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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Lithium-Mediated Ammonia Electrosynthesis with Ether-Based Electrolytes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(47), P. 25716 - 25725

Published: Nov. 15, 2023

Ammonia is of great importance in fertilizer production and chemical synthesis. It can also potentially serve as a carbon-free energy carrier for future hydrogen economy. Motivated by worldwide effort to lower carbon emissions, ammonia synthesis lithium-mediated electrochemical nitrogen reduction (LiNR) has been considered promising alternative the Haber-Bosch process. A significant performance improvement LiNR achieved recent years exploration favorable lithium salt proton donor electrolyte recipe, but solvent study still its infancy. In this work, systematic investigation on ether-based solvents toward conducted. The assessments candidates are built their conductivity, parasitic reactions, product distribution, faradaic efficiency. Notably, dimethoxyethane gives lowest potential loss among investigated systems, while tetrahydrofuran achieves an outstanding efficiency 58.5 ± 6.1% at ambient pressure. We found that molecules impact above characteristics dictating solvation configurations conductive ions inducing formation solid interphase with different compositions. This highlights process advances optimization better performance.

Language: Английский

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Stabilizing Interfaces in High‐Temperature NCM811‐Li Batteries via Tuning Terminal Alkyl Chains of Ether Solvents

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(28)

Published: May 11, 2023

Ether electrolytes are promising for lithium metal batteries. Despite the intensive research in recent years, most state-of-the-art ether still cannot form reliable electrode-electrolyte interfaces NCM811-Li batteries at diluted concentrations, especially those operating elevated temperatures. We report a simple but effective strategy to break this bottleneck and stabilize high-temperature electrolytes. propose that by gradually extending terminal groups of glycol diethers from methyl n-butyl groups, comprehensive stability is improved. An anion-dominated solvation structure realized concentration 1 M. Accordingly, interactions suppressed, thinner, denser, more inorganic-rich solid- /cathode-electrolyte interface achieved. Additionally, surface phase transition structural degradation NCM811 cathode alleviated. Consequently, ethylene dibutyl ether-based electrolyte, Coulombic efficiency Li-Cu cells working 60 °C boosted 99.41 % with cycling life over 200 cycles. The lifespan prolonged than 400 stable average 99.77 quasi-practical conditions 50 μm Li, lean electrolyte 10 μL mAh-1 , medium-high loading >2.2 mAh cm-2 .

Language: Английский

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Salt Anion Amphiphilicity-Activated Electrolyte Cosolvent Selection Strategy toward Durable Zn Metal Anode

ACS Nano, Journal Year: 2023, Volume and Issue: 17(22), P. 23065 - 23078

Published: Nov. 10, 2023

One effective solution to inhibit side reactions and Zn dendrite growth in aqueous Zn-ion batteries is add a cosolvent into the Zn(CF3SO3)2 electrolyte, which has potential form robust solid electrolyte interface composed of ZnF2 ZnS. Nevertheless, there still lack discussion on convenient selection method for cosolvents, can directly reflect interactions between solvent solute rationally design solvation structure. Herein, logP, where P octanol-water partition coefficient, general parameter describe hydrophilicity lipophilicity chemicals, proposed as standard selecting cosolvents demonstrated by testing seven different types solvents. The with logP value similar that salt anion CF3SO3- interact CF3SO3-, Zn2+, H2O, leading reconstruction To prove concept, methyl acetate (MA) an example due its CF3SO3-. Both experimental theoretical results illustrate MA molecules not only enter shell but also coordinate Zn2+ or forming involved core-shell special structure reduces H2O activity contributes anion-induced ZnCO3-ZnF2-rich interface. As result, Zn||Zn cell Zn||NaV3O8·1.5H2O MA-involved exhibit superior performances MA-free electrolyte. This work provides insight via chemistry high-performance batteries.

Language: Английский

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Eco‐Friendly Tetrahydropyran Enables Weakly Solvating “4S” Electrolytes for Lithium‐Metal Batteries

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(32)

Published: July 6, 2023

Abstract The growth of lithium dendrites hinders the commercial applications lithium‐metal batteries. Electrolytes play a crucial role in influencing electrode/electrolyte interfacial chemistry. Traditional electrolytes adopt strongly solvating solvents to dissolve Li salts, creating an organic‐rich solid electrolyte interface (SEI). + conductivity and mechanical strength SEI are poor, so derived cannot effectively suppress dendrites. weakly (WSE) system can realize inorganic‐rich SEI, demonstrating improved compatibility with metal. However, design rules for WSE not clear. Here, four kinds “4S” (single salt single solvent) designed investigate thickness, pore volume, porosity revealed via reactive force field. results show heterocyclic symmetric tetrahydropyran has most suitable power best stability battery system. This research provides route bridging molecular thermodynamic chemistry gap.

Language: Английский

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Eliminating water hazards and regulating electrode-electrolyte interfaces by multifunctional sacrificial electrolyte additives for long-life lithium metal batteries

Energy storage materials, Journal Year: 2024, Volume and Issue: 70, P. 103512 - 103512

Published: May 24, 2024

Language: Английский

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Unveiling the Role of Fluorination in Hexacyclic Coordinated Ether Electrolytes for High-Voltage Lithium Metal Batteries

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(9), P. 5964 - 5976

Published: Feb. 21, 2024

Fluorinated ethers have become promising electrolyte solvent candidates for lithium metal batteries (LMBs) because they are endowed with high oxidative stability and Coulombic efficiencies of stripping/plating. Up to now, most reported fluorinated ether electrolytes −CF3-based, the influence ion solvation in modifying degree fluorination has not been well-elucidated. In this work, we synthesize a hexacyclic coordinated (1-methoxy-3-ethoxypropane, EMP) its counterparts −CH2F (F1EMP), −CHF2 (F2EMP), or −CF3 (F3EMP) as terminal group. With bis(fluorosulfonyl)imide single salt, structure, Li-ion transport behavior, deposition kinetics, high-voltage were systematically studied. Theoretical calculations spectra reveal gradually reduced solvating power from nonfluorinated EMP fully F3EMP, which leads decreased ionic conductivity. contrast, weakly possess higher Li+ transference number exchange current density. Overall, partially is demonstrated desired Further full cell testing using (4.4 V) high-loading (3.885 mAh cm–2) LiNi0.8Co0.1Mn0.1O2 cathode demonstrates that F2EMP enables 80% capacity retention after 168 cycles under limited Li (50 μm) lean (5 mL Ah−1) conditions 129 extremely (1.8 anode-free conditions. This work deepens fundamental understanding on interphase dynamics various degrees provides feasible approach toward design practical LMBs.

Language: Английский

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A Low‐Cost, Fluorine‐Free Localized Highly Concentrated Electrolyte Toward Ultra‐High Loading Lithium Metal Batteries

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(17)

Published: Feb. 21, 2024

Abstract Localized highly concentrated electrolytes have revitalized the advancement of secondary batteries. However, fluorinated diluents typically drawbacks high toxicity, serious environmental pollution, challenging synthesis, and cost. This work develops a low‐cost, eco‐friendly localized electrolyte by utilizing benzene as diluent, simultaneously achieving reversible lithium‐metal anodes long‐term stable cycling single crystal LiNi 0.8 Co 0.1 Mn O 2 (SC811) cathode. The unique conjugated structure absence electron‐withdrawing groups provide decent redox stability inertness, which enables it to modulate solvation structure. PhH‐LHCE supports SC811‐Li cells with cathode loading 9 mg cm −2 87.3% capacity retention after 450 cycles. Cells consisting ultra‐high Ni83 (≈31 ) ultra‐thin Li (50 µm) anode achieve 70 cycles lean condition. can be generalized promising electrochemical energy storage systems such sodium potassium metal batteries solve cost pollution problems in large‐scale production process.

Language: Английский

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Low-Temperature and Fast-Charging Lithium Metal Batteries Enabled by Solvent–Solvent Interaction Mediated Electrolyte

Nano Letters, Journal Year: 2024, Volume and Issue: 24(24), P. 7499 - 7507

Published: June 10, 2024

Lithium metal batteries utilizing lithium as the anode can achieve a greater energy density. However, it remains challenging to improve low-temperature performance and fast-charging features. Herein, we introduce an electrolyte solvation chemistry strategy regulate properties of ethylene carbonate (EC)-based electrolytes through intermolecular interactions, weakly solvated fluoroethylene (FEC) replace EC, incorporating low-melting-point solvent 1,2-difluorobenzene (2FB) diluent. We identified that interaction between 2FB facilitate Li

Language: Английский

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Ether-Based Gel Polymer Electrolyte for High-Voltage Potassium Ion Batteries

Nano Letters, Journal Year: 2024, Volume and Issue: 24(37), P. 11419 - 11428

Published: Sept. 3, 2024

Low-concentration ether electrolytes cannot efficiently achieve oxidation resistance and excellent interface behavior, resulting in severe electrolyte decomposition at a high voltage ineffective electrode-electrolyte interphase. Herein, we utilize sandwich structure-like gel polymer (GPE) to enhance the stability of potassium-ion batteries (PIBs). The GPE contact layer facilitates stable interphase formation, transport maintains good ionic transport, which enabled exhibit wide electrochemical window performance. In addition, Al corrosion under is suppressed through restriction solvent molecules. Consequently, when using designed (based on 1 m), K||graphite cell exhibits cycling 450 cycles with capacity retention 91%, K||FeFe-Prussian blue (2-4.2 V) delivers average Coulombic efficiency 99.9% over 2200 100 mA g

Language: Английский

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