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All-purpose electrode materials (APEMs), which can be effectively available on not only alkali-ion batteries but also emerging Li metal batteries, are urgently pursued to open up cost-efficient tactics for practical application of energy storage systems (ESSs), but still remain challenging. Herein, the hierarchical porous carbon nanotubes network (NOPCT) with well-tailored nanoarchitecture and high N/O-co-doping content (20.6 at%) is developed to present large-span application on ESSs. As for Li/Na-ion batteries, the NOPCT delivered excellent cycle stability and robust rate performance in a conventional ester-based electrolyte. Moreover, NOPCT also serving as a metal Li host can effectively guide smooth and uniform Li nucleation/growth to enhance the cycle stability of hybrid Li metal anodes. In addition, the NOPCT played an important role in the sustainability of sulfur electrodes, promising the feasibility of shared NOPCT for practical Li-S batteries. First-principle calculations demonstrate that graphitic-N and CO function groups favor for improving electron conductivity while the pyridinic-N and CO function group make sense for improved Li/Na adsorption and affinity through Lewis acid-base interaction, enlightening the interplay between various doped categories on improved electrochemical performance of NOPCT. This work provides profound theoretical and experimental insight into the design and development of APEMs for advanced ESSs.
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The Fe-based transition metal oxides are promising anode candidates for lithium storage considering their high specific capacity, low cost, and environmental compatibility. However, the poor electron/ion conductivity and significant volume stress limit their cycle and rate performances. Furthermore, the phenomena of capacity rise and sudden decay for α-Fe2 O3 have appeared in most reports. Here, a uniform micro/nano α-Fe2 O3 nanoaggregate conformably enclosed in an ultrathin N-doped carbon network (denoted as M/N-α-Fe2 O3 @NC) is designed. The M/N porous balls combine the merits of secondary nanoparticles to shorten the Li+ transportation pathways as well as alleviating volume expansion, and primary microballs to stabilize the electrode/electrolyte interface. Furthermore, the ultrathin carbon shell favors fast electron transfer and protects the electrode from electrolyte corrosion. Therefore, the M/N-α-Fe2 O3 @NC electrode delivers an excellent reversible capacity of 901â mA h g-1 with capacity retention up to 94.0 % after 200â cycles at 0.2â A g-1 . Notably, the capacity rise does not happen during cycling. Moreover, the lithium storage mechanism is elucidated by ex situ XRD and HRTEM experiments. It is verified that the reversible phase transformation of αâγ occurs during the first cycle, whereas only the α-Fe2 O3 phase is reversibly transformed during subsequent cycles. This study offers a simple and scalable strategy for the practical application of high-performance Fe2 O3 electrodes.
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Lithium-ion batteries (LIBs) are one of the most significant energy storage devices applied in power supply facilities. However, a huge number of spent LIBs would bring harmful resource waste and environmental hazards. In this study, a benign hydrometallurgical method using phytic acid as precipitant is proposed to recover useful metallic Mn ions from spent LiMn2 O4 batteries. Besides Mn-based cathodes, this recovery process is also applicable for other commercial batteries. More importantly, for the first time, the as-obtained manganous complex is employed as a nanofiller in a polyethylene oxide matrix to largely improve Li+ conductivity and transference number. As a result, when applied in all-solid-state lithium batteries, high capacity and outstanding cyclic stability are achieved with capacity retention of 86.4 % after 60 cycles at 0.1â C. The recovery of spent lithium batteries not only has benefits for the environment and resources, but also shows great potential application in all-solid-state lithium batteries, which opens up a costless and efficient circulation pathway for clean and reliable energy storage systems.
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Owing to low ion/electron conductivity and large volume change, transitional metal dichalcogenides (TMDs) suffer from inferior cycle stability and rate capability when used as the anode of lithium-ion batteries (LIBs). To overcome these disadvantages, amorphous molybdenum sulfide (MoSx ) nanospheres were prepared and coated with an ultrathin carbon layer through a simple one-pot reaction. Combining X-ray photoelectron spectroscopy (XPS) with theoretical calculations, MoSx was confirmed as having a special chain molecular structure with two forms of S bonding (S2- and S2 2- ), the optimal adsorption sites of Li+ were located at S2 2- . As a result, the MoSx electrode exhibits superior cycle and rate capacities compared with crystalline 2H-MoS2 (e.g., delivering a high capacity of 612.4â mAh g-1 after 500â cycles at 1â A g-1 ). This is mainly attributed to more exposed active S2 2- sites for Li storage, more Li+ transfer pathways for improved ion conductivity, and suppressed electrode structure pulverization of MoSx derived from the inherent chain-like molecular structure. Quantitative charge storage analysis further demonstrates the improved pseudocapacitive contribution of amorphous MoSx induced by fast reaction kinetics. Moreover, the morphology contrast after cycling demonstrates the dispersion of active materials is more uniform for MoSx than 2H-MoS2 , suggesting the MoSx can well accommodate the volume stress of the electrode during discharging. Through regulating the molecular structure, this work provides an effective targeted strategy to overcome the intrinsic issues of TMDs for high-performance LIBs.
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MnO is a promising high-capacity anode material for lithium-ion batteries (LIBs), but pristine material suffers short cycle life and poor rate capability, thus hindering the practical application. In this work, a new type of porous MnO microballs stringed with N-doped porous carbon (3DHB-MnO@NC) with a well-connected hierarchical three-dimensional network structure was prepared by the facile self-template method. The 3DHB-MnO@NC electrode can effectively promote the ion/electron transfer and buffer the large volume change of electrode during the electrochemical reaction. As the anode for LIBs, the 3DHB-MnO@NC possesses outstanding cycling performance (1247.7â mA h g-1 after 90 cycles at 200â mA g-1 ) and good rate capabilities (949.6â mA h g-1 after 450 cycles at 1000â mA g-1 ). The facile self-template method of the prepared 3DHB-MnO@NC composite paves a new way for practical applications of MnO in high performance LIBs.
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A new hexadecahedron assembled by core-shell CoS2 particles@N-doped carbon (CoS2 @NCH) is prepared successfully through the self-templating method. The CoS2 @NCH hybrid electrode delivers a high lithium-storage capacity of 778â mA h g-1 after 1000â cycles at a high current density of 1â A g-1 , which is the longest cycle lifespan among the reported CoS2 anode materials in lithium-ion batteries. Furthermore, the CoS2 @NCH hybrid electrode shows excellent rate capability with a discharge capacity of 220â mA h g-1 at an extremely high current density of 20â A g-1 , and a charge capacity of 649â mA h g-1 is restored upon returning the current density back to 2â A g-1 . The superior performance is attributed to the unique construction of CoS2 @NCH. The N-doped interconnected porous carbon shells form highly conductive skeletons for quick electron transfer and prevent the electrode from collapsing. Moreover, the porous characteristic of the materials plays a key role: as some effective channels, the mesopores on the porous carbon shells provide greater access for lithium, and the mesopores derived from the particle interspace enables the complete immersion of the electrodes in electrolyte, which alleviates the volume expansion and ensures the integrity of the electrode. In addition, the nanosized CoS2 particles, which shorten the ion-transport path and provide extra electroactive sites, also improve the reaction kinetics.
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Bimetallic transition-metal oxides, which exhibit superior electrochemical properties compared with pristine single-metal oxides, have recently become a topic of significant research interest for applications in lithium-ion batteries (LIBs). Herein, we report a simple and scalable electrospinning method to synthesize porous CoTiO3 nanofibers as the precursor for nanostructured bimetallic transition-metal oxides formed electrochemically in situ. This strategy ensures uniform mixing and perfect contact between two constituent transition-metal oxides during the lithiation/delithiation process. Furthermore, CoTiO3 nanofibers based on ultrafine CoTiO3 nanocrystals are interconnected to form a nano/microstructured 3D network, which ensures the high stability of the in situ formed structure composed of bimetallic transition-metal oxides, and also fast ion/electron transfer and electrolyte penetration into the electrode. Electrochemical measurements revealed the excellent lithium storage (647â mAh g-1 at 0.1â Ag-1 ) and retention properties (600â mAh g-1 at 1â Ag-1 after 1200â cycles) of the CoO/TiO2 electrode. Moreover, the electrochemical reaction mechanism was explored by using ex situ X-ray photoelectric spectroscopy and cyclic voltammetry tests, which confirmed the two-phase reaction processes in the electrodes. These results clearly validate the potential of CoTiO3 with a unique nano/microstructured morphology as the precursor for a bimetallic transition-metal oxide for use as the anode material for long-life LIBs.
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In this work, oxygen-deficient anatase TiO2 nanosheets (A-TiO2-x NSs) are proposed as a substrate to improve the electrochemical properties of sulfur electrodes for lithium-sulfur (Li-S) batteries. The A-TiO2-x NSs are prepared by partly reducing pristine TiO2 nanosheets (A-TiO2 NSs) in NaBH4 solution. With some oxygen vacancies on the surface of the TiO2 nanosheets, A-TiO2-x NSs not only promote electronic transfer, but also act as more effective polysulfide reservoirs to minimize the dissolution of lithium polysulfides (LiPSs) than the A-TiO2 NSs control. Hence, upon utilization as modifiers for cathodes of Li-S batteries, the A-TiO2-x NSs-modified sulfur (A-TiO2-x NSs-S) cathode exhibits a higher reversible specific capacity and greater cycling performance and rate capability than the A-TiO2 NSs-modified one (A-TiO2 NSs-S). For example, A-TiO2-x NSs-S delivers an initial specific capacity of 1277.1â mAh g-1 at 0.1â C and maintains a stable Coulombic efficiency of approximately 99.2 % after the first five cycles; these values are higher than those of 997.3â mAh g-1 and around 96.7 %, respectively, for A-TiO2 NSs-S. The enhanced electrochemical properties of the A-TiO2-x NSs-S cathode can be ascribed mainly to the more effective adsorption of dissolvable and diffused LiPSs by the oxygen vacancies. Therefore, utilization of the structure of oxygen vacancies in Li-S batteries demonstrates great prospects for practical application.
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A novel kind of plum-pudding like mesoporous SiO2 nanospheres (MSNs) and flake graphite (FG) nanocomposite (pp-MSNs/FG) was designed and fabricated via a facile and cost-effective hydrothermal method. Transmission electron microscopy (TEM) analysis showed that most of the MSNs were well anchored on FG. This special architecture has multiple advantages, including FG that offers a conductive framework and hinders the volume expansion effect. Moreover, the porous structure of MSNs could provide more available lithium storage sites and extra free space to accommodate the mechanical strain caused by the volume change during the repeated reversible reaction between Li(+) and active materials. Due to the synergetic effects of its unique plum-pudding structure, the obtained pp-MSNs/FG nanocomposite exhibited a decent reversible capacity of 702 mA h g(-1) (based on the weight of MSNs in the electrode material) after 100 cycles with high Coulombic efficiency above 99% under 100 mA g(-1) and a charge capacity of 239.6 mA h g(-1) could be obtained even under 5000 mA g(-1). Their high rate performance is among the best-reported performances of SiO2-based anode materials.
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The effect of graphene lateral size on the electrochemical performance of lithium-sulfur (Li-S) batteries is often ignored. In this study, the thermally exfoliated large lateral-sized graphene (denoted LTG) was employed as the conductive matrix to support sulfur, and its performance was then compared with that of a smaller lateral-sized graphene (denoted STG) for Li-S batteries. The results showed that the LTG-S composite exhibited much higher capacity retention (53%) versus the STG-S (29%) and better rate capabilities. Because they were both identical in morphology, in terms of sulfur content and sulfur distribution, the improved properties probably resulted from the potential prevention of polysulfide diffusion upon cycling due to the larger graphene-based network and higher aspect ratio of the LTG matrix, referred as better polysulfide reservoirs. To further improve the cell performance, a reduced graphene oxide-coated carbon fiber paper (RCF) was inserted between the LTG-S cathode and the separator by a simple drop-coat method, which provided an increased conductive surface area for polysulfides to be oxidized/reduced and buffered volume expansion. As expected, the discharge capacities of 1143 and 622 mA h g(-1) at first use and after 100th cycles were obtained with an average Coulombic efficiency of 99.7%, which were higher than 847 and 455 mA h g(-1) for the cathode without the RCF, respectively. This study highlights the significance of large graphene sheets and interlayers on the inhibition of polysulfide diffusion and offers a new way to solve the problems of Li-S batteries.
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SnS2 as the promising anode for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) still encounters the undesirable rate performance and cycle stability. Herein, a unique stable structure is developed, where the SnS2 nanocrystals (NCs) are sturdily encapsulated by carbon shells anchored on a reduced graphene oxide (rGO) via the one-pot solvothermal process. The well-controlled carbon shells provide the enduring protection for SnS2 NCs through C-S covalent bonds from the corrosion of electrolyte and pulverization of structure. Moreover, both experimental results and density functional theory (DFT) calculations demonstrate that the carbon protective shell effectively enhances the structure stability and conductivity of the resulting materials. Interestingly, the size of SnS2 NCs and the thickness of carbon shells are accurately controlled by regulating the content of glucose. Aided by the advanced electron/ion transfer kinetics and structure stability, the SnS2-based electrode exhibits desired lithium/sodium storage performance and unprecedented long-term cycling stability (capacity retention of 74.7% after 1000 cycles at 2 A g-1 for LIBs and 102% after 200 cycles at 500 mA g-1 for SIBs). This work develops a method for promoting the practical applications and large-scale production of SnS2 composites for energy storage devices.
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The intrinsic charge-transfer property bears the primary responsibility for the sluggish redox kinetics of the common electrode materials, especially operated at low temperatures. Herein, we report the crafting of homogeneously confined Fe7Se8 nanoparticles with a well-defined graphitic carbon matrix that demonstrate a highly efficient charge-transfer system in a designed natural coral-like structure (cl-Fe7Se8@C). Notably, the intricate architecture as well as highly conductive peculiarity of C concurrently satisfy the demands of achieving fast ionic/electrical conductivities for both Li/Na-ion batteries in a wide temperature range. For example, when cl-Fe7Se8@C is employed as the anode material to assemble full batteries with the cathode of Na3V2(PO4)2O2F (NVPOF), decent capacities of 323.1 and 175.9 mA h g-1 can be acquired at temperatures of 25 and -25 °C, respectively. This work is significant for further developing potential anode materials for advanced energy storage and conversion under low-temperature conditions.
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In order to develop promising anode materials for lithium-ion batteries (LIBs), a unique nanocomposite abbreviated as Gâ¥FP@C-NA, in which a carbon-coated FeP nanorod array (FP@C-NA) is vertically grown on a conductive reduced graphene oxide (G) network, has been successfully prepared via a scalable strategy. Benefiting from the distinctive structure, Gâ¥FP@C-NA exhibits much improved conductivity, structural stability and pseudocapacitance-boosted ultrafast electrochemical kinetics for Li storage. As a result, the Gâ¥FP@C-NA delivers a high Li-storage capacity (1106 mA h g-1 at 50 mA g-1), outstanding rate capability (565 mA h g-1 at 5000 mA g-1) and long-term cycling stability (1009 mA h g-1 at 500 mA g-1 after 500 cycles and 310 mA h g-1 at 2000 mA g-1 after 2000 cycles) when used as an anode material for LIBs. As expected, this kind of nanoarray structure is attractive and can also be extended to other electrode materials for various energy storage systems.
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Solid-state lithium metal batteries have emerged as a promising alternative to existing liquid Li-ion batteries and can power the future storage market considering their higher energy outputs and better safety. Among various solid electrolytes, polymer electrolytes have received more attention due to their potential advantages, including wide electrochemical windows, ease of processing, low interface impedance and low cost. Polymeric electrolytes based on poly(ethylene oxide) (PEO) as a well-known polymer matrix have been extensively studied because of their highly flexible EO segments in the amorphous phase that can provide channels for lithium ion transport. However, obtaining a PEO-based solid electrolyte with high Li ion conductivity and without sacrificing mechanical strength is still a huge challenge. In this study, polymethylhydrogen-siloxane (PMHS) with low glass transition temperature and good flexibility was blended into the PEO to optimize ion transportation by the solution casting technique. The hybrid electrolyte membrane with 40% PMHS exhibited high ionic conductivity (2.0 × 10-2 S cm-1 at 80 °C), large electrochemical windows (5.2 V), a high degree of flexibility, and thermal stability. When assembling a Li/LiFePO4 battery, a reversible capacity close to 140 mA h g-1 (0.1 C) at 60 °C was delivered. In addition, a cell with this polymer electrolyte exhibits excellent stability. These results demonstrate that solid polymer electrolyte systems are eligible for next-generation high energy density all-solid-state lithium ion batteries.
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A three-dimensional hierarchical Ni3Se2 nanorod array (NA) grown in situ on foam Ni is the first to act as a carbon/binder-free electrode of SIBs via a one-step reversible conversion reaction. By a special decomposition-fusion process, the morphology and composition of the NA are regulated to obtain ultrahigh areal capacity, which is three times greater than that reported for other metal selenides.
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A three-layered cathode structure was designed to minimize the shuttle effect of polysulfides and improve active material utilization. The three-layered configuration was fabricated by directly dropping pure sulfur composite slurry into multifunctional dual-barrier layers consisting of a self-standing TiO2/C interlayer and a very thin acetylene black layer (0.35 mg cm-2). In consequence, a decent discharge capacity of 963 mA h g-1 was acquired after 100 cycles at 0.1 C. With cycling at 0.1, 0.2, 0.5, 1, and 2 C, the cells displayed excellent reversible capacities of 1203, 1145, 1035, 934, and 820 mA h g-1, respectively. Furthermore, the cells still delivered a satisfactory discharge capacity of 799 mA h g-1 after 300 cycles at 0.5 C. The light mass of the three-layered configuration guarantees that the energy density is effectively improved, considering the overall mass of the cathode. The energy density (603 W h kg-1 after 100 cycles) was at a high level compared with those of the reported ones. Therefore, it is believed that the synergistic design for the three-layered cathode structure, which combines the mass-produced layer-by-layer structure, provides a novel protocol to the practical application of lithium-sulfur batteries.
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In this work, a flexible and self-supporting P-doped carbon cloth (FPCC), which is composed of interwoven mesh of hollow microtubules with porous carbon walls, is prepared via a vacuum-sealed doping technology by employing the commercially available cotton cloth as sustainable and scalable raw material. When directly used as binder-free anode for sodium-ion batteries, the as-prepared FPCC delivers superior Na-storage properties in terms of specific capacity up to 242.4 mA h g-1, high initial Coulombic efficiency of â¼72%, excellent rate capabilities (e.g., 123.1 mA h g-1 at a high current of 1 A g-1), and long-term cycle life (e.g., â¼88% capacity retention after even 600 cycles). All these electrochemical data are better than the undoped carbon cloth control, demonstrating the significance of P-doping to enhance the Na-storage properties of cotton-derived carbon anode. Furthermore, the technologies of electrochemical impedance spectroscopy and galvanostatic intermittent titration technique are implemented to disclose the decrease of charge transfer resistance and improvement of Na-migration kinetics, respectively.
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Marcasite (m-FeS2) exhibits higher electronic conductivity than that of pyrite (p-FeS2) because of its lower semiconducting gap (0.4 vs 0.7 eV). Meanwhile, as demonstrates stronger Fe-S bonds and less S-S interactions, the m-FeS2 seems to be a better choice for electrode materials compared to p-FeS2. However, the m-FeS2 has been seldom studied due to its sophisticated synthetic methods until now. Herein, a hierarchical m-FeS2 and carbon nanofibers composite (m-FeS2/CNFs) with grape-cluster structure was designed and successfully prepared by a straightforward hydrothermal method. When evaluated as an electrode material for lithium ion batteries, the m-FeS2/CNFs exhibited superior lithium storage properties with a high reversible capacity of 1399.5 mAh g-1 after 100 cycles at 100 mA g-1 and good rate capability of 782.2 mAh g-1 up to 10 A g-1. The Li-storage mechanism for the lithiation/delithiation processes of m-FeS2/CNFs was systematically investigated by ex situ powder X-ray diffraction patterns and scanning electron microscopy. Interestingly, the hierarchical m-FeS2 microspheres assembled by small FeS2 nanoparticles in the m-FeS2/CNFs composite converted into a mimosa with leaves open shape during Li+ insertion process and vice versa. Accordingly, a "CNFs accelerated decrystallization-recrystallization" mechanism was proposed to explain such morphology variations and the decent electrochemical performance of m-FeS2/CNFs.
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In this paper, gelatin as a natural biomass was selected to successfully prepare an oxygen-enriched carbon with layered sedimentary rocks structure, which exhibited ultrahigh-rate performance and excellent cycling stability as supercapacitors. The specific capacitance reached 272.6 F g(-1) at 1 A g(-1) and still retained 197.0 F g(-1) even at 100 A g(-1) (with high capacitance retention of 72.3%). The outstanding electrochemical performance resulted from the special layered structure with large surface area (827.8 m(2) g(-1)) and high content of oxygen (16.215 wt %), which effectively realized the synergistic effects of the electrical double-layer capacitance and pseudocapacitance. Moreover, it delivered an energy density of 25.3 Wh kg(-1) even with a high power density of 34.7 kW kg(-1) and ultralong cycling stability (with no capacitance decay even over 10,000 cycles at 2 A g(-1)) in a symmetric supercapacitor, which are highly desirable for their practical application in energy storage devices and conversion.
Assuntos
Carbono/química , Capacitância Elétrica , Sedimentos Geológicos/química , Oxigênio/químicaRESUMO
In this work, carbon-free, porous, and micro/nanostructural Zn2GeO4 nanofibers (p-ZGONFs) have been prepared via a dissolution-recrystallization-assisted electrospinning technology. The successful electrospinning to fabricate the uniform p-ZGONFs mainly benefits from the preparation of completely dissolved solution, which avoids the sedimentation of common Ge-containing solid-state precursors. Electrochemical tests demonstrate that the as-prepared p-ZGONFs exhibit superior Li-storage properties in terms of high initial reversible capacity of 1075.6 mA h g-1, outstanding cycling stability (no capacity decay after 130 cycles at 0.2 A g-1), and excellent high-rate capabilities (e.g., still delivering a capacity of 384.7 mA h g-1 at a very high current density of 10 A g-1) when used as anode materials for lithium ion batteries (LIBs). All these Li-storage properties are much better than those of Zn2GeO4 nanorods prepared by a hydrothermal process. The much enhanced Li-storage properties should be attributed to its distinctive structural characteristics including the carbon-free composition, plentiful pores, and macro/nanostructures. Carbon-free composition promises its high theoretical Li-storage capacity, and plentiful pores cannot only accommodate the volumetric variations during the successive lithiation/delithiation but can also serve as the electrolyte reservoirs to facilitate Li interaction with electrode materials.