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Lithium-metal (Li0) anodes potentially enable all-solid-state batteries with high energy density. However, it shows incompatibility with sulfide solid-state electrolytes (SEs). One strategy is introducing an interlayer, generally made of a mixed ionic-electronic conductor (MIEC). Yet, how Li behaves within MIEC remains unknown. Herein, we investigated the Li dynamics in a graphite interlayer, a typical MIEC, by using operando neutron imaging and Raman spectroscopy. This study revealed that intercalation-extrusion-dominated mechanochemical reactions during cell assembly transform the graphite into a Li-graphite interlayer consisting of SE, Li0, and graphite-intercalation compounds. During charging, Li+ preferentially deposited at the Li-graphite|SE interface. Upon further plating, Li0-dendrites formed, inducing short circuits and the reverse migration of Li0. Modeling indicates the interface has the lowest nucleation barrier, governing lithium transport paths. Our study elucidates intricate mechano-chemo-electrochemical processes in mixed conducting interlayers. The behavior of Li+ and Li0 in the interlayer is governed by multiple competing factors.
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Anode-free all-solid-state lithium metal batteries (ASLMBs) promise high energy density and safety but suffer from a low initial Coulombic efficiency and rapid capacity decay, especially at high cathode loadings. Using operando techniques, we concluded these issues were related to interfacial contact loss during lithium stripping. To address this, we introduce a conductive carbon felt elastic layer that self-adjusts the pressure at the anode side, ensuring consistent lithium-solid electrolyte contact. This layer simultaneously provides electronic conduction and releases the plating pressure. Consequently, the first Coulombic efficiency dramatically increases from 58.4% to 83.7% along with a >10-fold improvement in cycling stability. Overall, this study reveals an approach for enhancing anode-free ASLMB performance and longevity by mitigating lithium stripping inefficiency through self-adjusting interfacial pressure enabled by a conductive elastic interlayer.
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Conventional ion-selective membranes, that is ion-exchange and porous membranes, are unable to perform high conductivity and selectivity simultaneously due to the contradictions between their ion selecting and conducting mechanisms. In this work, a bifunctional ion-selective layer is developed via the combination of nanoporous boron nitride (PBN) and ion exchange groups from Nafion to achieve high ion conductivity through dual ion conducting mechanisms as well as high ion selectivity. A template-free method is adopted to synthesize flake-like PBN, which is further enmeshed with Nafion resin to form the bifunctional layer coated onto a porous polyetherimide membrane. The double-layer membrane exhibits excellent ion selectivity (1.49 × 108 mS cm-3 min), which is 22 times greater than that of the pristine porous polyetherimide membrane, with outstanding ion conductivity (64 mS cm-1 ). In a vanadium flow battery, the double-layer membrane achieves a high Coulombic efficiency of 97% and outstanding energy efficiency of 91% at 40 mA cm-2 with a stable cycling performance for over 700 cycles at 100 mA cm-2 . PBN with ion exchange groups may therefore offer a potential solution to the limitation between ion selectivity and conductivity in ion-selective membranes.
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Due to its outstanding safety and high energy density, all-solid-state lithium-sulfur batteries (ASLSBs) are considered as a potential future energy storage technology. The electrochemical reaction pathway in ASLSBs with inorganic solid-state electrolytes is different from Li-S batteries with liquid electrolytes, but the mechanism remains unclear. By combining operando Raman spectroscopy and ex situ X-ray absorption spectroscopy, we investigated the reaction mechanism of sulfur (S8 ) in ASLSBs. Our results revealed that no Li2 S8, Li2 S6, and Li2 S4 were formed, yet Li2 S2 was detected. Furthermore, first-principles structural calculations were employed to disclose the formation energy of solid state Li2 Sn (1≤n≤8), in which Li2 S2 was a metastable phase, consistent with experimental observations. Meanwhile, partial S8 and Li2 S2 remained at the full lithiation stage, suggesting incomplete reaction due to sluggish reaction kinetics in ASLSBs.
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Porous carbon plays a significant role in all-solid-state lithium-sulfur batteries (ASSLSBs) to enhance the electronic conductivity of sulfur. However, the conventional porous carbon used in cell with liquid electrolyte exhibits low efficiency in ASSLSBs because the immobile solid electrolyte (SE) cannot reach sulfur confined in the deep pores. The structure and distribution of pores in carbon highly impact the electrochemical performance of ASSLSBs. Herein, a N-doped carbon fiber with micropores located only at the surface with an ultrahigh surface area of 1519 m2 g-1 is designed. As the porous layer is only on the surface, the sulfur hosted in the pores can effectively contact SE; meanwhile the dense core provides excellent electrical conductivity. Therefore, this structurally designed carbon fiber enhances both electron and ion accessibilities, promotes charge transfer, and thus dramatically improves the reaction kinetic in the ASSLSBs and boosts sulfur utilization. Compared to the vapor grown carbon fibers, the ASSLSBs using PAN-derived porous carbon fibers exhibit three times enhancement in the initial capacity of 1166 mAh g-1 at C/20. An exceedingly cycling stability of 710 mAh g-1 is maintained after 220 cycles at C/10, and satisfactory rate capability of 889 mAh g-1 at C/2 is achieved.
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Large-scale salinity gradient power energy harvesting has generated broad attention in recent years, in which affordable ion-selective membranes (ISMs) are essential for its practical implementation. In this study, for the first time, ISMs derived from natural loofah sponge are reported, which have features of high hydrophilicity, superior ion conductivity, and 3D interconnected long fibers. The permselectivity and ion conductivity of loofah-based anion-selective membranes (ASMs) and cation-selective membranes (CSMs) are designed by chemical modification of the surface functional groups of loofah fibers and followed with compression and the resin filling. The charged nanochannels inside the ISMs are served as ion conductive and selective channels based on the nanofluidic effects and Donnan exclusion. Meanwhile, the unique isotropic structure endows excellent dimensional stability under the NaCl solution for months. When ISMs are used for salinity gradient power generation from the gradient of artificial seawater and river water, the maximum power density is 18.3 mW m-2 . When ten units of loofah-based ISMs are stacked in series, a voltage as high as 1.55 V is achieved. The results highlight the great potential of natural fibers for fabricating affordable, durable, and high performance ISMs, paving a sustainable pathway for developing high-performance, durable, and low-cost salinity gradient power generators.
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Luffa , Salinidade , Água Doce/química , Membranas Artificiais , Água do Mar/químicaRESUMO
All-solid-state lithium batteries (ASLBs) are promising for the next generation energy storage system with critical safety. Among various candidates, thiophosphate-based electrolytes have shown great promise because of their high ionic conductivity. However, the narrow operation voltage and poor compatibility with high voltage cathode materials impede their application in the development of high energy ASLBs. In this work, we studied the failure mechanism of Li6PS5Cl at high voltage through in situ Raman spectra and investigated the stability with high-voltage LiNi1/3Mn1/3Co1/3O2 (NMC) cathode. With a facile wet chemical approach, we coated a thin layer of amorphous Li0.35La0.5Sr0.05TiO3 (LLSTO) with 15-20 nm at the interface between NMC and Li6PS5Cl. We studied different coating parameters and optimized the coating thickness of the interface layers. Meanwhile, we studied the effect of NMC dimension to the ASLBs performance. We further conducted the first-principles thermodynamic calculations to understand the electrochemical stability between Li6PS5Cl and carbon, NMC, LLSTO, NMC/LLSTO. Attributed to the high stability of Li6PS5Cl with NMC/LLSTO and outstanding ionic conductivity of the LLSTO and Li6PS5Cl, at room temperature, the ASLBs exhibit outstanding capacity of 107 mAh g-1 and keep stable for 850 cycles with a high capacity retention of 91.5% at C/3 and voltage window 2.5-4.0 V (vs Li-In).
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The design of chemically stable ion-exchange membranes with high selectivity for applications in an aqueous redox flow battery (RFB) at high acid concentrations remains a significant challenge. Herein, this study designed a stable and highly ion-selective membrane by utilizing proton conductive cellulose nanocrystals (CNCs) incorporated in a semicrystalline hydrophobic poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix. The high hydrophobicity of the PVDF-HFP matrix mitigates crossover of the electrolytes, whereas the abundant and low-cost CNCs derived from wood provide high proton conductivity. The fundamental contributors for CNCs' excellent proton conductivity are the hydroxyl (-OH) functional groups, highly acidic sulfonate (-SO3H) functional groups, and the extensive intramolecular hydrogen bonding network. In addition, CNCs exhibit a mechanically and chemically stable structure in the harsh acidic electrolyte attributed to the high crystallinity (crystalline index of â¼86%). Therefore, because of the high proton conductivity, excellent ion selectivity, high chemical stability, and structural robustness, the vanadium redox flow battery (VRFB) assembled with the homogeneous CNCs and PVDF-HFP (CNC/PVDF-HFP) membrane achieved a Coulombic efficiency (CE) of 98.2%, energy efficiency (EE) of 88.2%, and a stable cycling performance for more than 650 cycles at a current density of 100 mA cm-2. The obtained membrane possesses excellent flexibility, high mechanical tensile strength, and superior selectivity. Meanwhile, the applied casting method is scalable for large-scale manufacturing.
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Lithium metal-sulfur (Li-S) batteries are attracting broad interest because of their high capacity. However, the batteries experience the polysulfide shuttle effect in cathode and dendrite growth in the Li metal anode. Herein, a bifunctional and tunable mesoporous carbon sphere (MCS) that simultaneously boosts the performance of the sulfur cathode and the Li anode is designed. The MCS homogenizes the flux of Li ions and inhibits the growth of Li dendrites due to its honeycomb structure with high surface area and abundance of nitrogen sites. The Li@MCS cell exhibits a small overpotential of 29 mV and long cycling performance of 350 h under the current density of 1 mA cm-2 . Upon covering one layer of amorphous carbon on the MCS (CMCS), an individual carbon cage is able to encapsulate sulfur inside and reduce the polysulfide shuttle, which improves the cycling stability of the Li-S battery. As a result, the S@CMCS has a maximum capacity of 411 mAh g-1 for 200 cycles at a current density of 3350 mA g-1 . Based on the excellent performance, the full Li-S cell assembled with Li@MCS anode and S@CMCS cathode shows much higher capacity than a cell assembled with Li@Cu anode and S@CMCS cathode.
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Hierarchical-structured electrodes having merits of superior cycling stability and high rate performance are highly desired for next-generation energy storage. For the first time, we reported a compressible and hierarchical porous carbon nanofiber foam (CNFF) derived from a sustainable and abundant biomaterial resource, bacterial cellulose, for boosting the electrochemical performance of potassium-ion batteries. The CNFF free-standing electrode with a hierarchical porous three-dimensional structure demonstrated excellent rate performance and outstanding cyclic stability in the extended cycling test. Specifically, in the long-term cycling-stability test, the CNFF electrode maintained a stable capacity of 158 mA h g-1 after 2000 cycles at a high current density of 1000 mA g-1, which has an average capacity decay of 0.006% per cycle. After that, the CNFF electrode maintained a capacity of 141 mA h g-1 at a current density of 2000 mA g-1 for another 1500 cycles, and a capacity of 122 mA h g-1 at a current density of 5000 mA g-1 for an additional 1000 cycles. The mechanism for the outstanding performance is that the hierarchical porous and stable CNFF with high surface area and high electronic conductivity provides sufficient sites for potassium-ion storage. Furthermore, quantitative kinetics analysis has validated the capacitive- and diffusion-controlled charge-storage contributions in the carbon-foam electrode. This work will inspire the search for cost-effective and sustainable materials for potassium electrochemical energy storage.
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Celulose/química , Condutividade Elétrica , Gluconacetobacter xylinus/química , Nanofibras/química , Potássio/química , Eletrodos , PorosidadeRESUMO
Metallic phase 2D molybdenum disulfide (MoS2 ) is an emerging class of materials with remarkably higher electrical conductivity and catalytic activities. The goal of this study is to review the atomic structures and electrochemistry of metallic MoS2 , which is essential for a wide range of existing and new enabling technologies. The scope of this paper ranges from the atomic structure, band structure, electrical and optical properties to fabrication methods, and major emerging applications in electrochemical energy storage and energy conversion. This paper also thoroughly covers the atomic structure-properties-application relationships of metallic MoS2 . Understanding the fundamental properties of these structures is crucial for designing and manufacturing products for emerging applications. Today, a more holistic understanding of the interplay between the structure, chemistry, and performance of metallic MoS2 is advancing actual applications of this material. This new level of understanding also enables a myriad of new and exciting applications, which motivated this review. There are excellent reviews already on the traditional semiconducting MoS2 , and this review, for the first time, focuses on the uniqueness of conducting metallic MoS2 for energy applications and offers brand new materials for clean energy application.
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Nanostructured phosphorus-carbon composites are promising materials for Li-ion and Na-ion battery anodes. A hierarchical phosphorus hybrid, SiC@graphene@P, has been synthesized by the chemical vapor deposition of phosphorus on the surfaces of barbed nanowires, where the barbs are vertically grown graphene nanosheets and the cores are SiC nanowires. A temperature-gradient vaporization-condensation method has been used to remove the unhybridized phosphorus particles formed by homogeneous nucleation. The vertically grown barb shaped graphene nanosheets and a high concentration of edge carbon atoms induced a fibrous red phosphorus (f-RP) growth with its {001} planes in parallel to {002} planes of nanographene sheets and led to a strong interpenetrated interface interaction between phosphorus and the surfaces of graphene nanosheets. This hybridization has been demonstrated to significantly enhance the electrochemical performances of phosphorus.
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Biomass-based hydrogels have displayed excellent potential in flexible strain sensors due to their adequacy, biocompatibility, nontoxic and degradability. Nevertheless, their inferior mechanical properties, particularly at cryogenic temperatures, impeded their extensive utilization. Herein, we reported a rationally designed strain sensor fabricated from a gelatin and cellulose-derived hydrogel with superior mechanical robustness, cryogenic endurance, and flexibility, owing to a triple dynamic bond strategy (TDBS), namely the synergistic reinforcement among potent hydrogen bonds, imine bonds, and sodium bonds. Beyond conventional sacrificing bonds consisting of hydrogen bonds, dynamic covalent bonds and coordinate bonds, synergetic triple dynamic bonds dominated by strong hydrogen bonds and assisted by imine and sodium bonds with higher strength can dissipate more mechanical energy endowing the hydrogel with 38-fold enhancement in tensile strength (6.4 MPa) and 39-fold improvement in toughness (2.9 MPa). We further demonstrated that this hydrogel can work as a robust and biodegradable strain sensor exhibiting remarkable flexibility, broad detection range, considerable sensitivity and excellent sensing stability. Furthermore, owing to the improved nonfreezing performance achieved from incorporating sodium salts, the sensor delivered outstanding sensing properties under subzero conditions such as -20 and -4 °C. It is anticipated that the TDBS can create diverse high-performance soft-electronics for broad applications in human-machine interfaces, energy and healthcare.
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Celulose , Hidrogéis , Humanos , Biomassa , Iminas , SódioRESUMO
The development of fast-charging technologies is crucial for expediting the progress and promotion of electric vehicles. In addition to innovative material exploration, reduction in the tortuosity of electrodes is a favored strategy to enhance the fast-charging capability of lithium-ion batteries by optimizing the ion-transfer kinetics. To realize the industrialization of low-tortuosity electrodes, a facile, cost-effective, highly controlled, and high-output continuous additive manufacturing roll-to-roll screen printing technology is proposed to render customized vertical channels within electrodes. Extremely precise vertical channels are fabricated by applying the as-developed inks, using LiNi0.6 Mn0.2 Co0.2 O2 as the cathode material. Additionally, the relationship between the electrochemical properties and architecture of the channels, including the pattern, channel diameter, and edge distance between channels, is revealed. The optimized screen-printed electrode exhibited a seven-fold higher charge capacity (72 mAh g-1 ) at a current rate of 6 C and superior stability compared with that of the conventional bar-coated electrode (10 mAh g-1 , 6 C) at a mass loading of 10 mg cm-2 . This roll-to-roll additive manufacturing can potentially be applied to various active materials printing to reduce electrode tortuosity and enable fast charging in battery manufacturing.
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Achieving high energy density in all-solid-state lithium batteries will require the design of thick cathodes, and these will need to operate reversibly under normal use conditions. We use high-energy depth-profiling X-ray diffraction to measure the localized lithium content of Li1-xNi1/3Mn1/3Co1/3O2 (NMC111) through the thickness of 110 µm thick composite cathodes. The composite cathodes consisted of NMC111 of varying mass loadings mixed with argyrodite solid electrolyte Li6PS5Cl (LPSC). During cycling at C/10, substantial lithiation gradients developed, and varying the NMC111 loading altered the nature of these gradients. Microstructural analysis and cathode modeling showed this was due to high tortuosities in the cathodes. This was particularly true in the solid electrolyte phase, which experienced a marked increase in tortuosity factor during the initial charge. Our results demonstrate that current distributions are observed in sulfide-based composites and that these will be an important consideration for practical design of all-solid-state batteries.
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The anode plays a critical role relating to the energy density in all-solid-state lithium batteries (ASLBs). Silicon (Si) and lithium (Li) metal are two of the most attractive anodes because of their ultrahigh theoretical capacities. However, most investigations focus on Li metal, leaving the great potential of Si underrated. This work investigates the stability, processability, and cost of Si anodes in ASLBs and compares them with Li metal. Moreover, single-crystal LiNi0.8 Mn0.1 Co0.1 O2 is stabilized with lithium silicate (Li2 SiOx ) through a scalable sol-gel method. ASLBs with a cell-level energy density of 285 Wh kg-1 are obtained by sandwiching the Si anode, the thin sulfide solid-state electrolyte membrane, and the interface stabilized LiNi0.8 Mn0.1 Co0.1 O2 . The full cell delivers a high capacity of 145 mAh g-1 at C/3 and maintains stability for 1000 cycles. This work inspires commercialization of ASLBs on a large scale with exciting manufacturing lines for large-scale, safe, and economical energy storage.
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Personal protective equipment (PPE) has been highly recommended by the U.S. Centers for Disease Control and Prevention for self-protection during the disastrous SARS-CoV-2 (COVID-19) pandemic. Nevertheless, massive utilization of PPE encounters significant challenges in recycling and sterilizing the used masks. To tackle the associated plastic pollution of used masks, in this work, we designed a reusable, biodegradable, and antibacterial mask. The mask was fabricated by the electrospinning of polyvinyl alcohol (PVA), poly(ethylene oxide) (PEO), and cellulose nanofiber (CNF), followed by esterification and the deposition of a nitrogen-doped TiO2 (N-TiO2) and TiO2 mixture. The fabricated mask containing photocatalytic N-TiO2/TiO2 reached 100% bacteria disinfection under either 0.1 sun simulation (200-2500 nm, 106 W m-2) or natural sunlight for only 10 min. Thus, the used mask can be rejuvenated through light irradiation and reused, which represents one of the handiest technologies for handling used masks. Furthermore, intermolecular interactions between PVA, PEO, and CNF enhanced the electrospinnability and mechanical performance of the resultant mask, which possesses a 10-fold elastic modulus and 2-fold tensile strength higher than a commercial single-use mask. The porous structures of electrospun nanofibers along with strong electrostatic attraction enabled breathability (83.4 L min-1 of air flow rate) and superior particle filterability (98.7%). The prepared mask also had excellent cycling performance, wearability, and stable filtration efficiency even after 120 min wearing. Therefore, this mask could be a great alternative to current masks to address the urgent need for a sustainable, reusable, environmentally friendly, and efficient PPE under the ongoing COVID-19 contagion.
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COVID-19 , Estados Unidos , Humanos , COVID-19/prevenção & controle , Máscaras , SARS-CoV-2 , Rejuvenescimento , Álcool de Polivinil , CeluloseRESUMO
Current sulfide solid-state electrolyte (SE) membranes utilized in all-solid-state lithium batteries (ASLBs) have a high thickness (0.5-1.0 mm) and low ion conductance (<25 mS), which limit the cell-level energy and power densities. Based on ethyl cellulose's unique amphipathic molecular structure, superior thermal stability, and excellent binding capability, this work fabricates a freestanding SE membrane with an ultralow thickness of 47 µm. With ethyl cellulose as an effective disperser and a binder, the Li6 PS5 Cl is uniformly dispersed in toluene and possesses superior film formability. In addition, an ultralow areal resistance of 4.32 Ω cm-2 and a remarkable ion conductance of 291 mS (one order higher than the state-of-the-art sulfide SE membrane) are achieved. The ASLBs assembled with this SE membrane deliver cell-level high gravimetric and volumetric energy densities of 175 Wh kg-1 and 675 Wh L-1 , individually.
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Due to their high ionic conductivity and adeciduate mechanical features for lamination, sulfide composites have received increasing attention as solid electrolyte in all-solid-state batteries. Their smaller electronegativity and binding energy to Li ions and bigger atomic radius provide high ionic conductivity and make them attractive for practical applications. In recent years, noticeable efforts have been made to develop high-performance sulfide solid-state electrolytes. However, sulfide solid-state electrolytes still face numerous challenges including: 1) the need for a higher stability voltage window, 2) a better electrode-electrolyte interface and air stability, and 3) a cost-effective approach for large-scale manufacturing. Herein, a comprehensive update on the properties (structural and chemical), synthesis of sulfide solid-state electrolytes, and the development of sulfide-based all-solid-state batteries is provided, including electrochemical and chemical stability, interface stabilization, and their applications in high performance and safe energy storage.
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Batteries constructed via 3D printing techniques have inherent advantages including opportunities for miniaturization, autonomous shaping, and controllable structural prototyping. However, 3D-printed lithium metal batteries (LMBs) have not yet been reported due to the difficulties of printing lithium (Li) metal. Here, for the first time, high-performance LMBs are fabricated through a 3D printing technique using cellulose nanofiber (CNF), which is one of the most earth-abundant biopolymers. The unique shear thinning properties of CNF gel enables the printing of a LiFePO4 electrode and stable scaffold for Li. The printability of the CNF gel is also investigated theoretically. Moreover, the porous structure of the CNF scaffold also helps to improve ion accessibility and decreases the local current density of Li anode. Thus, dendrite formation due to uneven Li plating/stripping is suppressed. A multiscale computational approach integrating first-principle density function theory and a phase-field model is performed and reveals that the porous structures have more uniform Li deposition. Consequently, a full cell built with a 3D-printed Li anode and a LiFePO4 cathode exhibits a high capacity of 80 mA h g-1 at a charge/discharge rate of 10 C with capacity retention of 85% even after 3000 cycles.