Salt‐Free Solid Polymer Electrolytes Enabling Inorganic‐Rich Solid‐Electrolyte Interphase for Stable and Cost‐Effective Li‐Metal Batteries

Small, Journal Year: 2025, Volume and Issue: unknown

Published: April 7, 2025

Abstract Constructing robust solid‐electrolyte interphase (SEI) on electrodes is crucial for achieving stable lithium metal batteries in liquid electrolytes. However, intrinsic issues associated with electrolytes remain unavoidable, such as the continuous corrosion of SEI and high costs involved. Herein, a novel salt‐free solid‐state polymer electrolyte (SPE) introduced enabled by situ polymerization 1,3‐dioxolane 1,3,5‐trioxane addition ionic to eliminate drawbacks electrolyte. The homogeneous interaction between constructs synergistic Li + conduction pathway, promoting extraction out cathode/anode smooth transport throughout network endow higher transference number (0.63) comparable conductivity (1.21 mS cm −1 ) conventional (0.45 5.51 ). absence salt prevents oxidative decomposition salts generate hazardous corrosive acidic species. More intriguingly, an anion‐dominated solvation configuration can be realized incorporation matrix, inducing formation inorganic‐rich anti‐corrosive electrodes. resulting SPE enables superior cycling stability lithium||LiFePO 4 battery capacity retention over 92% after 780 cycles.

Language: Английский

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High Li⁺ Coordination Entropy Reducing the Interaction between Li⁺ and Polymer Chains to Improve Li⁺ Transport for Solid‐State Lithium Metal Batteries

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: April 15, 2025

Abstract High ionic conductivity and Li + transference number are crucial for ensuring the high safety energy density of solid‐state batteries, particularly those using lithium metal anodes (LMAs). However, performance current polymer electrolytes in these areas remains suboptimal, primarily due to insufficient transport properties hindered by strong coordination between ions chains. In this work, entropy is modulated through four types anions (TFSI − , DFOB BF 4 FSI ) reduce strength chains, thereby lowering barrier transport. Additionally, promote formation a uniform F‐ B‐rich solid electrolyte interphase on LMA surface. As result, fabricated with (HESPE) exhibits 0.238 mS cm −1 0.707 at room temperature. The assembled Li/HESPE/LiFePO batteries demonstrate improved plating/stripping behavior present stable cycling 1000 cycles without short circuit 1.5 C. high‐entropy strategy presents promising approach design industrial application enhanced stability safety.

Language: Английский

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In Situ Polymerized Polyfluorinated Crosslinked Polyether Electrolytes for High‐Voltage Lithium Metal Batteries

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: May 2, 2025

Abstract In situ polymerized polyether electrolytes are promising for solid‐state Li metal batteries due to their high ionic conductivity and excellent interfacial contact. However, practical application is hindered by dendrite formation, degradation, limited oxidative stability. Herein, we propose an in polyfluorinated crosslinked electrolyte (PDOL‐OFHDBO), synthesized copolymerizing 1,3‐dioxolane (DOL) with 2,2′‐(2,2,3,3,4,4,5,5‐octafluorohexane‐1,6‐diyl)bis(oxirane) (OFHDBO) as a crosslinker. The electron‐withdrawing groups endow PDOL‐OFHDBO enhanced stability compatibility, while reducing the solvation power of polymer matrix promote anion‐derived inorganic‐rich solid interphase uniform deposition. Consequently, exhibits wide electrochemical window (>5.6 V) enables long‐term stable plating/stripping over 1100 h. Furthermore, Li||LiNi 0.8 Co 0.1 Mn O 2 (NCM811) full cells utilizing demonstrate outstanding cycling high‐loading cathodes (≈3.8 mAh cm −2 ) thin anodes (50 µm), achieving capacity retention 95.5% 89.1% 100 cycles at cut‐off voltages 4.3 4.5 V, respectively. Remarkably, Ah‐level Li||NCM811 pouch deliver impressive specific energy 401.8 Wh kg −1 , highlighting potential batteries.

Language: Английский

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Stabilizing Residual Monomers within In Situ Polymerized Electrolytes for High-Voltage Lithium Metal Batteries

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 16, 2025

Poly(1,3-dioxolane) (PDOL)-based electrolyte has gained wide attention due to its high compatibility with the lithium metal anode, intimate contact electrodes, and ionic conductivity. However, application in high-voltage batteries is limited because residual DOL monomers are prone oxidation at voltage. Here, we report that LiDFOB-initiated situ polymerization stabilizes these monomers, thus overcoming oxidation-related limitations of PDOL-based electrolytes. This approach promotes formation a thermodynamically stable Li+-DOL-DFOB- solvation structure DOL-PDOL clusters, reducing oxidative decomposition extending electrochemical stability window up 5.0 V vs Li+/Li. It also enhances conductivity (4.39 mS cm-1), facilitates uniform, F-rich cathode-electrolyte interphase. Electrochemical tests computational simulations reveal reduced Li+-PDOL interactions designed PDOL promote higher mobility stability. Consequently, Li||LiCoO2 cells using exhibit remarkable cycling performance, maintaining 80% capacity retention over 760 cycles cut-off voltage 4.35 V. These findings establish as transformative for batteries.

Language: Английский

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Weakly Solvating Electrolyte: Regulating Polysulfide Intermediates for High‐Performance Lithium‐Sulfurized Polyacrylonitrile Batteries

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: May 29, 2025

Abstract Electrolyte engineering plays a crucial role in the design of high energy‐density lithium‐sulfurized polyacrylonitrile (Li‐SPAN) batteries, promising energy storage technology. However, current predominant electrolyte systems face challenges anode dendrite growth and cathode polysulfide loss, which limit cycling stability Li‐SPAN batteries. Here, weakly solvating (WSE) primarily composed diethoxy methane (DEM) is proposed to simultaneously address at both electrodes. At anode, DEM's capability accelerates Li + diffusion desolvation, preventing out‐of‐plane deposition formation caused by concentration gradients surface. More significantly cathode, solvated exhibits stronger Lewis acidity, preferentially stabilizing S 3 2− intermediates via hard acid‐base interaction. These higher‐reduction‐state promote faster subsequent lithiation reactions, reducing loss while improving rate performance enhancements corresponding mechanisms are supported electrochemical spectroscopic characterizations. With this WSE, batteries achieve exceptional (0.087% capacity fade per cycle over 500 cycles 1 C), pouch cell life increases from 9 35 with 90.6% retention. This strategy provides valuable insights for developing high‐performance

Language: Английский

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Multifunctional Subnanowires Modulating In Situ Polymerization for High-Voltage Solid-State Batteries

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: May 29, 2025

In situ polymerized poly(1,3-dioxolane) (PDOL) electrolytes endow excellent interfacial contact and satisfactory compatibility in lithium metal batteries (LMBs). However, their limited oxidative stability hinders with high-voltage cathodes. Herein, an effective molecular weight modulation-induced strategy via multifunctional subnanowires (SNWs) was proposed to realize the superior of PDOL narrow distribution (MWD). Specifically, ring-opening polymerization DOL promoted by oxygen vacancies (Ov) on SNWs, which enhanced monomer conversion rate. Simultaneously, speed during process regulated weak adsorption monomers induced protonated oleylamine (PO). Furthermore, dual Lewis acid sites (Ov PO) SNWs facilitate salt dissociation, releasing more movable Li+ for transport. Thus, SNWs-induced MWD 1.42 exhibit remarkable exceeding 5.1 V while achieving a lithium-ion transference number 0.81. Consequently, assembled NCM811||Li cells maintain stable operation 100 cycles at 4.5 capacity retention rate 89.2%. This research first modulates using enhance ability, presenting unique inspire development high-performance LMBs.

Language: Английский

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Decoupling Interfacial Stability and Ion Transport in Solid Polymer Electrolyte by Tailored Ligand Chemistry for Lithium Metal Battery

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 29, 2024

Abstract Achieving fast ion transport kinetics and high interfacial stability simultaneously is challenging for polymer electrolytes in solid‐state lithium batteries, as the coordination environment optimal Li + conduction struggles to generate desirable interphase chemistry. Herein, adjustable property of organic ligands exploited metal–organic frameworks (MOFs) develop a hierarchical composite electrolyte, incorporating heterogeneous spatially confined MOF nanofillers into poly‐1,3‐dioxolane matrix. The defect‐engineered University Oslo‐66 MOFs (UiO‐66d) with tailored Lewis acidity can separate pairs optimize migration through weakened solvation effects, thereby enhancing conductivity by over sixfold (0.85 mS cm −1 @25 °C). At anode side, densified Oslo‐67 (UiO‐67) layer conjugated π electrons facilitates anion participation sheath, promoting reduction forming LiF/Li 3 N‐dominated solid electrolyte isotropic deposition. as‐assembled Li||LiFePO 4 full cell delivers superior cycling 92.7% capacity retained 2000 cycles at 2 C. Notably, developed demonstrates excellent compatibility high‐voltage cathodes, achieving 80% retention LiNi 0.5 Co 0.2 Mn 0.3 O 630 cycles. This work provides valuable insights decoupling challenges paving way advanced battery technologies.

Language: Английский

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