes active. Moreover, this barrier does not appear again in the following cycling. Subsequent cycling shows that the material behaves similar to common sulfur cathodes with high energy efficiency. The initial discharge capacity is greater than 800 mAh/g for even 10 μm Li 2 S particles. Moreover, after 10 cycles, the capacity is stabilized around 500−550 mAh/g with a capacity decay rate of only ∼0.25% per cycle. The origin of the initial barrier is found to be the phase nucleation of polysulfides, but the amplitude of barrier is mainly due to two factors: (a) charge transfer directly between Li 2 S and electrolyte without polysulfide and (b) lithium-ion diffusion in Li 2 S. These results demonstrate a simple and scalable approach to utilizing Li 2 S as the cathode material for rechargeable lithium-ion batteries with high specific energy. ■ INTRODUCTIONRechargeable lithium-ion batteries have been widely used in portable electronics and are promising for applications in electric vehicles and smart grids. 1−4 However, due to limited capacity in both electrodes, the specific energy of Li-ion batteries needs to be improved significantly to fulfill the requirements in these applications. 5,6 Significant improvement has been achieved in the development of high-capacity materials to replace carbon-based anodes, such as silicon 7−12 and tin. 13 However, state-of-the-art cathode materials have a capacity less than one-half of the carbon anode. Accordingly, breakthroughs in cathodes are urgently needed to increase the specific energy of lithium-ion batteries. Current metal oxide and phosphate cathodes possess an intrinsic capacity limit of ∼300 mAh/g, with a potential of maximum 130% increase in the specific energy if all the capacity can be used. 14,15 In contrast, Li 2 S has a specific capacity of 1166 mAh/g, four times that of the limit in oxide/phosphate cathodes. 15,16 Considering pairing with Si anodes with 2000 mAh/g capacity, the specific energy of a Li 2 S-based lithium-ion battery could be 60% higher than the theoretical limit of metal oxide/phosphate counterparts ( Figure 1A, see Supporting Information for details) and three times that of the current LiCoO 2 /graphite system. Moreover, Li 2 S could be paired with a lithium-free anode, preventing safety concerns and low Coulomb efficiency of lithium metal in Li/S batteries. 17,18 The main hindrance for utilizing Li 2 S is that it is both electronically and ionically insulating. Therefore, Li 2 S was...

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In Operando X-ray Diffraction and Transmission X-ray Microscopy of Lithium Sulfur Batteries

Cited by 477 publications

References 37 publications

A chemistry and material perspective on lithium redox flow batteries towards high-density electrical energy storage

A chemistry and material perspective on lithium redox flow batteries towards high-density electrical energy storage

Capacity Fade Analysis of Sulfur Cathodes in Lithium–Sulfur Batteries

High-Capacity Micrometer-Sized Li₂S Particles as Cathode Materials for Advanced Rechargeable Lithium-Ion Batteries

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In Operando X-ray Diffraction and Transmission X-ray Microscopy of Lithium Sulfur Batteries

Cited by 477 publications

References 37 publications

A chemistry and material perspective on lithium redox flow batteries towards high-density electrical energy storage

A chemistry and material perspective on lithium redox flow batteries towards high-density electrical energy storage

Capacity Fade Analysis of Sulfur Cathodes in Lithium–Sulfur Batteries

High-Capacity Micrometer-Sized Li2S Particles as Cathode Materials for Advanced Rechargeable Lithium-Ion Batteries

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High-Capacity Micrometer-Sized Li₂S Particles as Cathode Materials for Advanced Rechargeable Lithium-Ion Batteries