Ambient‐temperature sodium–sulfur (Na–S) batteries are considered a promising energy storage system due to their high theoretical energy density and low costs. However, great challenges remain in ...achieving a high rechargeable capacity and long cycle life. Herein we report a stable quasi‐solid‐state Na‐S battery enabled by a poly(S‐pentaerythritol tetraacrylate (PETEA))‐based cathode and a (PETEA‐tris2‐(acryloyloxy)ethyl isocyanurate (THEICTA))‐based gel polymer electrolyte. The polymeric sulfur electrode strongly anchors sulfur through chemical binding and inhibits the shuttle effect. Meanwhile, the in situ formed polymer electrolyte with high ionic conductivity and enhanced safety successfully stabilizes the Na anode/electrolyte interface, and simultaneously immobilizes soluble Na polysulfides. The as‐developed quasi‐solid‐state Na‐S cells exhibit a high reversible capacity of 877 mA h g−1 at 0.1 C and an extended cycling stability.
Energy storage: A stable quasi‐solid‐state Na–S battery has been obtained using a poly(S‐pentaerythritol tetraacrylate (PETEA)) cathode and a (PETEA‐tris2‐(acryloyloxy)ethyl isocyanurate (THEICTA)) gel polymer electrolyte. The electrode strongly anchors sulfur by chemical binding, meanwhile the polymer electrolyte with high ionic conductivity and stable Na/electrolyte interface effectively suppresses the shuttle of polysulfides.
Lithium–sulfur (Li–S) batteries are considered to be one of the most promising candidate systems for next‐generation electrochemical energy storage. The major challenge of this system is the ...polysulfide shuttle, which results in poor cycling efficiency. In this work, a highly N‐doped carbon/graphene (NC/G) sheet is designed as a sulfur host, which combines the merits of abundant N active sites and high electrical conductivity to achieve in situ anchoring–conversion of lithium polysulfides (LiPSs). Such a host not only has strong binding with LiPSs but also promotes redox kinetics, which are revealed by both experimental investigations and theoretical studies. The sulfur cathode based on the NC/G host exhibits a high initial capacity of 1380 mA h g−1 and a superior cycle stability with a low capacity decay of 0.037% per cycle within 500 cycles at 2 C. Steady areal capacity with a high sulfur loading (5.6 mg cm−2) is also attained even without the addition of LiNO3 in the electrolyte. This work proposes and illustrates the importance of in situ anchoring–conversion of LiPSs, offering a new strategy to design multifunctional sulfur hosts for high‐performance Li–S batteries.
A highly N‐doped carbon/graphene host combines the merits of being attractively conductive, which accelerates efficient electron transfer, having sufficient binding affinity, which renders effective anchoring, and having abundant reactive sites with effective catalytic effects that facilitate redox kinetics to accomplish in situ anchoring–conversion of lithium polysulfides (LiPSs). Such a multifunctional host effectively alleviates the polysulfides' shuttle and hence improves the performance of Li–S batteries.
Room‐temperature sodium–sulfur (RT‐Na/S) batteries possess high potential for grid‐scale stationary energy storage due to their low cost and high energy density. However, the issues arising from the ...low S mass loading and poor cycling stability caused by the shuttle effect of polysulfides seriously limit their operating capacity and cycling capability. Herein, sulfur‐doped graphene frameworks supporting atomically dispersed 2H‐MoS2 and Mo1 (S@MoS2‐Mo1/SGF) with a record high sulfur mass loading of 80.9 wt.% are synthesized as an integrated dual active sites cathode for RT‐Na/S batteries. Impressively, the as‐prepared S@MoS2‐Mo1/SGF display unprecedented cyclic stability with a high initial capacity of 1017 mAh g−1 at 0.1 A g−1 and a low‐capacity fading rate of 0.05% per cycle over 1000 cycles. Experimental and computational results including X‐ray absorption spectroscopy, in situ synchrotron X‐ray diffraction and density‐functional theory calculations reveal that atomic‐level Mo in this integrated dual‐active‐site forms a delocalized electron system, which could improve the reactivity of sulfur and reaction reversibility of S and Na, greatly alleviating the shuttle effect. The findings not only provide an effective strategy to fabricate high‐performance dual‐site cathodes, but also deepen the understanding of their enhancement mechanisms at an atomic level.
An integrated dual‐active‐site cathode is developed by wreathing monolayered MoS2 and Mo1 on sulfur‐doped graphene frameworks for high‐performance room‐temperature sodium–sulfur batteries. The constructed atomic level MoS2‐Mo1 with delocalized electron effects facilitates substantial charge transfer and a completely reversible reaction between S and Na, thus alleviating the shuttle effect.
High‐energy density and ultra‐long cycling lifespan are of great significance in pursuit of practical lithium–sulfur (Li‐S) batteries, in which the construction of ultrathick, high‐areal‐capacity, ...and stable‐cycling sulfur cathodes remains challenging. Here, a unique layered reinforced concrete structure (LRCS) is reported by integrating an ice‐template method with incorporating carbon fibers in the thick electrodes for Li‐S batteries. The LRCS enables aligned through‐channel structure and intertwined conductive network, which lead to both fast kinetics of ions/electrons transport and strengthened electrode integrity to tolerate the volume change during cycling and the dimensional deformation under a high compaction density. Benefiting from the unique structure, the ultra‐thick Se0.05S0.95 @ pPAN cathode (20.2 mg cm−2) delivers a high capacity of 10 mAh cm−2 and excellent capacity retention of 80.8% over 140 cycles at a low electrolyte‐to‐sulfur ratio of 2 and a negative‐to‐positive capacity ratio of 2.7, corresponding to a calculated energy density of 390 Wh kg−1. This investigation not only provides guidance for the design of thick sulfur electrodes but also paves the way for the development of practical Li‐S batteries.
The layered reinforced concrete structure enables sulfur cathode with aligned through‐channel and intertwined conductive network, leading to fast kinetics and strengthened integrity during cycling. Benefiting from the unique structure, the ultra‐thick sulfur cathode delivers a high capacity of 10 mAh cm−2 and excellent cycling life (80.8%) over 140 cycles under lean electrolyte (E/S=2) and limited lithium (N/P=2.7).
The room‐temperature (RT) Na/S battery is a promising energy storage system owing to suitable operating temperature, high theoretical energy density, and low cost. However, it has a poor cycle life ...and low reversible capacity. In this work, we report a long‐life RT‐Na/S battery with amorphous porous silica as a sulfur host. The sulfur is loaded into amorphous silica by a dipping method; the optimal sulfur loading is up to 73.48 wt %. Molecular dynamics simulation and first‐principles calculations suggest that the complex pores, acting as micro‐containers and the formation of Na‐O chemical bonds between amorphous silica and sodium polysulfide, give the electrodes a strong ability to inhibit sodium polysulfide shuttle. This would give rise to effectively avoiding the loss of active sulfur, corresponding to a superior capacity and an excellent cyclability even at 10 A gsulfur−1 (nearly 100 % coulomb efficiency and high reversible capacity of 955.8 mAh gsulfur−1 after 1460 cycles).
Sulfur as an electrode is loaded into amorphous silica by a facile dipping method. In charge/discharge process, the complex pores of amorphous silica, acting as micro‐containers and the formation of Na‐O chemical bonds between amorphous silica and sodium polysulfide, give the electrodes a strong ability to inhibit sodium polysulfide shuttle.
A High‐Energy Aqueous All‐Sulfur Battery Wang, Huimin; Bi, Songshan; Zhang, Yanyu ...
Angewandte Chemie International Edition,
March 4, 2024, Letnik:
63, Številka:
10
Journal Article
Recenzirano
Rechargeable aqueous batteries are promising energy storage devices because of their high safety and low cost. However, their energy densities are generally unsatisfactory due to the limited ...capacities of ion‐inserted electrode materials, prohibiting their widespread applications. Herein, a high‐energy aqueous all‐sulfur battery was constructed via matching S/Cu2S and S/CaSx redox couples. In such batteries, both cathodes and anodes undergo the conversion reaction between sulfur/metal sulfides redox couples, which display high specific capacities and rational electrode potential difference. Furthermore, during the charge/discharge process, the simultaneous redox of Cu2+ ion charge‐carriers also takes place and contributes to a more two‐electron transfer, which doubles the capacity of cathodes. As a result, the assembled aqueous all‐sulfur batteries deliver a high discharge capacity of 447 mAh g−1 based on total mass of sulfur in cathode and anode at 0.1 A g−1, contributing to an enhanced energy density of 393 Wh kg−1. This work will widen the scope for the design of high‐energy aqueous batteries.
A high‐energy aqueous all‐sulfur battery was constructed by matching the S/Cu2S and S/CaSx redox couples with rational electrode potential difference. The aqueous all‐sulfur batteries deliver a high specific capacity and discharge voltage, contributing to an enhanced energy density.
The modular assembly of microstructures from simple nanoparticles offers a powerful strategy for creating materials with new functionalities. Such microstructures have unique physicochemical ...properties originating from confinement effects. Here, the modular assembly of scattered ketjen black nanoparticles into an oval‐like microstructure via double “Fischer esterification,” which is a form of surface engineering used to fine‐tune the materials surface characteristics, is presented. After carbonization, the oval‐like carbon microstructure shows promise as a candidate sulfur host for the fabrication of thick sulfur electrodes. Indeed, a specific discharge capacity of 8.417 mAh cm−2 at 0.1 C with a high sulfur loading of 8.9 mg cm−2 is obtained. The large‐scale production of advanced lithium–sulfur battery pouch cells with an energy density of 460.08 Wh kg−1@18.6 Ah is also reported. This work provides a radically different approach for tuning the performance of a variety of surfaces for energy storage materials and biological applications by reconfiguring nanoparticles into desired structures.
The modular assembly of microstructures from simple nanoparticles offers a powerful strategy to create materials with new functionalities. A modular‐assembled oval‐like microstructure is proposed and used as sulfur host for thick electrodes. By tuning the surface of nanoparticles, double Fischer esterification that is conducted among phytic, ethylene glycol, and the functionalized nanoparticles reconfigures scattered nanoparticles into oval‐like carbon microstructures.
Rechargeable aqueous batteries are promising energy storage devices because of their high safety and low cost. However, their energy densities are generally unsatisfactory due to the limited ...capacities of ion‐inserted electrode materials, prohibiting their widespread applications. Herein, a high‐energy aqueous all‐sulfur battery was constructed via matching S/Cu2S and S/CaSx redox couples. In such batteries, both cathodes and anodes undergo the conversion reaction between sulfur/metal sulfides redox couples, which display high specific capacities and rational electrode potential difference. Furthermore, during the charge/discharge process, the simultaneous redox of Cu2+ ion charge‐carriers also takes place and contributes to a more two‐electron transfer, which doubles the capacity of cathodes. As a result, the assembled aqueous all‐sulfur batteries deliver a high discharge capacity of 447 mAh g−1 based on total mass of sulfur in cathode and anode at 0.1 A g−1, contributing to an enhanced energy density of 393 Wh kg−1. This work will widen the scope for the design of high‐energy aqueous batteries.
A high‐energy aqueous all‐sulfur battery was constructed by matching the S/Cu2S and S/CaSx redox couples with rational electrode potential difference. The aqueous all‐sulfur batteries deliver a high specific capacity and discharge voltage, contributing to an enhanced energy density.
Mechanism of Cathodic Reduction of Sulfur Kulova, T. L.; Li, S. A.; Ryzhikova, E. V. ...
Russian Journal of Physical Chemistry A,
10/2021, Letnik:
95, Številka:
10
Journal Article
Recenzirano
The mechanism of the cathodic reduction of sulfur is studied via cyclic voltammetry. An analysis of cyclic voltammograms using normalized coordinates shows that insoluble products (particularly Li
2
...S
2
) form not as a result of an electrochemical process, but due to the disproportionation of Li
2
S
4.
The degradation of sulfur electrodes during cycling is associated with incomplete oxidation of the products of the cathodic reaction to elemental sulfur.
PDF
