Electronegativity Matching of Asymmetrically Coordinated Single‐Atom Catalysts for High‐Performance Lithium–Sulfur Batteries

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(19)

Published: March 13, 2024

Abstract Asymmetrically coordinated single‐atom catalysts are attractive for the implementation of high‐performance lithium–sulfur (Li─S) batteries. However, design principle asymmetric coordination that can efficiently promote bidirectional conversion polysulfides has not been fully realized. Herein, a series Co─N 3 X 1 ( refers to F, O, Cl, S, or P) configurations established, and theoretically unravel relative electronegativity value (REV) be used as an index parameter characterizing catalytic activity. By virtue enhanced chemical affinity with sulfur species lowered Li 2 S decomposition, chlorine‐atom‐constructed optimal REV exhibit stronger effect inhibit shuttling. Such REV‐related is termed effect. Following this principle, novel catalyst dominated Cl configuration successfully synthesized through inside‐out thermal reaction strategy modified layer on cathode‐side separator. Interestingly, assembled Li─S batteries quite high rate capacity (804.3 mAh g −1 at 5.0 C), durable cyclability (0.023% decay per cycle), competitive areal (7.0 cm −2 under 7.5 mg loading lean electrolyte). The guideline provided in work gives impetus pursuit highly efficient practical

Language: Английский

---

Accelerated Sulfur Redox Kinetics on Transition Metal Sulfide Electrocatalysts by Modulating Electronic‐State of Active Sites

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(25)

Published: April 5, 2024

Abstract Lithium‐sulfur (Li‐S) batteries are considered a competitive next‐generation electrochemical energy storage device, while the shuttle effect of soluble lithium polysulfides (LiPSs) resulting from sluggish redox kinetics severely impedes their practical applications. Herein, novel cation doping strategy is demonstrated for substantially accelerating sulfur on transition metal sulfide (TMS) electrocatalysts by partially substituting cobalt atoms with in situ dissolved Ni dopants (Ni x Co 3‐x S 4 , 0<x≤1). Theoretical calculations revealed that spinel 3 phase enables electronic‐state modulation active sites realizing upshift d‐orbital center, thus leading to good chemical adsorption intermediates and low conversion barriers between LiPSs solid Li 2 products. This confirmed in‐depth dynamics Raman characterizations, which obtained 0.5 2.5 hierarchical nanosheet structure delivers stronger affinity 6 higher precipitation/dissociation capacity comparison monometallic sulfides. Benefiting these outstanding attributes, assembled Li‐S incorporating into S@carbon nanotube cathode (S@Ni /CNT) exhibit high specific 1189 mAh g −1 excellent rate performance 596 at 5 C long‐term cycling over 600 cycles decay 0.06% per cycle 1 C. More importantly, an ultrahigh reversible areal 6.6 cm −2 can be achieved S@Ni /CNT even loading 6.1 mg . work demonstrates new insight designing TMS toward rapid batteries.

Language: Английский

---

Juice Vesicles Bioreactors Technology for Constructing Advanced Carbon‐Based Energy Storage

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(24)

Published: Feb. 20, 2024

The construction of high-quality carbon-based energy materials through biotechnology has always been an eager goal the scientific community. Herein, juice vesicles bioreactors (JVBs) bio-technology based on hesperidium (e.g., pomelo, waxberry, oranges) is first reported for preparation composites with controllable components, adjustable morphologies, and sizes. JVBs serve as miniature reaction vessels that enable sophisticated confined chemical reactions to take place, ultimately resulting in formations complex carbon composites. newly developed approach highly versatile can be compatible a wide range including metals, alloys, metal compounds. growth self-assembly mechanisms via are explained. For illustration, NiCo alloy nanoparticles successfully situ implanted into pomelo crosslinked (PCC) by JVBs, their applications sulfur/carbon cathodes lithium-sulfur batteries explored. well-designed PCC/NiCo-S electrode exhibits superior high-rate properties enhanced long-term stability. Synergistic reinforcement transportation ions/electrons interface catalytic conversion lithium polysulfides arising from architecture proposed aid DFT calculations. research provides novel biosynthetic route rational design fabrication advanced storage.

Language: Английский

---

Lithiophilic V₂CT_x/MoO₃ Hosts with Electronic/Ionic Dual Conductive Gradients for Ultrahigh‐Rate Lithium Metal Anodes

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: July 24, 2024

Abstract Lithium (Li) metal is considered as a promising anode material for high‐energy batteries; yet, its practical application hindered by uncontrolled Li dendrite growth, especially at high rate. Herein, dual conductive gradient V 2 CT x /MoO 3 (DG‐V ) host that integrates electronic/ionic gradients and lithiophilicity prepared layer‐by‐layer assembly dendrite‐free anodes. Gradient LiF deriving from different amount of endows good ionic gradient; while, MoO regarded spacer to avoid the restacking , increasing space deposition. The effectively optimize current density + flux distribution bottom, achieving fast reduction “bottom–up” deposition mode. Meanwhile, lithiophilic guide homogeneous growth. As result, symmetrical half‐cells based on DG‐V @Li anodes conduct 700 h 5 mAh cm −2 20 mA . @Li||LiFePO 4 full‐cells maintain capacity retention 85.4% after 1350 cycles C. Remarkably, @Li||LiNi 0.6 Co 0.2 Mn O can run 150 with 80.6% even harsh conditions. well‐adjusted materials structures both properties will bring inspiration novel design other batteries.

Language: Английский

---

Co-Fe dual-atom isolated in N-doped graphydine as an efficient sulfur conversion catalyst in Li-S batteries

Journal of Alloys and Compounds, Journal Year: 2024, Volume and Issue: 988, P. 174136 - 174136

Published: March 15, 2024

Language: Английский

---

Progresses and Prospects of Asymmetrically Coordinated Single Atom Catalysts for Lithium−Sulfur Batteries

Energy & environment materials, Journal Year: 2024, Volume and Issue: 7(4)

Published: Feb. 11, 2024

Lithium–sulfur batteries (LSBs) are widely regarded as promising next‐generation due to their high theoretical specific capacity and low material cost. However, the practical applications of LSBs limited by shuttle effect lithium polysulfides (LiPSs), electronic insulation charge discharge products, slow LiPSs conversion reaction kinetics. Accordingly, introduction catalysts into is one effective strategy solve issues sluggished LiPS conversion. Because nearly 100% atom utilization electrocatalytic activity, single‐atom (SACs) have been used mediators for LSBs' reactions. Excitingly, SACs with asymmetric coordination structures exhibited intriguing superior catalytic activities when compared traditional M–N 4 active sites. In this review, we systematically describe recent advancements in installation asymmetrically coordinated structure reactions LSBs, including nitrogen SACs, heteroatom support bimetallic SACs. Particularly noteworthy discussion mechanism spanning Finally, a perspective on future developments LSB provided.

Language: Английский

---

Structural Regulation Strategies of Atomic Cobalt Catalysts for Oxygen Electrocatalysis

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 3, 2025

Abstract Oxygen electrocatalysis is a core reaction in renewable energy devices, greatly promoting the transformation and upgrading of structure. Nonetheless, performance conversion devices hindered by large overpotential slow kinetics oxygen electrocatalytic reactions. Recently, single‐atom catalysts (SACs) have emerged as promising contenders field because their exceptional metal atom utilization, distinctive coordination environment, adjustable electronic properties. This review presents latest advancements design Co‐based SACs for electrocatalysis. First, OER ORR mechanisms are introduced. Subsequently, strategies regulating structure summarized three aspects, including centers, support carriers. A particular emphasis given to relationship between properties catalysts. Afterward, applications explored. Ultimately, challenges prospects prospected.

Language: Английский

---

Synergistic enhancement of chemisorption and catalytic conversion in lithium-sulfur batteries via Co3Fe7/Co5.47N separator mediator

Journal of Colloid and Interface Science, Journal Year: 2023, Volume and Issue: 657, P. 757 - 766

Published: Dec. 5, 2023

Language: Английский

---

Steering Bidirectional Sulfur Redox via Geometric/Electronic Mediator Comodulation for Li–S Batteries

ACS Nano, Journal Year: 2023, Volume and Issue: 17(6), P. 6002 - 6010

Published: March 13, 2023

Mediator design has stimulated ever-increasing attention to help tackle a surge of detrimental caveats in Li-S realms, mainly pertaining rampant polysulfide shuttling and sluggish redox kinetics. Nevertheless, universal designing philosophy, despite being highly sought-after, remains still elusive date. Herein, we present generic simple material strategy allow the target fabrication advanced mediator toward boosted sulfur electrochemistry. This trick is done by geometric/electronic comodulation prototype VN mediator, where interplay its triple-phase interface, favorable catalytic activity, facile ion diffusivity conducive steering bidirectional In laboratory tests, thus-derived cells manifest impressive cyclic performances with capacity decay rate 0.07% per cycle over 500 cycles at 1.0 C. Moreover, under loading 5.0 mg cm-2, cell could sustain durable areal 4.63 mAh cm-2. Our work anticipated lay theory-to-application foundation for rationalizing modulation reliable mediators working batteries.

Language: Английский

---

Operating Lithium–Sulfur Batteries in an Ultrawide Temperature Range from ‒50 °C to 70 °C

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(48)

Published: Sept. 3, 2023

Abstract Lithium–sulfur (Li–S) batteries, boasting a high theoretical energy density, have garnered significant attention. However, their application across wide temperature range remains hindered by the exacerbation of polysulfide shuttle effect and sluggish reaction kinetics. Herein, this work designs nanocomposite electrocatalyst consisting Ni nanoparticles anchored onto carbon nanotubes (denoted as Ni@C/CNT) directly carbonizing metal‐organic framework/CNT (MOF/CNT) composite. This is then coated commercial separator, acting trapper kinetics accelerator for Li–S batteries. In design, Ni@C/CNT features uniform distribution ultrafine nanoparticles, derived from an MOF precursor with ordered metal sites, which facilitates conversion at low chemisorption polysulfides temperatures. Therefore, Ni@C/CNT‐modified cells can stably cycle range, ‒50 °C to 70 °C. They also demonstrate excellent performance high‐sulfur loading (9.0 mg cm −2 ) room exhibit ultralow self‐discharge capacity attenuation 2.59% after 48‐h resting period. These promising results may guide advanced design batteries broad operating‐temperature capabilities.

Language: Английский

---