Near‐ and Long‐Range Electronic Modulation of Single Metal Sites to Boost CO₂ Electrocatalytic Reduction

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(19)

Published: Feb. 27, 2023

Tuning the electronic structure of active center is effective to improve intrinsic activity single-atom catalysts but realization precise regulation remains challenging. Herein, a strategy "synergistically near- and long-range regulation" reported effectively modulate sites. ZnN4 sites decorated with axial sulfur ligand in first coordination surrounded phosphorus atoms carbon matrix are successfully constructed hollow supports (ZnN4 S1 /P-HC). /P-HC exhibits excellent performance for CO2 reduction reaction (CO2 RR) Faraday efficiency CO close 100%. The coupling RR thermodynamically favorable hydrazine oxidation replace oxygen evolution two-electrode electrolyzer can greatly lower cell voltage by 0.92 V at current density 5 mA cm-2 , theoretically saving 46% energy consumption. Theoretical calculation reveals that near-range thiophene-S neighboring P synergistically lead increase electron localization around Zn sites, which strengthens adsorption *COOH intermediate therefore boosts RR.

Language: Английский

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Atomically Dispersed Fe–N₄ and Ni–N₄ Independent Sites Enable Bidirectional Sulfur Redox Electrocatalysis

Nano Letters, Journal Year: 2023, Volume and Issue: 23(9), P. 4000 - 4007

Published: April 26, 2023

Single-atom catalysts (SACs) with high atom utilization and outstanding catalytic selectivity are useful for improving battery performance. Herein, atomically dispersed Ni-N4 Fe-N4 dual sites coanchored on porous hollow carbon nanocages (Ni-Fe-NC) fabricated deployed as the sulfur host Li-S battery. The conductive matrix promotes electron transfer also accommodates volume fluctuation during cycling. Notably, d band center of Fe in site demonstrates strong polysulfide affinity, leading to an accelerated reduction reaction. Meanwhile, Li2S delivers a metallic property S 2p density states around Femi energy level, enabling low evolution reaction barrier. effect Ni-Fe-NC endows cathode density, prolonged lifespan, polarization.

Language: Английский

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MoC‐MoSe₂ Heterostructures as Multifunctional Catalyst Toward Promoting the Stepwise Polysulfide Conversion for Lithium‐Sulfur Batteries

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(33)

Published: April 10, 2024

Abstract Catalyzing polysulfides conversion for lithium‐sulfur batteries is an efficient strategy to overcome the sluggish kinetics of as well its serious shuttling effect. Due multistep and complicated phase transformation sulfur species, monofunctional catalyst can hardly promote overall redox process. Herein, a molybdenum‐based heterostructure proposed, that facilitates entire reduction process by tandemly catalyzing liquid‐liquid liquid‐solid conversion. It uncovered MoC physiochemically immobilizes soluble long‐chain polysulfide accelerates between S 8 Li 2 4 through adsorbing extending S─S bond distance. Then, precipitation enhanced facilitating migration from MoSe . This driven internal electric field at heterogeneous interface low diffusion energy barrier on Li2S Moreover, MoC‐MoSe exhibits smallest degree disproportionation throughout Consequently, cell with /C/S cathode delivers initial discharge‐specific capacity 841.1 mAh g −1 long‐term cycling stability attenuation rate 0.08% per cycle 1.0 C. work presents novelty view design rational multifunction sequentially accelerating stepwise polysulfides.

Language: Английский

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Three Birds with One Stone: Multifunctional TiN‐MXene‐Co@CNTs Network as Sulfur/Lithium Host for High‐Areal‐Capacity Lithium‐Sulfur Batteries

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(35)

Published: June 13, 2024

Abstract The inevitable shuttling and slow redox kinetics of lithium polysulfides (LiPSs) as well the uncontrolled growth Li dendrites have strongly limited practical applications lithium‐sulfur batteries (LSBs). To address these issues, we innovatively constructed carbon nanotubes (CNTs) encapsulated Co nanoparticles in situ grown on TiN‐MXene nanosheets, denoted TiN‐MXene‐Co@CNTs, which could serve simultaneously both sulfur/Li host to kill “three birds with one stone” (1) efficiently capture soluble LiPSs expedite their conversion, (2) accelerate nucleation/decomposition solid 2 S, (3) induce homogeneous deposition. Benefiting from synergistic effects, TiN‐MXene‐Co@CNTs/S cathode a sulfur loading 2.5 mg cm −2 show high reversible specific capacity 1129.1 mAh g −1 after 100 cycles at 0.1 C, ultralong cycle life over 1000 1.0 C. More importantly, it even achieves areal 6.3 50 under 8.9 low E/S ratio 5.0 μL . Besides, TiN‐MXene‐Co@CNTs deliver stable plating/striping behavior h.

Language: Английский

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A Lewis Acid–Lewis Base Hybridized Electrocatalyst for Roundtrip Sulfur Conversion in Lithium–Sulfur Batteries

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(21)

Published: March 29, 2024

Abstract Electrocatalysts can optimize the sulfur/sulfide reaction kinetics in Li–S batteries to compete with loss of lithium polysulfides (LiPSs) caused by shuttling effect. However, design rationale electrocatalysts drive roundtrip conversion is lacking. Here, pairing Lewis acidic and basic active sites reach collective adsorption LiPSs simultaneous activation electrophiles nucleophiles proposed. This concept validated doping polyaniline protonated metatungstate anions, which enables reduced energies for both sulfur reduction sulfide oxidation results significantly improved kinetics. Such enable a battery low capacity‐decay rate 0.029% per cycle 1000 cycles. work would offer insights into technologies where electrocatalysis will play pivotal roles.

Language: Английский

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Defect engineering enables an advanced separator modification for high-performance lithium-sulfur batteries

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 487, P. 150574 - 150574

Published: March 23, 2024

Language: Английский

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MXenes for Sulfur‐Based Batteries

Advanced Energy Materials, Journal Year: 2022, Volume and Issue: 13(4)

Published: Dec. 8, 2022

Abstract Sulfur‐based batteries are regarded as potent candidates for next‐generation high‐energy and low‐cost energy storage systems. However, sulfur‐based still face substantial obstacles on the cathode side (e.g., low conductivity sluggish reaction kinetics of sulfur) anode dendrite growth), severely hindering their utilization. MXenes (i.e., 2D transition metal carbides, nitrides, carbonitrides), an emerging member material family, possess unique electrochemical electronic properties, which make them attractive materials to enhance performance batteries. In this article, a comprehensive review research progress using in is provided. The basics MXene introduced first, wherein merits applying discussed. Subsequently, field systematically summarized terms roles batteries, including sulfur host, MXene‐based composite separator modification, advanced electrodes. end, recommendations specific future directions advance development outlined.

Language: Английский

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Status and prospects of electrocatalysts for lithium-sulfur battery under lean electrolyte and high sulfur loading conditions

Chemical Engineering Journal, Journal Year: 2022, Volume and Issue: 452, P. 139344 - 139344

Published: Sept. 22, 2022

Language: Английский

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Li–S Chemistry of Manganese Phosphides Nanoparticles With Optimized Phase

Advanced Science, Journal Year: 2023, Volume and Issue: 10(9)

Published: Feb. 3, 2023

The targeted synthesis of manganese phosphides with target phase remains a huge challenge because their various stoichiometries and phase-dependent physicochemical properties. In this study, phosphorus-rich MnP, manganese-rich Mn2 P, heterostructure MnP-Mn2 P nanoparticles evenly dispersed on porous carbon are accurately synthesized by convenient one-pot heat treatment phosphate resin combined Mn2+ . Moreover, electrochemical properties systematically investigated as sulfur hosts in lithium-sulfur batteries. Density functional theory calculations demonstrate the superior adsorption, catalysis capabilities, electrical conductivity P/C, compared MnP/C P/C. P/C@S exhibits an excellent capacity 763.3 mAh g-1 at 5 C decay rate only 0.013% after 2000 cycles. A evolution product (MnS) is detected during P/C polysulfides redox through situ X-ray diffraction Raman spectroscopy. At loading up to 8 mg cm-2 , achieves area 6.4 0.2 C. pouch cell cathode initial energy density 360 Wh kg-1

Language: Английский

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Flexible solid-state lithium-sulfur batteries based on structural designs

Energy storage materials, Journal Year: 2023, Volume and Issue: 57, P. 429 - 459

Published: Feb. 22, 2023

Language: Английский

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