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

Chemical Reviews, Год журнала: 2024, Номер 124(6), С. 3494 - 3589

Опубликована: Март 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

Язык: Английский

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Work‐Function‐Induced Interfacial Electron/Ion Transport in Carbon Hosts toward Dendrite‐Free Lithium Metal Anodes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(44)

Опубликована: Сен. 15, 2023

Coupled electron/ion transport is a decisive feature of Li plating/stripping, wherein the compatibility rates determines morphology deposited Li. Local Li+ hotspots form due to inhomogeneous interfacial charge transfer and lead uncontrolled deposition, which decreases utilization rate safety metal anodes. Herein, we report method obtain dendrite-free anodes by driving electron pumping accumulating boosting ion diffusion tuning work function carbon host using cobalt-containing catalysts. The results reveal that increasing provides an deviation from C Co, electron-rich Co shows favorable binding . catalysts boost on fiber scaffolds without local aggregation reducing migration barrier. as-obtained anode exhibits Coulombic efficiency 99.0 %, cycle life over 2000 h, 50 capacity retention 83.4 % after 130 cycles in pouch cells at negative/positive ratio 2.5. These findings provide novel strategy stabilize regulating materials electrocatalysts.

Язык: Английский

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Ultra‐Sleek High Entropy Alloy Tights: Realizing Superior Cyclability for Anode‐Free Battery

Advanced Materials, Год журнала: 2023, Номер 36(11)

Опубликована: Дек. 16, 2023

The development of Li-free anodes to inhibit Li dendrite formation and provide high energy density batteries is highly applauded. However, the lithiophobic interphase heterogeneous deposition hindered practical application. In this work, a 20 nm ultra-sleek entropy alloy (HEA, NiCdCuInZn) tights loaded with HEA nanoparticles are developed by thermodynamically driven phase transition method on carbon fiber (HEA/C). Multiple

Язык: Английский

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Heterogeneous structure design for stable Li/Na metal batteries: Progress and prospects

eScience, Год журнала: 2024, Номер unknown, С. 100281 - 100281

Опубликована: Май 1, 2024

The growth of dendrites in Li/Na metal batteries is a multifaceted process that controlled by several factors such as electric field, ion transportation, temperature, and pressure. Rational design battery components has become viable approach to address this challenge. Among the various strategies, heterogeneous structures have been demonstrated be effective mitigating uneven deposition reducing local current density regulating sites. In review, we discuss comprehensively underlying principles influence dendrite growth, well synthesis approaches for structures. Furthermore, provide an overview diverse applications components. Finally, highlight existing challenges future directions use deposition.

Язык: Английский

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An ultralight, pulverization-free integrated anode toward lithium-less lithium metal batteries

Science Advances, Год журнала: 2024, Номер 10(13)

Опубликована: Март 29, 2024

The high-capacity advantage of lithium metal anode was compromised by common use copper as the collector. Furthermore, pulverization associated with “dead” Li accumulation and electrode cracking deteriorates long-term cyclability batteries, especially under realistic test conditions. Here, we report an ultralight, integrated polyimide-Ag/Li dual anti-pulverization functionality. silver layer initially chemically bonded to polyimide surface then spontaneously diffused in solid solution self-evolved into a fully lithiophilic Li-Ag phase, mitigating dendrites growth or dead Li. Further, strong van der Waals interaction between bottommost affords structural integrity electrical continuity, thus circumventing pulverization. Compared cutting-edge anode-free cells, batteries pairing LiNi 0.8 Mn 0.1 Co O 2 afford nearly 10% increase specific energy, safer characteristics better cycling stability conditions 1× excess high areal-loading cathode (4 milliampere hour per square centimeter).

Язык: Английский

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Directing Fluorinated Solid Electrolyte Interphase by Solubilizing Crystal Lithium Fluoride in Aprotic Electrolyte for Lithium Metal Batteries

Advanced Energy Materials, Год журнала: 2024, Номер 14(16)

Опубликована: Фев. 21, 2024

Abstract Lithium fluoride (LiF) facilitates robust and fast‐ion‐transport solid electrolyte interphase (SEI) in lithium metal batteries. Fluorinated solvents/salts are ubiquitously employed to introduce LiF into SEI through electrochemical decomposition, but this approach is usually at the expense of their continuous consumption. A direct fluorinate that employs crystal limited by its poor solubility current battery formulation. Dissolving high‐dielectric‐constant solvents, like ethylene carbonate (EC) nearly neglected. Herein, feasibility directly fluorinating addition aprotic with assistance EC verified, mechanisms fluorination anti‐acidification explored. The dissolved encapsulated solvent‐/salt‐derived organic skins promote fluorinated SEI. Meanwhile, presence alters hazardous thermodynamic equilibrium, suppressing production acid species mitigate acidification degradation. Such collective benefits yield a capacity retention ratio ≈88% after 150 cycles high areal (4.5 mAh cm −2 ) Li||NCM622 cells. This facile effective contributes an in‐depth understanding formation rational design well‐performing

Язык: Английский

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A Lithiophilic–Lithiophobic Gradient Solid Electrolyte Interface Toward a Highly Stable Solid‐State Polymer Lithium Metal Batteries

Advanced Functional Materials, Год журнала: 2024, Номер 34(27)

Опубликована: Март 7, 2024

Abstract The functional lithiophilic−lithiophobic gradient solid electrolyte interphase (SEI) between Li‐metal anode and solid‐state polymer electrolytes may be effective in addressing the long‐standing issue of side reactions Li‐dendrite growth during repeated deposition or dissolution polymer‐based high‐energy‐density batteries. Herein, a reliable lithiophilic–lithiophobic SEI (G‐SEI) LiAg‐LiF/Li 3 N is situ formed by AgTFSI, used as an additive for polyethylene oxide‐based (PEO‐Ag). upper layer consists lithiophobic LiF/Li N‐rich layer, wherein LiF possesses high interfacial energy, while Li enables fast + diffusion, which synergistically facilitates uniform . Lithiophilic Li–Ag alloy can effectively reduce nucleation overpotential promote more planar lithium. Furthermore, such G‐SEI mechanical modulus, mitigating penetration dendrites through thereby preventing continuous degradation PEO‐based electrolyte. As result, over three times improvement lifespan | PEO‐Ag LFP cell achieved, demonstrating 81.4% capacity retention rate after 500 cycles at 1C, compared to PEO with common SEI. Thus, developments lithiophilic‐lithiophobic provide substantial path toward high‐performance lithium

Язык: Английский

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Balanced Mass Transfer and Active Sites Density in Hierarchical Porous Catalytic Metal–Organic Framework for Enhancing Redox Reaction in Lithium–Sulfur Batteries

ACS Nano, Год журнала: 2024, Номер 18(20), С. 12820 - 12829

Опубликована: Май 9, 2024

Developing highly efficient catalysts, characterized by controllable pore architecture and effective utilization of active sites, is paramount in addressing the shuttle effect sluggish redox kinetics lithium polysulfides (LiPSs) lithium–sulfur batteries (LSBs), which, however, remains a formidable challenge. In this study, hierarchical porous catalytic metal–organic framework (HPC-MOF) with both appropriate porosity abundant exposed sites achieved through time-controlled precise engineering. It revealed that evolution structure site density time-dependent during etching processes. The moderately etched HPC-MOF-M attains heterogeneous pores at various scales, where large apertures ensure fast mass transfer micropores inherit high-density enhancing internal sites. Capitalizing on these advantages, LSB incorporating interlayer demonstrates 164.6% improvement discharge capability an 83.3% lower decay rate over long-term cycling 1.0C. Even under high sulfur loading 7.1 mg cm–2 lean electrolyte conditions, exhibits stable for 100 cycles. This work highlights significance balancing relationship between chemical regulation MOFs, which are anticipated to inspire development advanced catalysts LSBs.

Язык: Английский

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Interfacial Lithium-Ion Transportation in Solid-State Batteries: Challenges and Prospects

Nano Energy, Год журнала: 2025, Номер 136, С. 110749 - 110749

Опубликована: Фев. 7, 2025

Язык: Английский

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Composite Quasi‐Solid‐State Electrolytes with Organic–Inorganic Interface Engineering for Fast Ion Transport in Dendrite‐Free Sodium Metal Batteries

Advanced Materials, Год журнала: 2023, Номер 36(13)

Опубликована: Дек. 19, 2023

Abstract Quasi‐solid‐state electrolytes (QSSE) are a promising candidate for addressing the limitations of liquid and solid electrolytes. However, different ion transport capacities between solvents polymers can cause localized heterogeneous distribution Na + fluxes. In addition, continuous side reactions occurring at interface QSSE sodium anode lead to uncontrollable dendrites growth. Herein, novel strategy is designed integrate composite electrospun membrane 3 Zr 2 Si PO 12 poly(vinylidene fluoride‐ co ‐hexafluoropropylene) (PVDF‐HFP) into QSSE, aiming introduce new fast conducting channels organic–inorganic interface. The efficient transfer pathways effectively promote homogenization migration, enabling achieve an ultrahigh ionic conductivity 4.1 mS cm −1 room temperature, with transference number as high 0.54. Moreover, PVDF‐HFP preferentially reduced upon contact form “NaF‐rich” electrolyte interphase, which suppresses growth dendrites. synergistic combination multiple strategies realize exceptional long‐term cycling stability in both symmetric batteries (≈700 h) full (2100 cycles). This study provides insight constructing performance dendrite‐free solid‐state metal batteries.

Язык: Английский

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