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Poly(vinylidene fluoride) (PVDF)-based solid electrolytes with a Li salt-polymer-little residual solvent configuration are promising candidates for solid-state batteries. Herein, we clarify the microstructure of PVDF-based composite electrolyte at the atomic level and demonstrate that the Li+-interaction environment determines both interfacial stability and ion-transport capability. The polymer works as a "solid diluent" and the filler realizes a uniform solvent distribution. We propose a universal strategy of constructing a weak-interaction environment by replacing the conventional N,N-dimethylformamide (DMF) solvent with the designed 2,2,2-trifluoroacetamide (TFA). The lower Li+ binding energy of TFA forms abundant aggregates to generate inorganic-rich interphases for interfacial compatibility. The weaker interactions of TFA with PVDF and filler achieve high ionic conductivity (7.0 × 10-4 S cm-1) of the electrolyte. The solid-state Li||LiNi0.8Co0.1Mn0.1O2 cells stably cycle 4900 and 3000 times with cutoff voltages of 4.3 and 4.5 V, respectively, as well as deliver superior stability at -20 to 45 °C and a high energy density of 300 Wh kg-1 in pouch cells.
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This paper addresses the problem of path following and dynamic obstacle avoidance for an underwater biomimetic vehicle-manipulator system (UBVMS). Firstly, the general kinematic and dynamic models of underwater vehicles are presented; then, a nonlinear model predictive control (NMPC) scheme is employed to track a reference path and collision avoidance simultaneously. Moreover, to minimize the tracking error and for a higher degree of robustness, improved extended state observers are used to estimate model uncertainties and disturbances to be fed into the NMPC prediction model. On top of this, the proposed method also considers the uncertainty of the state estimator, while combining a priori estimation of the Kalman filter to reasonably predict the position of dynamic obstacles during short periods. Finally, simulations and experimental results are carried out to assess the validity of the proposed method in case of disturbances and constraints.
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Solid-state lithium metal batteries (SSLMBs) are promising candidates for high-energy-density energy storage devices. However, there still lacks an evaluation criterion to estimate real research status and compare overall performance of the developed SSLMBs. Herein, we propose a comprehensive descriptor, Li+ transport throughput ( φ L i + ${{\phi{} }_{{{\rm L}{\rm i}}^{+}}}$ ), to estimate actual conditions and output performance of the SSLMBs. The φ L i + ${{\phi{} }_{{{\rm L}{\rm i}}^{+}}}$ is defined as molar number of Li+ passing through unit area of electrode/electrolyte interface in an hour (mol m-2 h-1 ) during cycling of battery, which is a quantizable value after taking complex aspects including cycle rate, electrode areal capacity and polarization into account. On this basis, we evaluate the φ L i + ${{\phi{} }_{{{\rm L}{\rm i}}^{+}}}$ of liquid, quasi-solid-state and solid-state batteries, and highlight three key aspects to achieve high value of φ L i + ${{\phi{} }_{{{\rm L}{\rm i}}^{+}}}$ via building highly efficient cross-phase, cross-gap and cross-interface ion transport in the solid-state battery systems. We believe that the new concept of φ L i + ${{\phi{} }_{{{\rm L}{\rm i}}^{+}}}$ provides milestone guidelines towards large-scale commercialization of SSLMBs.
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Bimetallic alloy nanomaterials are promising anode materials for potassium-ion batteries (KIBs) due to their high electrochemical performance. The most well-adopted fabrication method for bimetallic alloy nanomaterials is tube furnace annealing (TFA) synthesis, which can hardly satisfy the trade-off among granularity, dispersity and grain coarsening due to mutual constraints. Herein, we report a facile, scalable and ultrafast high-temperature radiation (HTR) method for the fabrication of a library of ultrafine bimetallic alloys with narrow size distribution (≈10-20â nm), uniform dispersion and high loading. The metal-anchor containing heteroatoms (i.e., O and N), ultrarapid heating/cooling rate (≈103 â K s-1 ) and super-short heating duration (several seconds) synergistically contribute to the successful synthesis of small-sized alloy anodes. As a proof-of-concept demonstration, the as-prepared BiSb-HTR anode shows ultrahigh stability indicated by negligible degradation after 800â cycles. The in situ X-ray diffraction reveals the K+ storage mechanism of BiSb-HTR. This study can shed light on the new, rapid and scalable nanomanufacturing of high-quality bimetallic alloys toward extended applications of energy storage, energy conversion and electrocatalysis.
Assuntos
Ligas , Potássio , Biblioteca Gênica , Temperatura Baixa , Eletrodos , ÍonsRESUMO
Using 3D host is an effective way to solve the dendrite growth problem and accommodate volume changes of lithium (Li) metal anode. However, the preferred Li deposition on the top surface leads to the Li metal agglomeration at the surface. In addition, the large weight of the 3D host also greatly decreases the capacity based on the whole anode. Herein, a bidirectional lithiophilic gradient modification, including a top-down ZnO gradient and a bottom-up Sn gradient, is applied to an ultralight 3D carbon nanofiber host (density: 0.1 g cm-3 ) and ensures the evenly filling lithium deposition in the 3D host. ZnO transforms into highly ionic conductive Li-Zn alloy and Li2 O during cycling, enhancing the Li-ion transportation from top to bottom. The metallic Sn also lowers the Li nucleation potential, guiding the preferential Li deposition from the bottom. With such a host, a stable CE of 97.5% over 100 cycles at 1 mA cm-2 and 3 mAh cm-2 is achieved, and the full battery also delivers good cycling stability over 300 cycles with a high CE of 99.8% coupled with high loading LiFePO4 cathode (10 mg cm-2 ) and low N/P ratio (≈3).
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Lithium (Li) metal batteries (LMBs) face huge challenges to achieve long cycling life at wide temperature range owing to the severe dendrite growth at subambient temperature and the intense side reactions with electrolyte at high temperature. Herein, an ultrathin LiBO2 layer with an extremely high Young's modulus of 8.0 GPa is constructed on Li anode via an in situ reaction between Li metal and 4,4,5,5-tetramethyl-1,3,2-dioxa-borolane (TDB) to form LiBO2 @Li anode, which presents two times higher exchange current density than pristine Li anode. The LiBO2 layer presents a strong absorption to Li ions and greatly improves the interfacial dynamics of Li-ion migration, which induces homogenous lithium nucleation and deposition to form a dense lithium layer. Consequently, the Li dendrite growth during cycling at subambient temperature and the side reactions with electrolyte at high temperature are simultaneously suppressed. The LiBO2 @Li/LiNi0.8 Co0.1 Mn0.1 O2 (NCM811) full batteries with limited Li capacity and high cathode mass loading of 9.9 mg cm-2 can steadily cycle for 300 cycles with a capacity retention of 86.6%. The LiBO2 @Li/NCM811 full batteries and LiBO2 @Li/LiBO2 @Li symmetric batteries also present excellent cycling performance at both -20 and 60 °C. This work develops a strategy to achieve outstanding performance of LMBs at wide working temperature-range.
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WTe2nanostructures have intrigued much attention due to their unique properties, such as large non-saturating magnetoresistance, quantum spin Hall effect and topological surface state. However, the controllable growth of large-area atomically thin WTe2nanostructures remains a significant challenge. In the present work, we demonstrate the controllable synthesis of 1T' atomically thin WTe2nanoflakes (NFs) by water-assisted ambient pressure chemical vapor deposition method based on precursor design and substrate engineering strategies. The introduction of water during the growth process can generate a new synthesized route by reacting with WO3to form intermediate volatile metal oxyhydroxide. Using WO3foil as the growth precursor can drastically enhance the uniformity of as-prepared large-area 1T' WTe2NFs compared to WO3powders. Moreover, highly oriented WTe2NFs with distinct orientations can be obtained by using a-plane and c-plane sapphire substrates, respectively. Corresponding precursor design and substrate engineering strategies are expected to be applicable to other low dimensional transition metal dichalcogenides, which are crucial for the design of novel electronic and optoelectronic devices.
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Constructing stable surface modification layer is an effective strategy to suppress dendrite growth and side reactions of Zinc (Zn) metal anode in aqueous Zn-ion battery. Herein, a multicomponent Cu-Zn alloy interlayer with superior Zn affinity, high toughness and effective inhibition effect on lattice distortion is constructed on Zn foil (Cu-Zn@Zn) to fabricate ultra-stable Zn metal anode. Owning to the advantages of high binding energy of Cu-Zn alloy layer with Zn atoms and less contact area between metallic Zn and electrolyte, the as-prepared Cu-Zn@Zn electrode not only restricts the aggregation of Zn atoms, but also suppresses the pernicious hydrogen evolution and corrosion, leading to homogeneous Zn deposition and outstanding electrochemical performances. Accordingly, the symmetric battery with Cu-Zn@Zn electrode exhibits an ultra-long cycle life of 5496â h at 1â mA cm-2 for 1â mAh cm-2 , and the Cu-Zn@Zn//V2 O5 pouch cell demonstrates excellent cycling stability with a capacity retention of 88 % after 600 cycles.
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Catalysis is an effective remedy for the fast capacity decay of lithium-sulfur batteries induced by the shuttling of lithium polysulfides (LiPSs), but too strong adsorption ability of many catalysts toward LiPSs increases the risk of catalyst passivation and restricts the diffusion of LiPSs for conversion. Herein, perovskite bimetallic hydroxide (CoSn(OH)6 ) nanocages are prepared, which are further wrapped by reduced graphene oxide (rGO) as the catalytic host for sulfur. Because of the coordinated valence state of Co and Sn and the intrinsic defect of the perovskite structure, such bimetallic hydroxide delivers moderate adsorption ability and enhanced catalytic activity toward LiPS conversion. Coupled with the hollow structure and the wrapped rGO as double physical barriers, the redox reaction kinetics, and sulfur utilization are effectively improved with such a host. The assembled battery delivers a good rate performance with a high capacity of 644 mAh g-1 at 2 C and long stability with a capacity decay of 0.068% per cycle over 600 cycles at 1 C. Even with a higher sulfur loading of 3.2 mg cm-2 and a low electrolyte/sulfur ratio of 5 µL mg-1 , the battery still shows high sulfur utilization and good cycling stability.
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Constructing a stable solid electrolyte interphase (SEI) on high-specific-capacity silicon (Si) anode is one of the most effective methods to reduce the crack of SEI and improve the cycling performance of Si anode. Herein, the authors construct a reinforced and gradient SEI on Si nanoparticles by an in-situ thiol-ene click reaction. Mercaptopropyl trimethoxysilane (MPTMS) with thiol functional groups (SH) is first grafted on the Si nanoparticles through condensation reaction, which then in-situ covalently bonds with vinylene carbonate (VC) to form a reinforced and uniform SEI on Si nanoparticles. The modified SEI with sufficient elastic Lix SiOy can homogenize the stress and strain during the lithiation of Si nanoparticles to reduce their expansion and prevent the SEI from cracking. The Si nanoparticles-graphite blending anode with the reinforced SEI exhibits excellent performance with an initial coulombic efficiency of ≈90%, a capacity of 1053.3 mA h g-1 after 500 cycles and a high capacity of 852.8 mA h g-1 even at a high current density of 3 A g-1 . Moreover, the obtained anode shows superior cycling stability under both high loadings and lean electrolyte. The in-situ thiol-ene click reaction is a practical method to construct reinforced SEI on Si nanoparticles for next-generation high-energy-density lithium-ion batteries.
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Severe interfacial side reactions of polymer electrolyte with LiNi0.8 Co0.1 Mn0.1 O2 (NCM811) cathode and Li metal anode restrict the cycling performance of solid-state NCM811/Li batteries. Herein, we propose a chemically stable ceramic-polymer-anchored solvent composite electrolyte with high ionic conductivity of 6.0×10-4 â S cm-1 , which enables the solid-state NCM811/Li batteries to cycle 1500 times. The Li1.4 Al0.4 Ti1.6 (PO4 )3 nanowires (LNs) can tightly anchor the essential N, N-dimethylformamide (DMF) in poly(vinylidene fluoride) (PVDF), greatly enhancing its electrochemical stability and suppressing the side reactions. We identify the ceramic-polymer-liquid multiple ion transport mechanism of the LNs-PVDF-DMF composite electrolyte by tracking the 6 Li and 7 Li substitution behavior via solid-state NMR. The stable interface chemistry and efficient ion transport of LNs-PVDF-DMF contribute to superior performances of the solid-state batteries at wide temperature range of -20-60 °C.
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Sodium-ion batteries (SIBs) are promising for large-scale energy storage systems and carbon materials are the most likely candidates for their electrodes. The existence of defects in carbon materials is crucial for increasing the sodium storage ability. However, both the reversible capacity and efficiency need to be further improved. Functionalization is a direct and feasible approach to address this issue. Based on the structural changes in carbon materials produced by surface functionalization, three basic categories are defined: heteroatom doping, grafting of functional groups, and the shielding of defects. Heteroatom doping can improve the electrochemical reactivity, and the grafting of functional groups can promote both the diffusion-controlled bulk process and surface-confined capacitive process. The shielding of defects can further increase the efficiency and cyclic stability without sacrificing reversible capacity. In this Review, recent progresses in the ways to produce surface functionalization are presented and the related impact on the physical and chemical properties of carbon materials is discussed. Moreover, the critical issues, challenges, and possibilities for future research are summarized.
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Lithium (Li) metal is promising for high energy density batteries due to its low electrochemical potential (-3.04 V) and high specific capacity (3860 mAh g-1 ). However, the safety issues impede the commercialization of Li anode batteries. In this work, research of hierarchical structure designs for Li anodes to suppress Li dendrite growth and alleviate volume expansion from the interior (by the 3D current collector and host matrix) to the exterior (by the artificial solid electrolyte interphase (SEI), protective layer, separator, and solid state electrolyte) is concluded. The basic principles for achieving Li dendrite and volume expansion free Li anode are summarized. Following these principles, 3D porous current collector and host matrix are designed to suppress the Li dendrite growth from the interior. Second, artificial SEI, the protective layer, and separator as well as solid-state electrolyte are constructed to regulate the distribution of current and control the Li nucleation and deposition homogeneously for suppressing the Li dendrite growth from exterior of Li anode. Ultimately, this work puts forward that it is significant to combine the Li dendrite suppression strategies from the interior to exterior by 3D hierarchical structure designs and Li metal modification to achieve excellent cycling and safety performance of Li metal batteries.
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The garnet electrolyte presents poor wettability with Li metal, resulting in an extremely large interfacial impedance and drastic growth of Li dendrites. Herein, a novel ultra-stable conductive composite interface (CCI) consisting of Liy Sn alloy and Li3 N is constructed inâ situ between Li6.4 La3 Zr1.4 Ta0.6 O12 (LLZTO) pellet and Li metal by a conversion reaction of SnNx with Li metal at 300 °C. The Liy Sn alloy as a continuous and robust bridge between LLZTO and Li metal can effectively reduce the LLZTO/Li interfacial resistance from 4468.0â Ω to 164.8â Ω. Meanwhile, the Li3 N as a fast Li-ion channel can efficiently transfer Li ions and give their uniform distribution at the LLZTO/Li interface. Therefore, the Li/LLZTO@CCI/Li symmetric battery stably cycles for 1200â h without short circuit, and the all-solid-state high-voltage Li/LLZTO@CCI/LiNi0.5 Co0.2 Mn0.3 O2 battery achieves a specific capacity of 161.4â mAh g-1 at 0.25â C with a capacity retention rate of 92.6 % and coulombic efficiency of 100.0 % after 200â cycles at 25 °C.
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An in-depth understanding of (de)lithiation induced phase transition in electrode materials is crucial to grasp their structure-property relationships and provide guidance to the design of more desirable electrodes. By operando synchrotron XRD (SXRD) measurement and Density Functional Theory (DFT) based calculations, we discover a reversible first-order phase transition for the first time during (de)lithiation of CeO2 nanoparticles. The LixCeO2 compound phase is identified to possess the same fluorite crystal structure with FM3M space group as that of the pristine CeO2 nanoparticles. The SXRD determined lattice constant of the LixCeO2 compound phase is 0.551 nm, larger than that of 0.541 nm of the pristine CeO2 phase. The DFT calculations further reveal that the Li induced redistribution of electrons causes the increase in the Ce-O covalent bonding, the shuffling of Ce and O atoms, and the jump expansion of lattice constant, thereby resulting in the first-order phase transition. Discovering the new phase transition throws light upon the reaction between lithium and CeO2, and provides opportunities to the further investigation of properties and potential applications of LixCeO2.
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V2 O5 decorated carbon nanofibers (CNFs) are prepared and used as a multifunctional interlayer for a lithium-sulfur (Li-S) battery. V2 O5 anchored on CNFs can not only suppress the shuttle effect of polysulfide by the strong adsorption and redox reaction, but also work as a high-potential dam to restrain the self-discharge behavior in the battery. As a result, Li-S batteries with a high capacity and long cycling life can be stored and rested for a long time without obvious capacity fading.
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Anovel lithiated Si-S battery exploiting an optimized solid-like electrolyte is presented. This electrolyte is fabricated by integrating ether-based liquid electrolyte with SiO2 hollow nanosphere layer to suppress the shuttle effect and fluoroethylene carbonate additive to optimize the anodic solid electrolyte interface. The prepared lithiated Si-S batteries exhibit enhanced cycle life, low flammability, and strong recovery ability against short-circuit.
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As a promising candidate for large-scale energy storage systems, sodium-ion batteries (SIBs) are experiencing a rapid development. Organic conjugated carboxylic acid anodes not only have tailorable electrochemical properties but also are easily accessible. However, the low stability and electrical conductivity hamper their practical applications. In this study, disodium terephthalate (Na2 TP), the most favorable organic conjugated carboxylic acid anode material for SIBs, was proposed to integrate with graphene oxide (GO) by an anti-solvent precipitation process, which ensures the uniform and tight coating of GO on the Na2 TP surface. GO is electrochemically reduced during the first several cycles of the electrochemical measurement, which buffers the volume change and improves the electrical conductivity of Na2 TP, resulting in a better cyclic and rate performance. The incorporation of only 5â wt % GO onto Na2 TP leads to a reversible capability of 235â mA h g-1 after 100 cycles at a current rate of 0.1â C, which is the best among the state of the art organic anodes for SIBs. The one-step synthesis together with the low costs of the raw materials show a promise for the scalable preparation of anode materials for practical SIBs.
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The effects of number of graphene layers (n) and size of multilayer graphene sheets on thermal conductivities (TCs) of their epoxy composites are investigated. Molecular dynamics simulations show that the in-plane TCs of graphene sheets and the TCs across the graphene/epoxy interface simultaneously increase with increasing n. However, such higher TCs of multilayer graphene sheets will not translate into higher TCs of bulk composites unless they have large lateral sizes to maintain their aspect ratios comparable to the monolayer counterparts. The benefits of using large, multilayer graphene sheets are confirmed by experiments, showing that the composites made from graphite nanoplatelets (n > 10) with over 30 µm in diameter deliver a TC of â¼1.5 W m(-1) K(-1) at only 2.8 vol %, consistently higher than those containing monolayer or few-layer graphene at the same graphene loading. Our findings offer a guideline to use cost-effective multilayer graphene as conductive fillers for various thermal management applications.
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Well-controlled nanostructures and a high fraction of Sn/Li2 O interface are critical to enhance the coulombic efficiency and cyclic performance of SnO2 -based electrodes for lithium-ion batteries (LIBs). Polydopamine (PDA)-coated SnO2 nanocrystals, composed of hundreds of PDA-coated "corn-like" SnO2 nanoparticles (diameter ca. 5â nm) decorated along a "cob", addressed the irreversibility issue of SnO2 -based electrodes. The PDA-coated SnO2 were crafted by capitalizing on rationally designed bottlebrush-like hydroxypropyl cellulose-graft-poly (acrylic acid) (HPC-g-PAA) as a template and was coated with PDA to construct a passivating solid-electrolyte interphase (SEI) layer. In combination, the corn-like nanostructure and the protective PDA coating contributed to a PDA-coated SnO2 electrode with excellent rate capability, superior long-term stability over 300 cycles, and high SnâSnO2 reversibility.