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1.
Tin oxide‐based materials attract increasing attention as anodes in lithium‐ion batteries due to their high theoretical capacity, low cost, and high abundance. Composites of such materials with a carbonaceous matrix such as graphene are particularly promising, as they can overcome the limitations of the individual materials. The fabrication of antimony‐doped tin oxide (ATO)/graphene hybrid nanocomposites is described with high reversible capacity and superior rate performance using a microwave assisted in situ synthesis in tert‐butyl alcohol. This reaction enables the growth of ultrasmall ATO nanoparticles with sizes below 3 nm on the surface of graphene, providing a composite anode material with a high electric conductivity and high structural stability. Antimony doping results in greatly increased lithium insertion rates of this conversion‐type anode and an improved cycling stability, presumably due to the increased electrical conductivity. The uniform composites feature gravimetric capacity of 1226 mAh g?1 at the charging rate 1C and still a high capacity of 577 mAh g?1 at very high charging rates of up to 60C, as compared to 93 mAh g?1 at 60C for the undoped composite synthesized in a similar way. At the same time, the antimony‐doped anodes demonstrate excellent stability with a capacity retention of 77% after 1000 cycles.  相似文献   

2.
To tackle the issue of inferior cycle stability and rate capability for MnO anode materials in lithium ion batteries, a facile strategy is explored to prepare a hybrid material consisting of MnO nanocrystals grown on conductive graphene nanosheets. The prepared MnO/graphene hybrid anode exhibits a reversible capacity as high as 2014.1 mAh g?1 after 150 discharge/charge cycles at 200 mA g?1, excellent rate capability (625.8 mAh g?1 at 3000 mA g?1), and superior cyclability (843.3 mAh g?1 even after 400 discharge/charge cycles at 2000 mA g?1 with only 0.01% capacity loss per cycle). The results suggest that the reconstruction of the MnO/graphene electrodes is intrinsic due to conversion reactions. A long‐term stable nanoarchitecture of graphene‐supported ultrafine manganese oxide nanoparticles is formed upon cycling, which yields a long‐life anode material for lithium ion batteries. The lithiation and delithiation behavior suggests that the further oxidation of Mn(II ) to Mn(IV ) and the interfacial lithium storage upon cycling contribute to the enhanced specific capacity. The excellent rate capability benefits from the presence of conductive graphene and a short transportation length for both lithium ions and electrons. Moreover, the as‐formed hybrid nanostructure of MnO on graphene may help achieve faster kinetics of conversion reactions.  相似文献   

3.
Metal–organic frameworks (MOFs) and relative structures with uniform micro/mesoporous structures have shown important applications in various fields. This paper reports the synthesis of unprecedented mesoporous NixCo3?xO4 nanorods with tuned composition from the Co/Ni bimetallic MOF precursor. The Co/Ni‐MOFs are prepared by a one‐step facile microwave‐assisted solvothermal method rather than surface metallic cation exchange on the preformed one‐metal MOF template, therefore displaying very uniform distribution of two species and high structural integrity. The obtained mesoporous Ni0.3Co2.7O4 nanorod delivers a larger‐than‐theoretical reversible capacity of 1410 mAh g?1 after 200 repetitive cycles at a small current of 100 mA g?1 with an excellent high‐rate capability for lithium‐ion batteries. Large reversible capacities of 812 and 656 mAh g?1 can also be retained after 500 cycles at large currents of 2 and 5 A g?1, respectively. These outstanding electrochemical performances of the ternary metal oxide have been mainly attributed to its interconnected nanoparticle‐integrated mesoporous nanorod structure and the synergistic effect of two active metal oxide components.  相似文献   

4.
Transition metal carbonates (TMCs) with complex composition and robust hybrid structure hold great potential as high‐performance electrode materials for lithium‐ion batteries (LIBs). However, poor ionic/electronic conductivities and large volume changes of TMCs during lithiation/delithiation processes have hindered their applications. Herein, single‐phase Mn? Co mixed carbonate composites encapsulated by reduced graphene oxide (MnxCo1?xCO3/RGO), in which Mn and Co species are distributed randomly in one crystal structure, are successfully synthesized through a facial liquid‐state method. When evaluated as LIB anodes, the MnxCo1?xCO3/RGO composites exhibit enhanced electrochemical performance compared with the reference CoCO3/RGO and MnCO3/RGO. Specifically, the Mn0.7Co0.3CO3/RGO delivers an ultrahigh capacity of 1454 mA h g?1 after 130 cycles at 100 mA g?1 and exhibits an ultralong cycling stability (901 mA h g?1 after 1500 cycles at 2000 mA g?1). This is the best lithium storage performance among carbonate‐based anodes reported up to date. Such superb performance is attributed to the hybrid structure and enhanced electroconductivity due to the integration of Co and Mn into one crystal structure, which is complemented by electrochemical impedance spectroscopy and density functional theory calculations. The facile synthesis, promising electrochemical results, and scientific understanding of the MnxCo1?xCO3/RGO provides a design principle and encourages more research on TMCs‐based electrodes.  相似文献   

5.
All‐solid‐state flexible asymmetric supercapacitors (ASCs) are developed by utilization of graphene nanoribbon (GNR)/Co0.85Se composites as the positive electrode, GNR/Bi2Se3 composites as the negative electrode, and polymer‐grafted‐graphene oxide membranes as solid‐state electrolytes. Both GNR/Co0.85Se and GNR/Bi2Se3 composite electrodes are developed by a facile one‐step hydrothermal growth method from graphene oxide nanoribbons as the nucleation framework. The GNR/Co0.85Se composite electrode exhibits a specific capacity of 76.4 mAh g?1 at a current density of 1 A g?1 and the GNR/Bi2Se3 composite electrode exhibits a specific capacity of 100.2 mAh g?1 at a current density of 0.5 A g?1. Moreover, the stretchable membrane solid‐state electrolytes exhibit superior ionic conductivity of 108.7 mS cm?1. As a result, the flexible ASCs demonstrate an operating voltage of 1.6 V, an energy density of 30.9 Wh kg?1 at the power density of 559 W kg?1, and excellent cycling stability with 89% capacitance retention after 5000 cycles. All these results demonstrate that this study provides a simple, scalable, and efficient approach to fabricate high performance flexible all‐solid‐state ASCs for energy storage.  相似文献   

6.
Flexible freestanding electrodes are highly desired to realize wearable/flexible batteries as required for the design and production of flexible electronic devices. Here, the excellent electrochemical performance and inherent flexibility of atomically thin 2D MoS2 along with the self‐assembly properties of liquid crystalline graphene oxide (LCGO) dispersion are exploited to fabricate a porous anode for high‐performance lithium ion batteries. Flexible, free‐standing MoS2–reduced graphene oxide (MG) film with a 3D porous structure is fabricated via a facile spontaneous self‐assembly process and subsequent freeze‐drying. This is the first report of a one‐pot self‐assembly, gelation, and subsequent reduction of MoS2/LCGO composite to form a flexible, high performance electrode for charge storage. The gelation process occurs directly in the mixed dispersion of MoS2 and LCGO nanosheets at a low temperature (70 °C) and normal atmosphere (1 atm). The MG film with 75 wt% of MoS2 exhibits a high reversible capacity of 800 mAh g?1 at a current density of 100 mA g?1. It also demonstrates excellent rate capability, and excellent cycling stability with no capacity drop over 500 charge/discharge cycles at a current density of 400 mA g?1.  相似文献   

7.
High capacity electrodes based on a Si composite anode and a layered composite oxide cathode, Ni‐rich Li[Ni0.75Co0.1Mn0.15]O2, are evaluated and combined to fabricate a high energy lithium ion battery. The Si composite anode, Si/C‐IWGS (internally wired with graphene sheets), is prepared by a scalable sol–gel process. The Si/C‐IWGS anode delivers a high capacity of >800 mAh g?1 with an excellent cycling stability of up to 200 cycles, mainly due to the small amount of graphene (~6 wt%). The cathode (Li[Ni0.75Co0.1Mn0.15]O2) is structurally optimized (Ni‐rich core and a Ni‐depleted shell with a continuous concentration gradient between the core and shell, i.e., a full concentration gradient, FCG, cathode) so as to deliver a high capacity (>200 mAh g?1) with excellent stability at high voltage (~4.3 V). A novel lithium ion battery system based on the Si/C‐IWGS anode and FCG cathode successfully demonstrates a high energy density (240 Wh kg?1 at least) as well as an unprecedented excellent cycling stability of up to 750 cycles between 2.7 and 4.2 V at 1C. As a result, the novel battery system is an attractive candidate for energy storage applications demanding a high energy density and long cycle life.  相似文献   

8.
A three‐tiered cake‐style composite is elaborately established, with the characteristic of a double‐deck of MoS2 nanosheets and reduction of graphene oxide (RGO) sheets dotted with CoS2 nanoparticles (CoS2@MoS2/RGO). Because of the prominent synergistic effect of graphene acting as conductive support, MoS2 and CoS2 providing abundant catalytically active sites, and the cake‐style structure promoting mechanical stability, the CoS2@MoS2/RGO exhibits a superior hydrogen evolution reaction activity with a small overpotential of 98 mV at cathodic current density of 10 mA cm?2, and a small Tafel slope of 37.4 mV dec?1, as well as excellent cycling stability. Density functional theory calculations reveal that the hydrogen adsorption free energy of CoS2@MoS2/RGO is close to zero.  相似文献   

9.
In this work, a new facile and scalable strategy to effectively suppress the initial capacity fading of iron oxides is demonstrated by reacting with lithium borohydride (LiBH4) to form a B‐containing nanocomposite. Multielement, multiphase B‐containing iron oxide nanocomposites are successfully prepared by ball‐milling Fe2O3 with LiBH4, followed by a thermochemical reaction at 25–350 °C. The resulting products exhibit a remarkably superior electrochemical performance as anode materials for Li‐ion batteries (LIBs), including a high reversible capacity, good rate capability, and long cycling durability. When cycling is conducted at 100 mA g?1, the sample prepared from Fe2O3–0.2LiBH4 delivers an initial discharge capacity of 1387 mAh g?1. After 200 cycles, the reversible capacity remains at 1148 mAh g?1, which is significantly higher than that of pristine Fe2O3 (525 mAh g?1) and Fe3O4 (552 mAh g?1). At 2000 mA g?1, a reversible capacity as high as 660 mAh g?1 is obtained for the B‐containing nanocomposite. The remarkably improved electrochemical lithium storage performance can mainly be attributed to the enhanced surface reactivity, increased Li+ ion diffusivity, stabilized solid‐electrolyte interphase (SEI) film, and depressed particle pulverization and fracture, as measured by a series of compositional, structural, and electrochemical techniques.  相似文献   

10.
Lithium–sulfur (Li–S) batteries are promising energy storage systems due to their large theoretical energy density of 2600 Wh kg?1 and cost effectiveness. However, the severe shuttle effect of soluble lithium polysulfide intermediates (LiPSs) and sluggish redox kinetics during the cycling process cause low sulfur utilization, rapid capacity fading, and a low coulombic efficiency. Here, a 3D copper, nitrogen co‐doped hierarchically porous graphitic carbon network developed through a freeze‐drying method (denoted as 3D Cu@NC‐F) is prepared, and it possesses strong chemical absorption and electrocatalytic conversion activity for LiPSs as highly efficient sulfur host materials in Li–S batteries. The porous carbon network consisting of 2D cross‐linked ultrathin carbon nanosheets provides void space to accommodate volumetric expansion upon lithiation, while the Cu, N‐doping effect plays a critical role for the confinement of polysulfides through chemical bonding. In addition, after sulfuration of Cu@NC‐F network, the in situ grown copper sulfide (CuxS) embedded within CuxS@NC/S‐F composite catalyzes LiPSs conversion during reversible cycling, resulting in low polarization and fast redox reaction kinetics. At a current density of 0.1 C, the CuxS@NC/S‐F composites' electrode exhibits an initial capacity of 1432 mAh g?1 and maintains 1169 mAh g?1 after 120 cycles, with a coulombic efficiency of nearly 100%.  相似文献   

11.
In the quest to develop next generation lithium ion battery anode materials, satisfactory electrochemical performance and low material/fabrication cost are the most desirable features. In this article, porous Si nanowires are synthesized by a cost‐effective metal‐assisted chemical etching method using cheap metallurgical silicon as feedstock. More importantly, a thin oxide layer (≈3 nm) formed on the surface of porous Si nanowires stabilizes the cycling performance of lithium ion batteries. Such an oxide coating is able to constrain the huge volume expansion of the underlying Si, yet it is thin enough to ensure good permeability for both lithium ions and electrons. Therefore, the extraordinary storage capacity of Si can be well retained in prolonged electrochemical cycles. Specifically, Si/SiOx nanowires deliver a reversible capacity of 1503 mAh g?1 at the 560th cycle at a current density of 600 mA g?1, demonstrating an average of only 0.04% drop per cycle compared with its initial capacity. Furthermore, the highly porous structure and thin Si wall facilitate the electrolyte penetration and shorten the solid‐state lithium transportation path, respectively. As a result, stable and satisfactory reversible capacities of 1297, 976, 761, 548, and 282 mAh g?1 are delivered at current densities of 1200, 2400, 3600, 4800, and 7200 mA g?1, respectively.  相似文献   

12.
Hybrid metal–organic frameworks (MOFs) demonstrate great promise as ideal electrode materials for energy‐related applications. Herein, a well‐organized interleaved composite of graphene‐like nanosheets embedded with MnO2 nanoparticles (MnO2@C‐NS) using a manganese‐based MOF and employed as a promising anode material for Li‐ion hybrid capacitor (LIHC) is engineered. This unique hybrid architecture shows intriguing electrochemical properties including high reversible specific capacity 1054 mAh g?1 (close to the theoretical capacity of MnO2, 1232 mAh g?1) at 0.1 A g?1 with remarkable rate capability and cyclic stability (90% over 1000 cycles). Such a remarkable performance may be assigned to the hierarchical porous ultrathin carbon nanosheets and tightly attached MnO2 nanoparticles, which provide structural stability and low contact resistance during repetitive lithiation/delithiation processes. Moreover, a novel LIHC is assembled using a MnO2@C‐NS anode and MOF derived ultrathin nanoporous carbon nanosheets (derived from other potassium‐based MOFs) cathode materials. The LIHC full‐cell delivers an ultrahigh specific energy of 166 Wh kg?1 at 550 W kg?1 and maintained to 49.2 Wh kg?1 even at high specific power of 3.5 kW kg?1 as well as long cycling stability (91% over 5000 cycles). This work opens new opportunities for designing advanced MOF derived electrodes for next‐generation energy storage devices.  相似文献   

13.
Exfoliating graphite to graphene has attracted great attention due to the fantastic properties of graphene available for designing graphene‐based materials or devices. Besides the classic solution method, herein a unique role of TiO2 in exfoliating graphite to be graphene layers effectively is reported. As a paradigm, this discovered effect of TiO2 is significant for preparing high‐performance graphene‐modified SiOx‐based anode in lithium‐ion batteries (LIBs), in which the graphite is in situ exfoliated mechanically by TiO2 to be multilayered graphene (i.e., MLG) and then the SiOx is wrapped by the MLG to construct a SiOx/TiO2@MLG. In this case, an extremely high capacity of 1484 mAh g?1, long lifespan over 1200 cycles at 2 A g?1, as well as good performance in full LIBs (vs nickel‐rich cathode) are demonstrated. It is confirmed that the MLG can enhance electric conductivity, mitigate electrolyte decomposition, and alleviate volume effect of the SiOx effectively. This result is hard to be achieved using other kinds of metal oxide besides TiO2. It is hoped that the SiOx/TiO2@MLG is practical for pursuing LIBs with an energy density beyond 300 Wh kg?1. In addition, it is believed the ingenious strategy is applicable for designing more functional materials with greater capabilities.  相似文献   

14.
Nanocomposites comprised of poly(ethylene oxide), molybdenum disulfide, and graphene were prepared by the hydrolysis of lithiated molybdenum disulfide in an aqueous solution of PEO and graphene. Structural analysis by XRD shows the nanocomposites are disordered with an expansion of ~6 Å in the interlayer spacing. During the first discharge, the nanocomposites electrochemically dissociates irreversibly into Li2S and Mo and are able to continously cycle as Li2S +Mo/Lix ? S + Mo + Lix+2 as shown by XRD of the discharged electrodes at different depth of discharge (DOD), cyclic voltammetry (CV), and high resolution TEM. A significant increase of the reversible capacity is found in as‐prepared MoS2/PEO/graphene composite. The results suggest a new electro‐interaction between lithium and molybdenum metal that only occurs in the nanoregime and is enhanced by PEO. The addition of 2 wt% of graphene to the nanocomposites greatly increases the rate capability with rates as high as 10000mA g?1 yielding > 250mAh g?1 and recovering to > 600 mAhr g?1 at 50mA g?1.  相似文献   

15.
Si‐based anodes with a stiff diamond structure usually suffer from sluggish lithiation/delithiation reaction due to low Li‐ion and electronic conductivity. Here, a novel ternary compound ZnSi2P3 with a cation‐disordered sphalerite structure, prepared by a facile mechanochemical method, is reported, demonstrating faster Li‐ion and electron transport and greater tolerance to volume change during cycling than the existing Si‐based anodes. A composite electrode consisting of ZnSi2P3 and carbon achieves a high initial Coulombic efficiency (92%) and excellent rate capability (950 mAh g?1 at 10 A g?1) while maintaining superior cycling stability (1955 mAh g?1 after 500 cycles at 300 mA g?1), surpassing the performance of most Si‐ and P‐based anodes ever reported. The remarkable electrochemical performance is attributed to the sphalerite structure that allows fast ion and electron transport and the reversible Li‐storage mechanism involving intercalation and conversion reactions. Moreover, the cation‐disordered sphalerite structure is flexible to ionic substitutions, allowing extension to a family of Zn(Cu)Si2+xP3 solid solution anodes (x = 0, 2, 5, 10) with large capacity, high initial Coulombic efficiency, and tunable working potentials, representing attractive anode candidates for next‐generation, high‐performance, and low‐cost Li‐ion batteries.  相似文献   

16.
The emergence of flexible and wearable electronic devices with shape amenability and high mobility has stimulated the development of flexible power sources to bring revolutionary changes to daily lives. The conventional rechargeable batteries with fixed geometries and sizes have limited their functionalities in wearable applications. The first‐ever graphene‐based fibrous rechargeable batteries are reported in this work. Ultralight composite fibers consisting of reduced graphene oxide/carbon nanotube filled with a large amount of sulfur (rGO/CNT/S) are prepared by a facile, one‐pot wet‐spinning method. The liquid crystalline behavior of high concentration GO sheets facilitates the alignment of rGO/CNT/S composites, enabling rational assembly into flexible and conductive fibers as lithium–sulfur battery electrodes. The ultralight fiber electrodes with scalable linear densities ranging from 0.028 to 0.13 mg cm?1 deliver a high initial capacity of 1255 mAh g?1 and an areal capacity of 2.49 mAh cm?2 at C /20. A shape‐conformable cable battery prototype demonstrates a stable discharge characteristic after 30 bending cycles.  相似文献   

17.
Na‐ion Batteries have been considered as promising alternatives to Li‐ion batteries due to the natural abundance of sodium resources. Searching for high‐performance anode materials currently becomes a hot topic and also a great challenge for developing Na‐ion batteries. In this work, a novel hybrid anode is synthesized consisting of ultrafine, few‐layered SnS2 anchored on few‐layered reduced graphene oxide (rGO) by a facile solvothermal route. The SnS2/rGO hybrid exhibits a high capacity, ultralong cycle life, and superior rate capability. The hybrid can deliver a high charge capacity of 649 mAh g?1 at 100 mA g?1. At 800 mA g?1 (1.8 C), it can yield an initial charge capacity of 469 mAh g?1, which can be maintained at 89% and 61%, respectively, after 400 and 1000 cycles. The hybrid can also sustain a current density up to 12.8 A g?1 (≈28 C) where the charge process can be completed in only 1.3 min while still delivering a charge capacity of 337 mAh g?1. The fast and stable Na‐storage ability of SnS2/rGO makes it a promising anode for Na‐ion batteries.  相似文献   

18.
Currently, development of suitable cathode materials for zinc‐ion batteries (ZIBs) is plagued by the sluggish kinetics of Zn2+ with multivalent charge in the host structure. Herein, it is demonstrated that interlayer Mn2+‐doped layered vanadium oxide (Mn0.15V2O5·nH2O) composites with narrowed direct bandgap manifest greatly boosted electrochemical performance as zinc‐ion battery cathodes. Specifically, the Mn0.15V2O5·nH2O electrode shows a high specific capacity of 367 mAh g?1 at a current density of 0.1 A g?1 as well as excellent retentive capacities of 153 and 122 mAh g?1 after 8000 cycles at high current densities up to 10 and 20 A g?1, respectively. Even at a low temperature of ?20 °C, a reversible specific capacity of 100 mAh g?1 can be achieved at a current density of 2.0 A g?1 after 3000 cycles. The superior electrochemical performance originates from the synergistic effects between the layered nanostructures and interlayer doping of Mn2+ ions and water molecules, which can enhance the electrons/ions transport kinetics and structural stability during cycling. With the aid of various ex situ characterization technologies and density functional theory calculations, the zinc‐ion storage mechanism can be revealed, which provides fundamental guidelines for developing high‐performance cathodes for ZIBs.  相似文献   

19.
Sodium ion batteries (SIBs) are a promising alternative to lithium ion batteries for a broader range of energy storage applications in the future. However, the development of high‐performance anode materials is a bottleneck of SIBs advancement. In this work, Sb2Se3 nanorods uniformly wrapped by reduced graphene oxide (rGO) as a promising anode material for SIBs are reported. The results show that such Sb2Se3/rGO hybrid anode yields a high reversible mass‐specific energy capacity of 682, 448, and 386 mAh g?1 at a rate of 0.1, 1.0, and 2.0 A g?1, respectively, and sustains at least 500 stable cycles at a rate of 1.0 A g?1 with an average mass‐specific energy capacity of 417 mAh g?1 and capacity retention of 90.2%. In situ X‐ray diffraction study on a live SIB cell reveals that the observed high performance is a result of the combined Na+ intercalation, conversion reaction between Na+ and Se, and alloying reaction between Na+ and Sb. The presence of rGO also plays a key role in achieving high rate capacity and cycle stability by providing good electrical conductivity, tolerant accommodation to volume change, and strong electron interactions to the base Sb2Se3 anode.  相似文献   

20.
A facile synthesis of selenium sulfide (SeSx)/carbonized polyacrylonitrile (CPAN) composites is achieved by annealing the mixture of SeS2 and polyacrylonitrile (PAN) at 600 °C under vacuum. The SeSx molecules are confined by N‐containing carbon (ring) structures in the carbonized PAN to mitigate the dissolution of polysulfide and polyselenide intermediates in carbonate‐based electrolyte. In addition, formation of solid electrolyte interphase (SEI) on the surface of SeSx/CPAN electrode in the first cycle further prevents polysulfide and polyselenide intermediates from dissolution. The synergic restriction of SeSx by both CPAN matrix and SEI layer allows SeSx/CPAN composites to be charged and discharged in a low‐cost carbonate‐based electrolyte (LiPF6 in EC/DEC) with long cycling stability and high rate capability. At a current density of 600 mA g?1, it maintains a reversible capacity of 780 mAh g?1 for 1200 cycles. Moreover, it retains 50% of the capacity at 60 mA g?1 even when the current density increases to 6 A g?1. The superior electrochemical performance of SeSx/CPAN composite demonstrates that it is a promising cathode material for long cycle life and high power density lithium ion batteries. This is the first report on long cycling stability and high rate capability of selenium sulfide‐based cathode material.  相似文献   

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