Unraveling Shuttle Effect and Suppression Strategy in Lithium/Sulfur Cells by In Situ/Operando X‐ray Absorption Spectroscopic Characterization

Energy & Environ Materials

Chen

Lin

et al. 2022

Self Cite

124

Lithium-sulfur batteries exhibit unparalleled merits in theoretical energy density (2600 W h kg −1 ) among next-generation storage systems. However, the sluggish electrochemical kinetics of sulfur reduction reactions, sulfide oxidation reactions in the sulfur cathode, and the lithium dendrite growth resulted from uncontrollable lithium behaviors in lithium anode have inhibited high-rate conversions and uniform deposition to achieve high performances. Thanks to the "adsorption-catalysis" synergetic effects, the reaction kinetics of sulfur reduction reactions/sulfide oxidation reactions composed of the delithiation of Li 2 S and the interconversions of sulfur species are propelled by lowering the delithiation/diffusion energy barriers, inhibiting polysulfide shuttling. Meanwhile, the anodic plating kinetic behaviors modulated by the catalysts tend to uniformize without dendrite growth. In this review, the various active catalysts in modulating lithium behaviors are summarized, especially for the defect-rich catalysts and single atomic catalysts. The working mechanisms of these highly active catalysts revealed from theoretical simulation to in situ/operando characterizations are also highlighted. Furthermore, the opportunities of future higher performance enhancement to realize practical applications of lithium-sulfur batteries are prospected, shedding light on the future practical development.

Section: Introductionmentioning

confidence: 99%

Electrochemical Kinetic Modulators in Lithium–Sulfur Batteries: From Defect‐Rich Catalysts to Single Atomic Catalysts

Energy & Environ Materials

Chen

Lin

et al. 2022

Self Cite

124

“…[ 6 ] More interestingly, the sulfur is abundantly available on earth's crust and more environmental friendly than metal‐based intercalated cathodes, making it more competitive and costless for future application [6c,7] . In spite of the overwhelming capacity superiority, the device application of Li–S batteries is still hindered by the insulation of sulfur/Li 2 S, large volume change of ≈80% between S and Li 2 S (80%), shuttle effect of the soluble lithium polysulfides (LiPSs), sluggish conversion kinetics ( Figure A), [ 8 ] and the lithium dendrites growth on the anode surface (Figure 1B), resulting in depressed cycling lifespan with insufficient sulfur utilization and safety concerns. [ 9 ]…”

Section: Introductionmentioning

confidence: 99%

Advances and Prospects of 2D Graphene‐Based Materials/Hybrids for Lithium Metal–Sulfur Full Battery: From Intrinsic Property to Catalysis Modification

Adv Energy and Sustain Res

Jia

Lin

et al. 2022

Self Cite

Rechargeable lithium–sulfur (Li–S) full batteries hold practical promise for next‐generation energy storage system owing to low cost and unparalleled theoretical energy density of 2600 W h kg−1. However, wide commercialization is severely hampered by the poor conductivity of S/Li2S, worrisome polysulfide shuttling effect, sluggish multistep reaction kinetics, and uncontrolled lithium dendrite growth. 2D materials show the advantages in suppressing polysulfide shuttling and boosting lithium diffusion kinetics through rational modifications of surface chemistry and nanostructure design, greatly enhancing battery performances. In this review, the recent developments of 2D graphene‐based materials in propelling the conversion/plating kinetics of Li–S full batteries are highlighted from intrinsic conductive property to adsorption and catalysis modifications. Specifically, with the functionalization of the pore morphology and heteroatom/metal atom doping in the pristine/hybrid matrix, the adsorption ability and the lithium diffusion kinetics are significantly enhanced in both cathodic and anodic side, so that the interconversion kinetics of sulfur species are propelled to inhibit polysulfide shuttling and lithium‐ion flux is homogenized to realize uniform deposition without any dendrite growth. Furthermore, challenges and opportunities for future fully development of Li–S batteries based on 2D graphene‐based materials are prospected from interfacial mechanisms at the atomic/molecular level to large‐scale production.

“…With the rapid evolution of smart grids, electronic vehicles, and smart devices, higher capacity and energy density storage systems are urgently needed 1–6 . As one of the most prospective candidates, lithium‐sulfur (Li‐S) batteries have been intensively studied, owing to their structural similarity to Li‐ion batteries but high energy density (2600 Wh kg −1 ), and low environmental impact of sulfur 7–12 .…”

Section: Introductionmentioning

confidence: 99%

“…With the rapid evolution of smart grids, electronic vehicles, and smart devices, higher capacity and energy density storage systems are urgently needed. [1][2][3][4][5][6] As one of the most prospective candidates, lithium-sulfur (Li-S) batteries have been intensively studied, owing to their structural similarity to Li-ion batteries but high energy density (2600 Wh kg À1 ), and low environmental impact of sulfur. [7][8][9][10][11][12] However, the practical application of a Li-S battery with high-energy density will only be realized at the conditions of low negative/positive (N/P) and electrolyte/sulfur (E/S) ratios.…”

Section: Introductionmentioning

confidence: 99%

Complex permittivity‐dependent plasma confinement‐assisted growth of asymmetric vertical graphene nanofiber membrane for high‐performance Li‐S full cells

Wang

et al. 2022

InfoMat

Vertical graphene (VG), possessing superior chemical, physical, and structural peculiarities, holds great promise as a building block for constructing a high‐energy density lithium‐sulfur (Li‐S) battery. Therefore, it is desirable to develop a new VG growth technique with a novel structure to enable wide applications. Herein, we devise a novel complex permittivity‐dependent plasma confinement‐assisted VG growth technique, via asymmetric growing a VG layer on one side of N‐doped carbon nanofibers for the first time, using a unique lab‐built high flux plasma‐enhanced chemical vapor deposition system, as a bifunctional nanofiber membrane to construct Li‐S batteries with low negative/positive (N/P) and electrolyte/sulfur (E/S) ratios. The unique nanofiber membrane could simultaneously protect the cathode and anode, enabling an excellent electrochemical performance with low N/P and E/S ratios in Li‐S batteries. Such a full cell delivers high gravimetric energy density and volumetric energy density of 340 Wh kg−1 and 547 Wh L−1, respectively, at low N/P (2:1) and E/S (4:1) ratios. Furthermore, a pouch cell achieves a high areal capacity of 7.1 mAh cm−2 at a sulfur loading of 6 mg cm−2. This work put forward a novel pathway for the design of high‐energy density Li‐S batteries.