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1.
High energy density is the major demand for next‐generation rechargeable batteries, while the intrinsic low alkali metal adsorption of traditional carbon–based electrode remains the main challenge. Here, the mechanochemical route is proposed to prepare nitrogen doped γ‐graphyne (NGY) and its high capacity is demonstrated in lithium (LIBs)/sodium (SIBs) ion batteries. The sample delivers large reversible Li (1037 mAh g?1) and Na (570.4 mAh g?1) storage capacities at 100 mA g?1 and presents excellent rate capabilities (526 mAh g?1 for LIBs and 180.2 mAh g?1 for SIBs) at 5 A g?1. The superior Li/Na storage mechanisms of NGY are revealed by its 2D morphology evolution, quantitative kinetics, and theoretical calculations. The effects on the diffusion barriers (Eb) and adsorption energies (Ead) of Li/Na atoms in NGY are also studied and imine‐N is demonstrated to be the ideal doping format to enhance the Li/Na storage performance. Besides, the Li/Na adsorption routes in NGY are optimized according to the experimental and the first‐principles calculation results. This work provides a facile way to fabricate high capacity electrodes in LIBs/SIBs, which is also instructive for the design of other heteroatomic doped electrodes.  相似文献   

2.
γ‐Graphyne is a new nanostructured carbon material with large theoretical Li+ storage due to its unique large conjugate rings, which makes it a potential anode for high‐capacity lithium‐ion batteries (LIBs). In this work, γ‐graphyne‐based high‐capacity LIBs are demonstrated experimentally. γ‐Graphyne is synthesized through mechanochemical and calcination processes by using CaC2 and C6Br6. Brunauer–Emmett–Teller, atomic force microscopy, X‐ray photoelectron spectroscopy, solid‐state 13C NMR and Raman spectra are conducted to confirm its morphology and chemical structure. The sample presents 2D mesoporous structure and is exactly composed of sp and sp2‐hybridized carbon atoms as the γ‐graphyne structure. The electrode shows high Li+ storage (1104.5 mAh g?1 at 100 mA g?1) and rate capability (435.1 mAh g?1 at 5 A g?1). The capacity retention can be up to 948.6 (200 mA g?1 for 350 cycles) and 730.4 mAh g?1 (1 A g?1 for 600 cycles), respectively. These excellent electrochemical performances are ascribed to the mesoporous architecture, large conjugate rings, enlarged interplanar distance, and high structural integrity for fast Li+ diffusion and improved cycling stability in γ‐graphyne. This work provides an environmentally benign and cost‐effective mechanochemical method to synthesize γ‐graphyne and demonstrates its superior Li+ storage experimentally.  相似文献   

3.
Lithium–oxygen (Li–O2) batteries are attracting more attention owing to their superior theoretical energy density compared to conventional Li‐ion battery systems. With regards to the catalytically electrochemical reaction on a cathode, the electrocatalyst plays a key role in determining the performance of Li–O2 batteries. Herein, a new 3D hollow α‐MnO2 framework (3D α‐MnO2) with porous wall assembled by hierarchical α‐MnO2 nanowires is prepared by a template‐induced hydrothermal reaction and subsequent annealing treatment. Such a distinctive structure provides some essential properties for Li–O2 batteries including the intrinsic high catalytic activity of α‐MnO2, more catalytic active sites of hierarchical α‐MnO2 nanowires on 3D framework, continuous hollow network and rich porosity for the storage of discharge product aggregations, and oxygen diffusion. As a consequence, 3D α‐MnO2 achieves a high specific capacity of 8583 mA h g?1 at a current density of 100 mA g?1, a superior rate capacity of 6311 mA h g?1 at 300 mA g?1, and a very good cycling stability of 170 cycles at a current density of 200 mA g?1 with a fixed capacity of 1000 mA h g?1. Importantly, the presented design strategy of 3D hollow framework in this work could be extended to other catalytic cathode design for Li–O2 batteries.  相似文献   

4.
A facile two‐step solution‐phase method has been developed for the preparation of hierarchical α‐MnO2 nanowires@Ni1‐xMnxOy nanoflakes core–shell nanostructures. Ultralong α‐MnO2 nanowires were synthesized by a hydrothermal method in the first step. Subsequently, Ni1‐xMnxOy nanoflakes were grown on α‐MnO2 nanowires to form core–shell nanostructures using chemical bath deposition followed by thermal annealing. Both solution‐phase methods can be easily scaled up for mass production. We have evaluated their application in supercapacitors. The ultralong one‐dimensional (1D) α‐MnO2 nanowires in hierarchical core–shell nanostructures offer a stable and efficient backbone for charge transport; while the two‐dimensional (2D) Ni1‐xMnxOy nanoflakes on α‐MnO2 nanowires provide high accessible surface to ions in the electrolyte. These beneficial features enable the electrode with high capacitance and reliable stability. The capacitance of the core–shell α‐MnO2@Ni1‐xMnxOy nanostructures (x = 0.75) is as high as 657 F g?1 at a current density of 250 mA g?1, and stable charging‐discharging cycling over 1000 times at a current density of 2000 mA g?1 has been realized.  相似文献   

5.
Carbonaceous materials as anodes usually exhibit low capacity for lithium ion batteries (LIBs) and sodium ion batteries (SIBs). Oxygen‐doped carbonaceous materials have the potential of high capacity and super rate performance. However, up to now, the reported oxygen‐doped carbonaceous materials usually exhibit inferior electrochemical performance. To overcome this problem, a high reactive oxygen‐doped 3D interdigital porous carbonaceous material is designed and synthesized through epitaxial growth method and used as anodes for LIBs and SIBs. It delivers high reversible capacity, super rate performance, and long cycling stability (473 mA h g?1after 500 cycles for LIBs and 223 mA h g?1 after 1200 cycles for SIBs, respectively, at the current density of 1000 mA g?1), with a capacity decay of 0.0214% per cycle for LIBs and 0.0155% per cycle for SIBs. The results demonstrate that constructing 3D interdigital porous structure with reactive oxygen functional groups can significantly enhance the electrochemical performance of oxygen‐doped carbonaceous material.  相似文献   

6.
It is of great importance to exploit electrode materials for sodium‐ion batteries (SIBs) with low cost, long life, and high‐rate capability. However, achieving quick charge and high power density is still a major challenge for most SIBs electrodes because of the sluggish sodiation kinetics. Herein, uniform and mesoporous NiS2 nanospheres are synthesized via a facile one‐step polyvinylpyrrolidone assisted method. By controlling the voltage window, the mesoporous NiS2 nanospheres present excellent electrochemical performance in SIBs. It delivers a high reversible specific capacity of 692 mA h g?1. The NiS2 anode also exhibits excellent high‐rate capability (253 mA h g?1 at 5 A g?1) and long‐term cycling performance (319 mA h g?1 capacity remained even after 1000 cycles at 0.5 A g?1). A dominant pseudocapacitance contribution is identified and verified by kinetics analysis. In addition, the amorphization and conversion reactions during the electrochemical process of the mesoporous NiS2 nanospheres is also investigated by in situ X‐ray diffraction. The impressive electrochemical performance reveals that the NiS2 offers great potential toward the development of next generation large scale energy storage.  相似文献   

7.
Rechargeable Zn/MnO2 batteries using mild aqueous electrolytes are attracting extensive attention due to their low cost, high safety, and environmental friendliness. However, the charge‐storage mechanism involved remains a topic of controversy so far. Also, the practical energy density and cycling stability are still major issues for their applications. Herein, a free‐standing α‐MnO2 cathode for aqueous zinc‐ion batteries (ZIBs) is directly constructed with ultralong nanowires, leading to a rather high energy density of 384 mWh g?1 for the entire electrode. Greatly, the H+/Zn2+ coinsertion mechanism of α‐MnO2 cathode for aqueous ZIBs is confirmed by a combined analysis of in situ X‐ray diffractometry, ex situ transmission electron microscopy, and electrochemical methods. More interestingly, the Zn2+‐insertion is found to be less reversible than H+‐insertion in view of the dramatic capacity fading occurring in the Zn2+‐insertion step, which is further evidenced by the discovery of an irreversible ZnMn2O4 layer at the surface of α‐MnO2. Hence, the H+‐insertion process actually plays a crucial role in maintaining the cycling performance of the aqueous Zn/α‐MnO2 battery. This work is believed to provide an insight into the charge‐storage mechanism of α‐MnO2 in aqueous systems and paves the way for designing aqueous ZIBs with high energy density and long‐term cycling ability.  相似文献   

8.
Fe2O3 is regarded as a promising anode material for lithium‐ion batteries (LIBs) and sodium‐ion batteries (SIBs) due to its high specific capacity. The large volume change during discharge and charge processes, however, induces significant cracking of the Fe2O3 anodes, leading to rapid fading of the capacity. Herein, a novel peapod‐like nanostructured material, consisting of Fe2O3 nanoparticles homogeneously encapsulated in the hollow interior of N‐doped porous carbon nanofibers, as a high‐performance anode material is reported. The distinctive structure not only provides enough voids to accommodate the volume expansion of the pea‐like Fe2O3 nanoparticles but also offers a continuous conducting framework for electron transport and accessible nanoporous channels for fast diffusion and transport of Li/Na‐ions. As a consequence, this peapod‐like structure exhibits a stable discharge capacity of 1434 mAh g?1 (at 100 mA g?1) and 806 mAh g?1 (at 200 mA g?1) over 100 cycles as anode materials for LIBs and SIBs, respectively. More importantly, a stable capacity of 958 mAh g?1 after 1000 cycles and 396 mAh g?1 after 1500 cycles can be achieved for LIBs and SIBs, respectively, at a large current density of 2000 mA g?1. This study provides a promising strategy for developing long‐cycle‐life LIBs and SIBs.  相似文献   

9.
Prussian blue and its analogs are regarded as the promising cathodes for sodium‐ion batteries (SIBs). Recently, various special structures are constructed to improve the electrochemical properties of these materials. In this study, a novel architecture of Prussian blue analogs with large cavity and multilayer shells is investigated as cathode material for SIBs. Because the hollow structure can relieve volume expansion and core–shell heterostructure can optimize interfacial properties, the complex structure materials exhibited a highly initial capacity of 123 mA h g?1 and a long cycle life. After 600 cycles, the reversible capacity of the electrode still maintains at 102 mA h g?1 without significant voltage decay, indicating a superior structure stability and sodium storage kinetics. Even at high current density of 3200 mA g?1, the electrode still delivers a considerable capacity above 52 mA h g?1. According to the electrochemical analysis and ex‐situ measurements, it can be inferred that the enhanced apparent diffusion coefficient and improved insertion/extraction performance of electrode have been obtained by building this new morphology.  相似文献   

10.
Supercapacitors suffer from lack of energy density and impulse the energy density limit, so a new class of hybrid electrode materials with promising architectures is strongly desirable. Here, the rational design of a 3D hierarchical sandwich Co9S8/α‐MnS@N–C@MoS2 nanowire architecture is achieved during the hydrothermal sulphurization reaction by the conversion of binary mesoporous metal oxide core to corresponding individual metal sulphides core along with the formation of outer metal sulphide shell at the same time. Benefiting from the 3D hierarchical sandwich architecture, Co9S8/α‐MnS@N–C@MoS2 electrode exhibits enhanced electrochemical performance with high specific capacity/capacitance of 306 mA h g?1/1938 F g?1 at 1 A g?1, and excellent cycling stability with a specific capacity retention of 86.9% after 10 000 cycles at 10 A g?1. Moreover, the fabricated asymmetric supercapacitor device using Co9S8/α‐MnS@N–C@MoS2 as the positive electrode and nitrogen doped graphene as the negative electrode demonstrates high energy density of 64.2 Wh kg?1 at 729.2 W kg?1, and a promising energy density of 23.5 Wh kg?1 is still attained at a high power density of 11 300 W kg?1. The hybrid electrode with 3D hierarchical sandwich architecture promotes enhanced energy density with excellent cyclic stability for energy storage.  相似文献   

11.
The development of manganese dioxide as the cathode for aqueous Zn‐ion battery (ZIB) is limited by the rapid capacity fading and material dissolution. Here, a highly reversible aqueous ZIB using graphene scroll‐coated α‐MnO2 as the cathode is proposed. The graphene scroll is uniformly coated on the MnO2 nanowire with an average width of 5 nm, which increases the electrical conductivity of the MnO2 nanowire and relieves the dissolution of the cathode material during cycling. An energy density of 406.6 Wh kg?1 (382.2 mA h g?1) at 0.3 A g?1 can be reached, which is the highest specific energy value among all the cathode materials for aqueous Zn‐ion battery so far, and good long‐term cycling stability with 94% capacity retention after 3000 cycles at 3 A g?1 are achieved. Meanwhile, a two‐step intercalation mechanism that Zn ions first insert into the layers and then the tunnels of MnO2 framework is proved by in situ X‐ray diffraction, galvanostatic intermittent titration technique, and X‐ray photoelectron spectroscopy characterizations. The graphene scroll‐coated metallic oxide strategy can also bring intensive interests for other energy storage systems.  相似文献   

12.
Yolk–shell nanostructures have received great attention for boosting the performance of lithium‐ion batteries because of their obvious advantages in solving the problems associated with large volume change, low conductivity, and short diffusion path for Li+ ion transport. A universal strategy for making hollow transition metal oxide (TMO) nanoparticles (NPs) encapsulated into B, N co‐doped graphitic nanotubes (TMO@BNG (TMO = CoO, Ni2O3, Mn3O4) through combining pyrolysis with an oxidation method is reported herein. The as‐made TMO@BNG exhibits the TMO‐dependent lithium‐ion storage ability, in which CoO@BNG nanotubes exhibit highest lithium‐ion storage capacity of 1554 mA h g?1 at the current density of 96 mA g?1, good rate ability (410 mA h g?1 at 1.75 A g?1), and high stability (almost 96% storage capacity retention after 480 cycles). The present work highlights the importance of introducing hollow TMO NPs with thin wall into BNG with large surface area for boosting LIBs in the terms of storage capacity, rate capability, and cycling stability.  相似文献   

13.
Fe3S4 @ S @ 0.9Na3SbS4?0.1NaI composite cathode is prepared through one‐step wet‐mechanochemical milling procedure. During milling process, ionic conduction pathway is self‐formed in the composite due to the formation of 0.9Na3SbS4?0.1NaI electrolyte without further annealing treatment. Meanwhile, the introduction of Fe3S4 can increase the electronic conductivity of the composite cathode by one order of magnitude and nearly double enhance the ionic conductivities. Besides, the aggregation of sulfur is effectively suppressed in the obtained Fe3S4 @ S @ 0.9Na3SbS4?0.1NaI composite, which will enhance the contact between sulfur and 0.9Na3SbS4?0.1NaI electrolyte, leading to a decreased interfacial resistance and improving the electrochemical kinetics of sulfur. Therefore, the resultant all‐solid‐state sodium–sulfur battery employing Fe3S4 @ S @ 0.9Na3SbS4?0.1NaI composite cathode shows discharge capacity of 808.7 mAh g?1 based on Fe3S4@S and a normalized discharge capacity of 1040.5 mAh g?1 for element S at 100 mA g?1 for 30 cycles at room temperature. Moreover, the battery also exhibits excellent cycling stability with a reversible capacity of 410 mAh g?1 at 500 mA g?1 for 50 cycles, and superior rate capability with capacities of 952.4, 796.7, 513.7, and 445.6 mAh g?1 at 50, 100, 200, and 500 mA g?1, respectively. This facile strategy for sulfur‐based composite cathode is attractive for achieving room‐temperature sodium–sulfur batteries with superior electrochemical performance.  相似文献   

14.
Sodium‐ion batteries (SIBs) have gained tremendous interest for grid scale energy storage system and power energy batteries. However, the current researches of anode for SIBs still face the critical issues of low areal capacity, limited cycle life, and low initial coulombic efficiency for practical application perspective. To solve this issue, a kind of hierarchical 3D carbon‐networks/Fe7S8/graphene (CFG) is designed and synthesized as freestanding anode, which is constructed with Fe7S8 microparticles well‐welded on 3D‐crosslinked carbon‐networks and embedded in highly conductive graphene film, via a facile and scalable synthetic method. The as‐prepared freestanding electrode CFG represents high areal capacity (2.12 mAh cm?2 at 0.25 mA cm?2) and excellent cycle stability of 5000 cycles (0.0095% capacity decay per cycle). The assembled all‐flexible sodium‐ion battery delivers remarkable performance (high areal capacity of 1.42 mAh cm?2 at 0.3 mA cm?2 and superior energy density of 144 Wh kg?1), which are very close to the requirement of practical application. This work not only enlightens the material design and electrode engineering, but also provides a new kind of freestanding high energy density anode with great potential application prospective for SIBs.  相似文献   

15.
Although graphite materials have been applied as commercial anodes in lithium‐ion batteries (LIBs), there still remain abundant spaces in the development of carbon‐based anode materials for sodium‐ion batteries (SIBs). Herein, an electrospinning route is reported to fabricate nitrogen‐doped carbon nanofibers with interweaved nanochannels (NCNFs‐IWNC) that contain robust interconnected 1D porous channels, produced by removal of a Te nanowire template that is coelectrospun within carbon nanofibers during the electrospinning process. The NCNFs‐IWNC features favorable properties, including a conductive 1D interconnected porous structure, a large specific surface area, expanded interlayer graphite‐like spacing, enriched N‐doped defects and active sites, toward rapid access and transport of electrolyte and electron/sodium ions. Systematic electrochemical studies indicate that the NCNFs‐IWNC exhibits an impressively high rate capability, delivering a capacity of 148 mA h g?1 at current density of as high as 10 A g?1, and has an attractively stable performance over 5000 cycles. The practical application of the as‐designed NCNFs‐IWNC for a full SIBs cell is further verified by coupling the NCNFs‐IWNC anode with a FeFe(CN)6 cathode, which displays a desirable cycle performance, maintaining acapacity of 97 mA h g?1 over 100 cycles.  相似文献   

16.
The intercalation of potassium ions into graphite is demonstrated to be feasible, while the electrochemical performance of potassium‐ion batteries (KIBs) remains unsatisfying. More effort is needed to improve the specific capacity while maintaining a superior rate capability. As an attempt, nitrogen/oxygen dual‐doped hierarchical porous hard carbon (NOHPHC) is introduced as the anode in KIBs by carbonizing and acidizing the NH2‐MIL‐101(Al) precursor. Specifically, the NOHPHC electrode delivers high reversible capacities of 365 and 118 mA h g?1 at 25 and 3000 mA g?1, respectively. The capacity retention reaches 69.5% at 1050 mA g?1 for 1100 cycles. The reasons for the enhanced electrochemical performance, such as the high capacity, good cycling stability, and superior rate capability, are analyzed qualitatively and quantitatively. Quantitative analysis reveals that mixed mechanisms, including capacitance and diffusion, account for the K‐ion storage, in which the capacitance plays a more important role. Specifically, the enhanced interlayer spacing (0.39 nm) enables the intercalation of large K ions, while the high specific surface area of ≈1030 m2 g?1 and the dual‐heteroatom doping (N and O) are conducive to the reversible adsorption of K ions.  相似文献   

17.
Development of effective oxygen evolution reaction (OER) electrocatalysts has been intensively studied to improve water splitting efficiency and cost effectiveness in the last ten years. However, it is a big challenge to obtain highly efficient and durable OER electrocatalysts with overpotentials below 200 mV at 10 mA cm?2 despite the efforts made to date. In this work, the successful synthesis of supersmall α‐Ni(OH)2 is reported through electro‐oxidation of NiSe2 loaded onto carbon nanoarrays. The obtained α‐Ni(OH)2 shows excellent activity and long‐term stability for OER, with an overpotential of only 190 mV at the current density of 10 mA cm?2, which represents a highly efficient OER electrocatalyst. The excellent activity could be ascribed to the large electrochemical surface area provided by the carbon nanoarray, as well as the supersmall size (≈10 nm) of α‐Ni(OH)2 which possess a large number of active sites for the reaction. In addition, the phase evolution of α‐Ni(OH)2 from NiSe2 during the electro‐oxidation process was monitored with in situ X‐ray absorption fine structure (XAFS) analysis.  相似文献   

18.
SnS2 has been widely studied as an anode material for sodium‐ion batteries (SIBs) based on the high theoretical capacity and layered structure. Unfortunately, rapid capacity decay associated with volume variation during cycling limits practical application. Herein, SnS2/Co3S4 hollow nanocubes anchored on S‐doped graphene are synthesized for the first time via coprecipitation and hydrothermal methods. When applied as the anode for SIBs, the sample delivers a distinguished charge specific capacity of 1141.8 mAh g?1 and there is no significant capacity decay (0.1 A g?1 for 50 cycles). When the rate is increased to 0.5 A g?1, it presents 845.7 mAh g?1 after cycling 100 times. Furthermore, the composite also exhibits an ultrafast sodium storage capability where 392.9 mAh g?1 can be obtained at 10 A g?1 and the charging time is less than 3 min. The outstanding electrochemical properties can be ascribed to the enhancement of conductivity for the addition of S‐doped graphene and the existence of p–n junctions in the SnS2/Co3S4 heterostructure. Moreover, the presence of mesopores between nanosheets can alleviate volume expansion during cycling as well as being beneficial for the migration of Na+.  相似文献   

19.
Rational synthesis of flexible electrodes is crucial to rapid growth of functional materials for energy‐storage systems. Herein, a controllable fabrication is reported for the self‐supported structure of CuCo2O4 nanodots (≈3 nm) delicately inserted into N‐doped carbon nanofibers (named as 3‐CCO@C); this composite is first used as binder‐free anode for sodium‐ion batteries (SIBs). Benefiting from the synergetic effect of ultrasmall CuCo2O4 nanoparticles and a tailored N‐doped carbon matrix, the 3‐CCO@C composite exhibits high cycling stability (capacity of 314 mA h g?1 at 1000 mA g?1 after 1000 cycles) and high rate capability (296 mA h g?1, even at 5000 mA g?1). Significantly, the Na storage mechanism is systematically explored, demonstrating that the irreversible reaction of CuCo2O4, which decomposes to Cu and Co, happens in the first discharge process, and then a reversible reaction between metallic Cu/Co and CuO/Co3O4 occurrs during the following cycles. This result is conducive to a mechanistic study of highly promising bimetallic‐oxide anodes for rechargeable SIBs.  相似文献   

20.
1T phase MoS2 possesses higher conductivity than the 2H phase, which is a key parameter of electrochemical performance for lithium ion batteries (LIBs). Herein, a 1T‐MoS2/C hybrid is successfully synthesized through facile hydrothermal method with a proper glucose additive. The synthesized hybrid material is composed of smaller and fewer‐layer 1T‐MoS2 nanosheets covered by thin carbon layers with an enlarged interlayer spacing of 0.94 nm. When it is used as an anode material for LIBs, the enlarged interlayer spacing facilitates rapid intercalating and deintercalating of lithium ions and accommodates volume change during cycling. The high intrinsic conductivity of 1T‐MoS2 also contributes to a faster transfer of lithium ions and electrons. Moreover, much smaller and fewer‐layer nanosheets can shorten the diffusion path of lithium ions and accelerate reaction kinetics, leading to an improved electrochemical performance. It delivers a high initial capacity of 920.6 mAh g?1 at 1 A g?1 and the capacity can maintain 870 mAh g?1 even after 300 cycles, showing a superior cycling stability. The electrode presents a high rate performance as well with a reversible capacity of 600 mAh g?1 at 10 A g?1. These results show that the 1T‐MoS2/C hybrid shows potential for use in high‐performance lithium‐ion batteries.  相似文献   

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