Interfacial‐Catalysis‐Enabled Layered and Inorganic‐Rich SEI on Hard Carbon Anodes in Ester Electrolytes for Sodium‐Ion Batteries

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(29)

Published: April 5, 2023

Abstract Constructing a homogenous and inorganic‐rich solid electrolyte interface (SEI) can efficiently improve the overall sodium‐storage performance of hard carbon (HC) anodes. However, thick heterogenous SEI derived from conventional ester electrolytes fails to meet above requirements. Herein, an innovative interfacial catalysis mechanism is proposed design favorable in by reconstructing surface functionality HC, which abundant CO (carbonyl) bonds are accurately homogenously implanted. The act as active centers that controllably catalyze preferential reduction salts directionally guide growth form homogenous, layered, SEI. Therefore, excessive solvent decomposition suppressed, Na + transfer structural stability on HC anodes greatly promoted, contributing comprehensive enhancement performance. optimal exhibit outstanding reversible capacity (379.6 mAh g −1 ), ultrahigh initial Coulombic efficiency (93.2%), largely improved rate capability, extremely stable cycling with decay 0.0018% for 10 000 cycles at 5 A . This work provides novel insights into smart regulation chemistry realize high‐performance sodium storage.

Language: Английский

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Temperature-dependent interphase formation and Li+ transport in lithium metal batteries

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: July 25, 2023

High-performance Li-ion/metal batteries working at a low temperature (i.e., <-20 °C) are desired but hindered by the sluggish kinetics associated with Li+ transport and charge transfer. Herein, temperature-dependent behavior during Li plating is profiled various characterization techniques, suggesting that diffusion through solid electrolyte interface (SEI) layer key rate-determining step. Lowering not only slows down transport, also alters thermodynamic reaction of decomposition, resulting in different pathways forming an SEI consisting intermediate products rich organic species. Such metastable unsuitable for efficient transport. By tuning solvation structure lower lowest unoccupied molecular orbital (LUMO) energy level polar groups, such as fluorinated electrolytes like 1 mol L-1 lithium bis(fluorosulfonyl)imide (LiFSI) methyl trifluoroacetate (MTFA): fluoroethylene carbonate (FEC) (8:2, weight ratio), inorganic-rich more readily forms, which exhibits enhanced tolerance to change (thermodynamics) improved (kinetics). Our findings uncover kinetic bottleneck provide directions enhance kinetics/thermodynamics low-temperature performance constructing interphases.

Language: Английский

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A Semisolvated Sole-Solvent Electrolyte for High-Voltage Lithium Metal Batteries

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(44), P. 24260 - 24271

Published: Oct. 27, 2023

Lithium metal batteries (LMBs) coupled with a high-voltage Ni-rich cathode are promising for meeting the increasing demand high energy density. However, aggressive electrode chemistry imposes ultimate requirements on electrolytes used. Among various optimized investigated, localized high-concentration (LHCEs) have excellent reversibility against lithium anode. because they consist of thermally and electrochemically unstable solvents, inferior stability at elevated temperatures cutoff voltages. Here we report semisolvated sole-solvent electrolyte to construct typical LHCE solvation structure but significantly improved using one bifunctional solvent. The designed exhibits exceptional both electrodes suppressed dendrite growth, phase transition, microcracking, transition dissolution. A Li||Ni0.8Co0.1Mn0.1O2 cell this operates stably over wide temperature range from -20 60 °C has capacity retention 95.6% after 100th cycle 4.7 V, ∼80% initial is retained even 180 cycles. This new indicates path toward future engineering safe LMBs.

Language: Английский

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Electrochemically and Thermally Stable Inorganics–Rich Solid Electrolyte Interphase for Robust Lithium Metal Batteries

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(1)

Published: Sept. 9, 2023

Abstract Severe dendrite growth and high‐level activity of the lithium metal anode lead to a short life span poor safety, seriously hindering practical applications batteries. With trisalt electrolyte design, an F‐/N‐containing inorganics–rich solid interphase on is constructed, which electrochemically thermally stable over long‐term cycles safety abuse conditions. As result, its Coulombic efficiency can be maintained 98.98% for 400 cycles. An 85.0% capacity retained coin‐type full cells with 3.14 mAh cm −2 LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode after 200 1.0 Ah pouch‐type 4.0 72 During thermal runaway tests cycled pouch cell, onset triggering temperatures were increased from 70.8 °C 117.4 100.6 153.1 °C, respectively, indicating greatly enhanced performance. This work gives novel insights into interface potentially paving way high‐energy‐density, long‐life‐span, safe

Language: Английский

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Correlating the Solvating Power of Solvents with the Strength of Ion‐Dipole Interaction in Electrolytes of Lithium‐ion Batteries

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(47)

Published: Oct. 9, 2023

The solvation structure of Li+ plays a significant role in determining the physicochemical properties electrolytes. However, to date, there is still no clear definition solvating power different electrolyte solvents, and even solvents that preferentially participate remain controversial. In this study, we comprehensively discuss process ions using both experimental characterizations theoretical calculations. Our findings reveal dependent on strength -solvent (ion-dipole) interaction. Additionally, uncover anions tend enter sheath most systems through -anion (ion-ion) interaction, which weakened by shielding effect solvents. competition between interactions ultimately determines final structures. This insight into fundamental understanding provides inspiration for design multifunctional mixed-solvent electrolytes advanced batteries.

Language: Английский

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Engineering Covalent Organic Frameworks Toward Advanced Zinc‐Based Batteries

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

Published: March 16, 2024

Zinc-based batteries (ZBBs) have demonstrated considerable potential among secondary batteries, attributing to their advantages including good safety, environmental friendliness, and high energy density. However, ZBBs still suffer from issues such as the formation of zinc dendrites, occurrence side reactions, retardation reaction kinetics, shuttle effects, posing a great challenge for practical applications. As promising porous materials, covalent organic frameworks (COFs) derivatives rigid skeletons, ordered structures, permanent porosity, which endow them with application in ZBBs. This review, therefore, provides systematic overview detailing on COFs structure pertaining electrochemical performance ZBBs, following an depth discussion challenges faced by includes dendrites reactions at anode, well dissolution, structural change, slow effect cathode. Then, COF-correlated materials roles various are highlighted. Finally, outlined outlook future development is provided. The review would serve valuable reference further research into utilization

Language: Английский

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Electrolyte Degradation During Aging Process of Lithium‐Ion Batteries: Mechanisms, Characterization, and Quantitative Analysis

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(18)

Published: Feb. 23, 2024

Abstract Given that the non‐aqueous electrolyte in Li‐ion battery plays a specific role as an ion‐transport medium and interfacial modifier for both cathode anode, understanding evaluating evolution degradation of electrolytes throughout life cycle is fundamental concern within lithium‐ion (LIB) community. This article provides comprehensive overview decomposition processes, mechanisms, effects on performance, characterization techniques, modeling analysis. First, it thoroughly discusses processes mechanisms involved from two primary perspectives: 1) formation electrode‐electrolyte interphase 2) bulk electrolyte. Subsequently, systematically outlines performance. The further introduces cutting‐edge detection techniques used to assess degradation, with emphasis quantitative methods analyzing residual practical cells. Moreover, summarizes advanced physical models decomposition. Finally, paper concludes by offering insights into future trends potential challenges research, offers valuable references guidance exploration LIBs.

Language: Английский

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High Voltage Electrolyte Design Mediated by Advanced Solvation Chemistry Toward High Energy Density and Fast Charging Lithium‐Ion Batteries

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(18)

Published: Feb. 25, 2024

Abstract Electrolyte is critical for transporting lithium‐ion (Li + ) in batteries (LIBs). However, there no universally applicable principle designing an optimal electrolyte. In most cases, the design process relies on empirical experiences and often treated as highly confidential proprietary information. Herein, a solvation structure‐related model quantitative of electrolytes introduced, focusing principles coordination chemistry. As paradigmatic example, high‐voltage electrolyte (i.e., 4.5 V vs anode) aimed at achieving high energy density fast charging LIB, which specifically composed emerging, well‐constructed hybrid hard carbon‐silicon/carbon‐based anode, lithium cobalt oxide cathode, developed. Not only functions each component molecular scale within Li structure are analyzed but also interfacial introduced to elucidate their relationship with battery performance. This study represents pioneering effort developing methodology guide design, mutual effects de‐solvation solid interface (SEI) electrode surface explored concurrently understand root cause superior innovative approach establishes new paradigm providing valuable insights level.

Language: Английский

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Building Stable Anodes for High‐Rate Na‐Metal Batteries

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(16)

Published: Jan. 5, 2024

Due to low cost and high energy density, sodium metal batteries (SMBs) have attracted growing interest, with great potential power future electric vehicles (EVs) mobile electronics, which require rapid charge/discharge capability. However, the development of high-rate SMBs has been impeded by sluggish Na

Language: Английский

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A Novel Potassium Salt Regulated Solvation Chemistry Enabling Excellent Li‐Anode Protection in Carbonate Electrolytes

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(25)

Published: March 31, 2023

In lithium-metal batteries (LMBs), the compatibility of Li anode and conventional lithium hexafluorophosphate-(LiPF6 ) carbonate electrolyte is poor owing to severe parasitic reactions. Herein, resolve this issue, a delicately designed additive potassium perfluoropinacolatoborate (KFPB) unprecedentedly synthesized. On one hand, KFPB can regulate solvation structure electrolyte, promoting formation Li+ FPB- K+ PF6- ion pairs with lower lowest unoccupied molecular orbital (LUMO) energy levels. other FPB- anion possesses strong adsorption ability on anode. Thus, anions preferentially adsorb decompose Li-anode surface form conductive robust solid-electrolyte interphase (SEI) layer. Only trace amount (0.03 m) in dendrites' growth be totally suppressed, Li||Cu Li||Li half cells exhibit excellent Li-plating/stripping stability upon cycling. Encouragingly, KFPB-assisted enables high areal capacity LiCoO2 ||Li, LiNi0.8 Co0.1 Mn0.1 O2 (NCM811)||Li, Co0.05 Al0.15 (NCA)||Li LMBs superior cycling stability, showing its universality. This work reveals importance designing novel additives electrolytes improving interface

Language: Английский

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