Ion Transport Kinetics in Low‐Temperature Lithium Metal Batteries

Advanced Energy Materials, Год журнала: 2022, Номер 12(42)

Опубликована: Сен. 6, 2022

Abstract The deployment of rechargeable batteries is crucial for the operation advanced portable electronics and electric vehicles under harsh environment. However, commercial lithium‐ion using ethylene carbonate electrolytes suffer from severe loss in cell energy density at extremely low temperature. Lithium metal (LMBs), which use Li as anode rather than graphite, are expected to push baseline low‐temperature devices level. Albeit promising, kinetic limitations standard chemistries subzero condition inevitably hamper cyclability LMBs, resulting a decline plating/stripping reversibility short‐circuit hazards due dendritic growth. Such performance degradation becomes more pronounced with decreasing temperature, ascribing sluggish ion transport kinetics during charging/discharging processes includes + solvation/desolvation, through bulk electrolyte, well diffusion within solid electrolyte interphase electrode materials In this review, critical limiting factors challenges behaviors systematically reviewed discussed. strategies enhance electrolytes, electrodes, electrolyte/electrode interface comprehensively summarized. Finally, perspective on future research direction LMBs toward practical applications proposed.

Язык: Английский

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Li‐Ion Transfer Mechanism of Ambient‐Temperature Solid Polymer Electrolyte toward Lithium Metal Battery

Advanced Energy Materials, Год журнала: 2023, Номер 13(16)

Опубликована: Март 9, 2023

Abstract The low ionic conductivity and short service life of solid polymer electrolytes (SPEs) limit the application ambient‐temperature lithium metal batteries, which is perhaps a result inherent restricted segment movement at room temperature. Herein, an dual‐layer electrolyte developed related working mechanisms are innovatively investigated. In strategy, poly(propylene carbonate) (PPC)/succinonitrile (SN) contacts with cathode while polyethylene oxide (PEO)/Li 7 La 3 Zr 2 O 12 adopted near anode. Molecular dynamics simulations demonstrate formation solvated sheath‐like structure [SN···Li + ], demonstrates strong interaction polymers (PPC···[SN···Li ]/PEO···[SN···Li ]). Further density functional theory calculations show that these structures, allow rapid transport Li ions through segments. These results confirmed Fourier transform infrared spectroscopy nuclear magnetic resonance. Therefore, Li‐ion mechanism for SPEs can be reasonably revealed. Remarkably, binding energy between PPC SN stronger than PEO, helps avoid parasitic reaction Li. A overpotential 55 mV exhibited Li/Li symmetrical cells after 1000 h. Notably, capacity retention 86.3% maintained LiNi 0.6 Co 0.2 Mn /Li cell 25 °C, implying good potential in high voltage batteries.

Язык: Английский

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Molecular‐level Designed Polymer Electrolyte for High‐Voltage Lithium–Metal Solid‐State Batteries

Advanced Functional Materials, Год журнала: 2022, Номер 33(3)

Опубликована: Ноя. 14, 2022

Abstract In solid polymer electrolytes (SPEs) based Li–metal batteries, the inhomogeneous migration of dual‐ion in cell results large concentration polarization and reduces interfacial stability during cycling. A special molecular‐level designed electrolyte (MDPE) is proposed by embedding a functional group (4‐vinylbenzotrifluoride) polycarbonate base. MDPE, matrix obtained copolymerization vinylidene carbonate 4‐vinylbenzotrifluoride coupled with anion lithium‐salt hydrogen bonding “σ‐hole” effect CF bond. This intermolecular interaction limits increases ionic transfer number MDPE ( t Li + = 0.76). The mechanisms enhanced are profoundly understood conducting first‐principles density theory calculation. Furthermore, has an electrochemical window (4.9 V) excellent due to CO trifluoromethylbenzene (ph‐CF 3 ) matrix. Benefited from these merits, LiNi 0.8 Co 0.1 Mn O 2 ‐based solid‐state cells as both host electrode binder exhibit good rate cycling performance. study demonstrates that at molecular level can provide broader platform for high‐performance design needs lithium batteries.

Язык: Английский

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Physicochemical Dual Cross‐Linking Conductive Polymeric Networks Combining High Strength and High Toughness Enable Stable Operation of Silicon Microparticle Anodes

Advanced Materials, Год журнала: 2023, Номер 35(29)

Опубликована: Апрель 8, 2023

The poor interfacial stability and insufficient cycling performance caused by undesirable stress hinder the commercial application of silicon microparticles (µSi) as next-generation anode materials for high-energy-density lithium-ion batteries. Herein, a conceptionally novel physicochemical dual cross-linking conductive polymeric network is designed combining high strength toughness coupling stiffness poly(acrylic acid) softness carboxyl nitrile rubber, which includes multiple H-bonds, introducing highly branched tannic acid physical cross-linker. Such design enables effective dissipation folded molecular chains slipping sequential cleavage thus stabilizing electrode interface enhancing cycle stability. As expected, resultant (µSi/PTBR) delivers an unprecedented capacity retention ≈97% from 2027.9 mAh g-1 at 19th to 1968.0 200th 2 A . Meanwhile, this unique strategy also suitable SiOx anodes with much lower loss ≈0.012% per over 1000 cycles 1.5 Atomic force microscopy analysis finite element simulations reveal excellent stress-distribution ability network. This work provides efficient energy-dissipation toward practical high-capacity energy-dense

Язык: Английский

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Ion–Dipole-Interaction-Induced Encapsulation of Free Residual Solvent for Long-Cycle Solid-State Lithium Metal Batteries

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(47), С. 25632 - 25642

Опубликована: Ноя. 9, 2023

Owing to high ionic conductivity and mechanical strength, poly(vinylidene fluoride) (PVDF) electrolytes have attracted increasing attention for solid-state lithium batteries, but highly reactive residual solvents severely plague cycling stability. Herein, we report a free-solvent-capturing strategy triggered by reinforced ion-dipole interactions between Li+ solvent molecules. Lithium difluoro(oxalato)borate (LiDFOB) salt additive with electron-withdrawing capability serves as redistributor of the electropositive state, which offers more binding sites solvents. Benefiting from modified coordination environment, kinetically stable anion-derived interphases are preferentially formed, effectively mitigating interfacial side reactions electrodes electrolytes. As result, assembled battery shows lifetime over 2000 cycles an average Coulombic efficiency 99.9% capacity retention 80%. Our discovery sheds fresh light on targeted regulation extend cycle life batteries.

Язык: Английский

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Monodispersed Sub‐1 nm Inorganic Cluster Chains in Polymers for Solid Electrolytes with Enhanced Li‐Ion Transport

Advanced Materials, Год журнала: 2023, Номер 35(47)

Опубликована: Авг. 26, 2023

Abstract The organic–inorganic interfaces can enhance Li + transport in composite solid‐state electrolytes (CSEs) due to the strong interface interactions. However, non‐conductive areas CSEs with inert fillers will hinder construction of efficient channels. Herein, fully active conductive networks are proposed improve by composing sub‐1 nm inorganic cluster chains and organic polymer chains. monodispersed matrix a brief mixed‐solvent strategy, their diameter ultrafine dispersion state eliminate interior filler‐agglomeration, respectively, providing rich surface for Therefore, 3D connected finally construct homogeneous, large‐scale, continuous fast Furthermore, conjecture about 1D oriented distribution along is optimize pathways. Consequently, as‐obtained possess high ionic conductivity at room temperature (0.52 mS cm −1 ), transference number (0.62), more mobile (50.7%). assembled LiFePO 4 /Li cell delivers excellent stability 1000 cycles 0.5 C 700 1 C. This research provides new strategy enhancing interfaces.

Язык: Английский

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Anode‐Free Lithium Metal Batteries Based on an Ultrathin and Respirable Interphase Layer

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(27)

Опубликована: Май 4, 2023

Anode-free lithium (Li) metal batteries are desirable candidates in pursuit of high-energy-density batteries. However, their poor cycling performances originated from the unsatisfactory reversibility Li plating/stripping remains a grand challenge. Here we show facile and scalable approach to produce high-performing anode-free using bioinspired ultrathin (250 nm) interphase layer comprised triethylamine germanate. The derived tertiary amine Lix Ge alloy showed enhanced adsorption energy that significantly promoted Li-ion adsorption, nucleation deposition, contributing reversible expansion/shrinkage process upon plating/stripping. Impressive Coulombic efficiencies (CEs) ≈99.3 % were achieved for 250 cycles Li/Cu cells. In addition, LiFePO4 full demonstrated maximal power densities 527 Wh kg-1 1554 W , respectively, remarkable stability (over with an average CE 99.4 %) at practical areal capacity ≈3 mAh cm-2 highest among state-of-the-art Our respirable presents promising way fully unlock large-scale production

Язык: Английский

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Recent progress on metal–organic framework/polymer composite electrolytes for solid-state lithium metal batteries: ion transport regulation and interface engineering

Energy & Environmental Science, Год журнала: 2024, Номер 17(5), С. 1854 - 1884

Опубликована: Янв. 1, 2024

This review provides an overview of different strategies to improve the ion transport MOF/polymer composite electrolytes and stabilize electrode/electrolyte interface.

Язык: Английский

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Fluorine‐Containing Phase‐Separated Polymer Electrolytes Enabling High‐Energy Solid‐State Lithium Metal Batteries

Advanced Functional Materials, Год журнала: 2024, Номер 34(19)

Опубликована: Янв. 10, 2024

Abstract Solid‐state lithium (Li) metal batteries (LMBs) have been developed as a promising replacement for conventional Li‐ion due to their potential higher energy. However, the current solid‐state electrolytes used in LMBs limitations regarding mechanical and electrochemical properties interfacial stability. Here, fluorine (F)‐containing solid polymer electrolyte (SPE) having bi‐continuous structure of F‐containing elastomers plastic crystals is reported. The trifluoroethyl acrylate‐based SPE (T‐SPE) exhibits high ionic conductivity over 10 −3 S cm −1 , superior elasticity, robust LiF‐rich interphases at both Li anode LiNi 0.83 Mn 0.06 Co 0.11 O 2 cathode. Full cells with thin T‐SPEs low negative/positive capacity ratios below 0.5 high‐operating voltage 4.5 V demonstrate specific energy 538 Wh kg anode+cathode+electrolyte maintain 393 power 804 W . phase‐separated system provides powerful strategy achieving high‐energy ‐power LMBs.

Язык: Английский

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Regulating the Solvation Structure in Polymer Electrolytes for High‐Voltage Lithium Metal Batteries

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(34)

Опубликована: Июнь 4, 2024

Solid polymer electrolytes are promising for safe and high-energy-density lithium metal batteries. However, traditional ether-based limited by their low lithium-ion conductivity narrow electrochemical window because of the well-defined intimated Li

Язык: Английский

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