Fluorine Chemistry in Rechargeable Batteries: Challenges, Progress, and Perspectives

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(6), P. 3494 - 3589

Published: March 13, 2024

The renewable energy industry demands rechargeable batteries that can be manufactured at low cost using abundant resources while offering high density, good safety, wide operating temperature windows, and long lifespans. Utilizing fluorine chemistry to redesign battery configurations/components is considered a critical strategy fulfill these requirements due the natural abundance, robust bond strength, extraordinary electronegativity of free fluoride formation, which enables fluorinated components with effectiveness, nonflammability, intrinsic stability. In particular, materials electrode|electrolyte interphases have been demonstrated significantly affect reaction reversibility/kinetics, tolerance batteries. However, underlining principles governing material design mechanistic insights atomic level largely overlooked. This review covers range topics from exploration fluorine-containing electrodes, electrolyte constituents, other for metal-ion shuttle constructing fluoride-ion batteries, dual-ion new chemistries. doing so, this aims provide comprehensive understanding structure–property interactions, features interphases, cutting-edge techniques elucidating role in Further, we present current challenges promising strategies employing chemistry, aiming advance electrochemical performance, operation, safety attributes

Language: Английский

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Anion Receptor Weakens ClO₄⁻ Solvation for High‐Temperature Sodium‐Ion Batteries

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(5)

Published: May 17, 2023

Abstract Sodium‐ion batteries (SIBs) with wide operating temperature are regarded as promising candidates for large‐scale energy storage systems. However, SIBs under elevated aggravate the electrolyte decomposition unstable cathode‐electrolyte interphase (CEI), causing a rapid capacity degradation. Herein, anion receptor tris(pentafluorophenyl)borane (TPFPB) is selected additive to construct robust NaF‐rich CEI. The strong interactions between and TPFPB via electron‐deficient boron atoms weaken ClO 4 − solvation promote coordination capability solvents Na + cations, demonstrating greatly improved oxidative stability. 3 V 2 (PO ) cathode in TPFPB‐containing delivers long‐term stability retention of 86.9% after 100 cycles at high cut‐off voltage 4.2 (vs. /Na) 60 °C. Besides, also works well enhanced performance over range from −30 This study proposes prospective method by manipulating chemistry constructing high‐temperature rechargeable SIBs.

Language: Английский

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Additive‐guided Solvation‐regulated Flame‐retardant Electrolyte Enables High‐voltage Lithium Metal Batteries with Robust Electrode Electrolyte Interphases

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(16)

Published: Jan. 2, 2024

Abstract Widening the voltage window of nickel‐rich layered oxide cathode‐based lithium metal batteries (LMBs) can effectively improve energy density rechargeable batteries. However, serious safety issues associated with high reactivity between LiNi 0.8 Co 0.1 Mn O 2 (NCM811) and electrolyte at cut‐off remains challenging. Herein, a flame‐retardant ability to form robust armor‐like electrode interphase (EEI) LiF Li x B y z compounds for stabilizing Li||NCM811 is proposed. Such exhibits thermal stability effect ensuring battery voltage. The EEI protect both NCM811 (Li) improving cycling performance. As result, capacity retention rate cathode such reached 68% after 150 cycles 4.6 V. This work provides an effective reference reasonable design high‐voltage, electrolytes LMBs.

Language: Английский

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Carbonate Ester-Based Electrolyte Enabling Rechargeable Zn Battery to Achieve High Voltage and High Zn Utilization

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9455 - 9464

Published: March 21, 2024

Owing to the high H

Language: Английский

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570 Wh kg⁻¹‐Grade Lithium Metal Pouch Cell with 4.9V Highly Li⁺ Conductive Armor‐Like Cathode Electrolyte Interphase via Partially Fluorinated Electrolyte Engineering

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

Published: March 4, 2024

Abstract Lithium‐rich manganese‐based layered oxides (LRMOs) are promisingly used in high‐energy lithium metal pouch cells due to high specific capacity/working voltage. However, the interfacial stability of LRMOs remains challenging. To address this question, a novel armor‐like cathode electrolyte interphase (CEI) model is proposed for stabilizing LRMO at 4.9 V by exploring partially fluorinated formulation. The fluoroethylene carbonate (FEC) and tris (trimethylsilyl) borate (TMSB) formulated largely contribute formation CEI with LiB x O y Li PO F z outer layer LiF‐ 3 4 ‐rich inner part. Such effectively inhibits lattice oxygen loss facilitates + migration smoothly guaranteeing deliver superior cycling rate performance. As expected, Li||LRMO batteries such achieve capacity retention 85.7% average Coulomb efficiency (CE) 99.64% after 300 cycles 4.8 V/0.5 C, even obtain 87.4% 100 higher cut‐off voltage V. Meanwhile, 9 Ah‐class show over thirty‐eight stable life energy density 576 Wh kg −1

Language: Английский

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Mechanically and Thermally Stable Cathode Electrolyte Interphase Enables High‐temperature, High‐voltage Li||LiCoO₂ Batteries

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(7)

Published: Dec. 12, 2023

Abstract The development of high‐energy‐density Li||LiCoO 2 batteries is severely limited by the instability cathode electrolyte interphase (CEI) at high voltage and temperature. Here we propose a mechanically thermally stable CEI designing for achieving exceptional performance 4.6 V 70 °C. 2,4,6‐tris(3,4,5‐trifluorophenyl)boroxin (TTFPB) as additive could preferentially enter into first shell structure PF 6 − solvation be decomposed on LiCoO surface low oxidation potential to generate LiB x O y ‐rich/LiF‐rich CEI. layer effectively maintained integrity provided excellent mechanical thermal stability while abundant LiF in further improved homogeneity Such drastically alleviated crack regeneration irreversible phase transformation cathode. As expected, with tailored achieved 91.9 % 74.0 capacity retention after 200 150 cycles 4.7 V, respectively. Moreover, such also delivered an unprecedented high‐temperature 73.6 100 °C V.

Language: Английский

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Porous and chemically robust MIL-100(V) MOF as an efficient cathode material for zinc‑ion batteries

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 470, P. 144340 - 144340

Published: June 25, 2023

Language: Английский

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Bi‐affinity Electrolyte Optimizing High‐Voltage Lithium‐Rich Manganese Oxide Battery via Interface Modulation Strategy

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: May 25, 2023

The practical implementation of high-voltage lithium-rich manganese oxide (LRMO) cathode is limited by the unanticipated electrolyte decomposition and dissolution transition metal ions. present study proposes a bi-affinity formulation, wherein sulfonyl group ethyl vinyl sulfone (EVS) imparts highly adsorptive nature to LRMO, while fluoroethylene carbonate (FEC) exhibits reductive towards Li metal. This interface modulation strategy involves synergistic use EVS FEC as additives form robust interphase layers on electrode. As-formed S-endorsed but LiF-assisted configuration with more dominant -SO2 - component may promote transport kinetics prevent Furthermore, incorporation S into solid reduction its poorly conducting can effectively inhibit growth lithium dendrites. Therefore, 4.8 V LRMO/Li cell optimized demonstrate remarkable retention capacity 97 % even after undergoing 300 cycles at 1 C.

Language: Английский

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Nonafluorobutane‐1‐Sulfonic Acid Induced Local High Concentration Additive Interface for Robust SEI Formation of High‐Voltage (5 V‐Class) Lithium Metal Batteries

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(24)

Published: May 9, 2023

Abstract To optimize anode and cathode degradation issues in high‐voltage (5 V‐class) lithium metal batteries (LMBs), robust solid–electrolyte interfaces (SEI) on the surface of both are highly desired. Here, a nonafluorobutane‐1‐sulfonic acid (NFSA) additive is introduced to assist formation more stable SEI protect cathode. Typically, local high concentrations nonafluorobutane‐1‐sulfonate (NFSALi) anion (NFSA − ) could be achieved at respectively, through spontaneous chemical processes. The lowest unoccupied molecular orbital energy NFSALi lower highest occupied (energy NFSA higher than electrolyte solvents. Thus, conformal dense passivation films generated derived from electrochemical decomposition , respectively. Consequently, operation Li realized. LiNi 0.5 Mn 1.5 O 4 (LNMO)//Li LMBs with NFSA‐containing show great cycling stability 93% capacity retention after 400 cycles Coulombic efficiency. This work specifies double functions as an interfacial layer forming solve problems LMBs, enabling high‐energy significantly improved battery performance.

Language: Английский

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Dual LiF/LiCl‐Rich Solid Electrolyte Interphases with Robust and Li⁺‐conductive Characteristics for 4.8 V Lithium Metal Batteries

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

Published: Feb. 29, 2024

Abstract Lithium metal batteries, which are constructed by lithium‐rich manganese‐based oxide (LRMO) cathode and Li anode, have attracted intensive attention due to its high energy density. However, the instability of both anode limits practical application undesirable electrolyte decomposition at voltage. To address these issues, an engineering strategy is proposed for constructing robust, highly + ‐conductive solid interphases on with chlorobenzene as additive. Due mechanical stability interface dynamics LiCl‐endorsed, LiF‐rich interphase, transition ion dissolution effectively inhibited. Meanwhile, robust LiF/LiCl‐rich interphase can repress overgrowth dendrites. The Li||LRMO battery optimized 2.0 wt.% demonstrates a high‐capacity retention 86.1% after 200 cycles 0.5 C.

Language: Английский

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