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1.
To develop high‐performance anode materials of lithium‐ion batteries (LIBs) instead of commercial graphite for practical applications, herein, a layer of silicon has been well‐anchored onto a 3D graphene/carbon nanotube (CNT) aerogels (CAs) framework with face‐to‐face contact and balanced open void by a simple chemical vapor deposition strategy. The engineered contact interface between CAs and Si creates high‐efficiency channels for the rapid electrons and lithium ions transport, and meanwhile, the balanced open‐void allows the free expansion of Si during cycling while maintaining high structural integrity due to the robust mechanical strength of 3D CAs framework. As a consequence, the as‐synthesized Si/CAs nanohybrids are highly stable anode materials for LIBs with a high reversible discharge capacity (1498 mAh g?1 at 200 mA g?1) and excellent rate capability (462 mAh g?1 at 10 000 mA g?1), which is much better than Si/graphene‐CNTs‐mixture (51 mAh g?1 at 10 000 mA g?1). More significantly, it is found that the Si/CAs nanohybrids display no obvious capacity decline even after 2000 cycles at a high current density of 10 000 mA g?1. The present Si/CAs nanohybrids are one of the most stable Si‐based anode materials ever reported for LIBs to date.  相似文献   

2.
Germanium is considered as a promising anode material because of its comparable lithium and sodium storage capability, but it usually exhibits poor cycling stability due to the large volume variation during lithium or sodium uptake and release processes. In this paper, germanium@graphene nanofibers are first obtained through electrospinning followed by calcination. Then atomic layer deposition is used to fabricate germanium@graphene@TiO2 core–shell nanofibers (Ge@G@TiO2 NFs) as anode materials for lithium and sodium ion batteries (LIBs and SIBs). Graphene and TiO2 can double protect the germanium nanofibers in charge and discharge processes. The Ge@G@TiO2 NFs composite as an anode material is versatile and exhibits enhanced electrochemical performance for LIBs and SIBs. The capacity of the Ge@G@TiO2 NFs composite can be maintained at 1050 mA h g?1 (100th cycle) and 182 mA h g?1 (250th cycle) for LIBs and SIBs, respectively, at a current density of 100 mA g?1, showing high capacity and good cycling stability (much better than that of Ge nanofibers or Ge@G nanofibers).  相似文献   

3.
Poly(thiophene) as a kind of n‐doped conjugated polymer with reversible redox behavior can be employed as anode material for lithium‐ion batteries (LIBs). However, the low redox activity and poor rate performance for the poly(thiophene)‐based anodes limit its further development. Herein, a structure‐design strategy is reported for thiophene‐containing conjugated microporous polymers (CMPs) with extraordinary electrochemical performance as anode materials in LIBs. The comparative study on the electrochemical performance of the structure‐designed thiophene‐containing CMPs reveals that high redox‐active thiophene content, highly crosslinked porous structure, and improved surface area play significant roles for enhancing electrochemical performances of the resulting CMPs. The all‐thiophene‐based polymer of poly(3,3′‐bithiophene) with crosslinked structure and a high surface area of 696 m2 g?1 exhibits a discharge capacity of as high as 1215 mAh g?1 at 45 mA g?1, excellent rate capability, and outstanding cycling stability with a capacity retention of 663 mAh g?1 at 500 mA g?1 after 1000 cycles. The structure–performance relationships revealed in this work offer a fundamental understanding in the rational design of CMPs anode materials for high performance LIBs.  相似文献   

4.
Graphdiyne (GDY), an emerging type of carbon allotropes, possesses fascinating electrical, chemical, and mechanical properties to readily spark energy applications in the realm of Li‐ion and Na‐ion batteries. Nevertheless, rational design of GDY architectures targeting advanced K‐ion storage has rarely been reported to date. Herein, the first example of synthesizing GDY frameworks in a scalable fashion to realize superb potassium storage for high‐performance K‐ion battery (KIB) anodes is showcased. To begin with, first principles calculations provide theoretical guidances for analyzing the intrinsic potassium storage capability of GDY. Meanwhile, the specific capacity is predicted to be as high as 620 mAh g?1, which is considerably augmented as compared with graphite (278 mAh g?1). Experimental tests then reveal that prepared GDY framework indeed harvests excellent electrochemical performance as a KIB anode, achieving high specific capacity (≈505 mAh g?1 at 50 mA g?1), outstanding rate performance (150 mAh g?1 at 5000 mA g?1) and favorable cycling stability (a high capacity retention of over 90% after 2000 cycles at 1000 mA g?1). Furthermore, kinetic analysis reveals that capacitive effect mainly accounts for the K‐ion storage, with operando Raman spectroscopy/ex situ X‐ray photoelectron spectroscopy identifying good electrochemical reversibility of GDY.  相似文献   

5.
Potassium‐ion batteries have been regarded as the potential alternatives to lithium‐ion batteries (LIBs) due to the low cost, earth abundance, and low potential of K (?2.936 vs standard hydrogen electrode (SHE)). However, the lack of low‐cost cathodes with high energy density and long cycle life always limits its application. In this work, high‐energy layered P2‐type hierarchical K0.65Fe0.5Mn0.5O2 (P2‐KFMO) microspheres, assembled by the primary nanoparticles, are fabricated via a modified solvent‐thermal method. Benefiting from the unique microspheres with primary nanoparticles, the K+ intercalation/deintercalation kinetics of P2‐KFMO is greatly enhanced with a stabilized cathodic electrolyte interphase on the cathode. The P2‐KFMO microsphere presents a highly reversible potassium storage capacity of 151 mAh g?1 at 20 mA g?1, fast rate capability of 103 mAh g?1 at 100 mA g?1, and long cycling stability with 78% capacity retention after 350 cycles. A full cell with P2‐KFMO microspheres as cathode and hard carbon as anode is constructed, which exhibits long‐term cycling stability (>80% of retention after 100 cycles). The present high‐performance P2‐KFMO microsphere cathode synthesized using earth‐abundant elements provides a new cost‐effective alternative to LIBs for large‐scale energy storage.  相似文献   

6.
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   

7.
This study reports the design and fabrication of ultrathin MoS2 nanosheets@metal organic framework‐derived N‐doped carbon nanowall array hybrids on flexible carbon cloth (CC@CN@MoS2) as a free‐standing anode for high‐performance sodium ion batteries. When evaluated as an anode for sodium ion battery, the as‐fabricated CC@CN@MoS2 electrode exhibits a high capacity (653.9 mA h g?1 of the second cycle and 619.2 mA h g?1 after 100 cycles at 200 mA g?1), excellent rate capability, and long cycling life stability (265 mA h g?1 at 1 A g?1 after 1000 cycles). The excellent electrochemical performance can be attributed to the unique 2D hybrid structures, in which the ultrathin MoS2 nanosheets with expanded interlayers can provide shortened ion diffusion paths and favorable Na+ insertion/extraction space, and the porous N‐doped carbon nanowall arrays on flexible carbon cloth are able to improve the conductivity and maintain the structural integrity. Moreover, the N‐doping‐induced defects also make them favorable for the effective storage of sodium ions, which enables the enhanced capacity and rate performance of MoS2.  相似文献   

8.
In this paper, a highly ordered three‐dimensional Co3O4@MnO2 hierarchical porous nanoneedle array on nickel foam is fabricated by a facile, stepwise hydrothermal approach. The morphologies evolution of Co3O4 and Co3O4@MnO2 nanostructures upon reaction times and growth temperature are investigated in detail. Moreover, the as‐prepared Co3O4@MnO2 hierarchical structures are investigated as anodes for both supercapacitors and Li‐ion batteries. When used for supercapacitors, excellent electrochemical performances such as high specific capacitances of 932.8 F g?1 at a scan rate of 10 mV s?1 and 1693.2 F g?1 at a current density of 1 A g?1 as well as long‐term cycling stability and high energy density (66.2 W h kg?1 at a power density of 0.25 kW kg?1), which are better than that of the individual component of Co3O4 nanoneedles and MnO2 nanosheets, are obtained. The Co3O4@MnO2 NAs are also tested as anode material for LIBs for the first time, which presents an improved performance with high reversible capacity of 1060 mA h g?1 at a rate of 120 mA g?1, good cycling stability, and rate capability.  相似文献   

9.
Metal oxide‐based nanomaterials are widely studied because of their high‐energy densities as anode materials in lithium‐ion batteries. However, the fast capacity degradation resulting from the large volume expansion upon lithiation hinders their practical application. In this work, the preparation of walnut‐like multicore–shell MnO encapsulated nitrogen‐rich carbon nanocapsules (MnO@NC) is reported via a facile and eco‐friendly process for long‐cycling Li‐ion batteries. In this hybrid structure, MnO nanoparticles are uniformly dispersed inside carbon nanoshells, which can simultaneously act as a conductive framework and also a protective buffer layer to restrain the volume variation. The MnO@NC nanocapsules show remarkable electrochemical performances for lithium‐ion batteries, exhibiting high reversible capability (762 mAh g?1 at 100 mA g?1) and stable cycling life (624 mAh g?1 after 1000 cycles at 1000 mA g?1). In addition, the soft‐packed full batteries based on MnO@NC nanocapsules anodes and commercial LiFePO4 cathodes present good flexibility and cycling stability.  相似文献   

10.
Carbon‐based materials are promising anodes for potassium‐ion batteries (PIBs). However, due to the significant volume expansion and structural instability, it is still a challenge to achieve a high capacity, high rate and long cycle life for carbonaceous anodes. Herein, oxygen/fluorine dual‐doped porous carbon nanopolyhedra (OFPCN) is reported for the first time as a novel anode for PIBs, which exhibits a high reversible capacity of 481 mA h g?1 at 0.05 A g?1 and excellent performance of 218 mA h g?1 after 2000 cycles at 1 A g?1 with 92% capacity retention. Even after 5000 robust cycles at 10 A g?1 with charging/discharging time of around 40 s, an unprecedented capacity of 111 mA h g?1 is still maintained. Such ultrafast potassium storage and unprecedented cycling stability have been seldom reported in PIBs. Quantitative kinetics analysis reveals that both diffusion and capacitance processes are involved in the potassium storage mechanism. Density functional theory calculations demonstrate that the O/F dual‐doped porous carbon promotes the K‐adsorption ability and can absorb multiple K atoms with slight structural distortion, which accounts for the high specific capacity, outstanding rate capability, and excellent cycling stability of the OFPCN anode.  相似文献   

11.
Sodium‐ion batteries (SIBs) are considered as promising alternatives to lithium‐ion batteries (LIBs) for energy storage due to the abundance of sodium, especially for grid distribution systems. The practical implementation of SIBs, however, is severely hindered by their low energy density and poor cycling stability due to the poor electrochemical performance of the existing electrodes. Here, to achieve high‐capacity and durable sodium storage with good rate capability, hierarchical hollow NiS spheres with porous shells composed of nanoparticles are designed and synthesized by tuning the reaction parameters. The formation mechanism of this unique structure is systematically investigated, which is clearly revealed to be Ostwald ripening mechanism on the basis of the time‐dependent morphology evolution. The hierarchical hollow structure provides sufficient electrode/electrolyte contact, shortened Na+ diffusion pathways, and high strain‐tolerance capability. The hollow NiS spheres deliver high reversible capacity (683.8 mAh g?1 at 0.1 A g?1), excellent rate capability (337.4 mAh g?1 at 5 A g?1), and good cycling stability (499.9 mAh g?1 with 73% retention after 50 cycles at 0.1 A g?1).  相似文献   

12.
Binder plays a key role in maintaining the mechanical integrity of electrodes in lithium‐ion batteries. However, the existing binders typically exhibit poor stretchability or low conductivity at large strains, which are not suitable for high‐capacity silicon (Si)‐based anodes undergoing severe volume changes during cycling. Herein, a novel stretchable conductive glue (CG) polymer that possesses inherent high conductivity, excellent stretchablity, and ductility is designed for high‐performance Si anodes. The CG can be stretched up to 400% in volume without conductivity loss and mechanical fracture and thus can accommodate the large volume change of Si nanoparticles to maintain the electrode integrity and stabilize solid electrolyte interface growth during cycling while retaining the high conductivity, even with a high Si mass loading of 90%. The Si‐CG anode has a large reversible capacity of 1500 mA h g?1 for over 700 cycles at 840 mA g?1 with a large initial Coulombic efficiency of 80% and high rate capability of 737 mA h g?1 at 8400 mA g?1. Moreover, the Si‐CG anode demonstrates the highest achieved areal capacity of 5.13 mA h cm?2 at a high mass loading of 2 mg cm?2. The highly stretchable CG provides a new perspective for designing next‐generation high‐capacity and high‐power batteries.  相似文献   

13.
With the increasing demand for low cost, long lifetime, high energy density storage systems, an extensive amount of effort has recently been focused on the development of sodium‐ion batteries (SIBs), and a variety of cathode materials have been discovered. However, looking for the most suitable anode material for practical application is a major challenge for SIBs. Herein, a high capacity sulfur‐doped black phosphorus‐TiO2 (TiO2‐BP‐S) anode material for SIBs is first synthesized by a feasible and large‐scale high‐energy ball‐milling approach, and its stability in air exposure is investigated through X‐ray photoelectron spectroscopy. The morphology of TiO2‐BP‐S is characterized using transmission electron microscopy, indicating that the TiO2 nanoparticles produce P? Ti bonds with BP. The TiO2‐BP‐S composite with P? S and P? Ti bonds exhibits excellent stability in air and the superior electrochemical performance. For example, the discharge specific capacity is up to 490 mA h g?1 after 100 cycles at 50 mA g?1, and it remains at 290 mA h g?1 after 600 cycles at 500 mA g?1. Meanwhile, the scientific insight that the formation of stable P? S and P? Ti bonds can provide a guide for the practical large‐scale application of SIBs in other titanium base and black phosphorus materials is looked forward.  相似文献   

14.
Although transition metal oxide electrodes have large lithium storage capacity, they often suffer from low rate capability, poor cycling stability, and unclear additional capacity. In this paper, CoO nanowire clusters (NWCs) composed of ultra‐small nanoparticles (≈10 nm) directly grown on copper current collector are fabricated and evaluated as an anode of binder‐free lithium‐ion batteries, which exhibits an ultra‐high capacity and good rate capability. At a rate of 1 C (716 mA g?1), a reversible capacity as high as 1516.2 mA h g?1 is obtained, and even when the current density is increased to 5 C, a capacity of 1330.5 mA h g?1 could still be maintained. Importantly, the origins of the additional capacity are investigated in detail, with the results suggesting that pseudocapacitive charge and the higher‐oxidation‐state products are jointly responsible for the large additional capacity. In addition, nanoreactors for the CoO nanowires are fabricated by coating the CoO nanowires with amorphous silica shells. This hierarchical core–shell CoO@SiO2 NWC electrode achieves an improved cycling stability without degrading the high capacity and good rate capability compared to the uncoated CoO NWCs electrode.  相似文献   

15.
A novel synergistic TiO2‐MoO3 (TO‐MO) core–shell nanowire array anode has been fabricated via a facile hydrothermal method followed by a subsequent controllable electrodeposition process. The nano‐MoO3 shell provides large specific capacity as well as good electrical conductivity for fast charge transfer, while the highly electrochemically stable TiO2 nanowire core (negligible volume change during Li insertion/desertion) remedies the cycling instability of MoO3 shell and its array further provides a 3D scaffold for large amount electrodeposition of MoO3. In combination of the unique electrochemical attributes of nanostructure arrays, the optimized TO‐MO hybrid anode (mass ratio: ca. 1:1) simultaneously exhibits high gravimetric capacity (ca. 670 mAh g?1; approaching the hybrid's theoretical value), excellent cyclability (>200 cycles) and good rate capability (up to 2000 mA g?1). The areal capacity is also as high as 3.986 mAh cm?2, comparable to that of typical commercial LIBs. Furthermore, the hybrid anode was assembled for the first time with commercial LiCoO2 cathode into a Li ion full cell, which shows outstanding performance with maximum power density of 1086 W kgtotal ?1 (based on the total mass of the TO‐MO and LiCoO2) and excellent energy density (285 Wh kgtotal ?1) that is higher than many previously reported metal oxide anode‐based Li full cells.  相似文献   

16.
Graphene encapsulated nanosheet‐assembled ZnO‐Mn‐C hierarchical hollow microspheres are produced through a simple yet effective dual electrostatic assembly strategy, followed by a heating treatment in inert atmosphere. The modification of graphene sheets, metal Mn, and in situ carbon leads to form 3D interconnected conductive framework as electron highways. The hollow structure and the open configuration of hierarchical microspheres guarantee good structural stability and rapid ionic transport. More importantly, according to the density functional theory calculations, the oxygen vacancies in the hierarchical microspheres would cause an imbalanced charge distribution and thus the formation of local in‐plane electric fields around oxygen vacancy sites, which is beneficial for the ionic/electronic transport during cycling. Due to this multiscale coordinated design, the as‐fabricated graphene encapsulated nanosheet‐assembled ZnO‐Mn‐C hierarchical hollow microspheres demonstrate good lithium storage properties in terms of high reversible capacity (1094 mA h g?1 at 100 mA g?1), outstanding high‐rate long‐term cycling stability (843 mA h g?1 after 1000 cycles at 2000 mA g?1), and remarkable rate capability (422 mA h g?1 after total 1600 cycles at 5000 mA g?1).  相似文献   

17.
GaN is demonstrated to be an ideal anode for Li‐ion batteries (LIBs) for the first time. Amorphous GaN@Cu nanorods (a‐GaN@Cu) freestanding electrode is designed via a low‐temperature pulsed laser deposition method, which exhibits prominent rate capability and untralong lifespan as an anode for LIBs. With porous interconnected metal nanorods substrate to improve the structure integrity and electronic conductivity, the a‐GaN@Cu electrode delivers a capacity recovery of 980 mAh g?1 after 150 cycles from 0.25 to 6.25 A g?1 and a high discharge capacity of 509 mAh g?1 after 3000 cycles at 10.0 A g?1. The lithium storage in the a‐GaN is also systematically studied, which suggests a redox reaction mechanism.  相似文献   

18.
Sodium‐ion batteries are attracting increasing interests as a promising alternative to lithium‐ion batteries due to the abundant resource and low cost of sodium. Despite phosphorus (P) has extremely high theoretical capacity of 2595 mAh g?1, its wide application for sodium‐ion battery is highly hampered by its fast capacity fading and low Coulombic efficiency as a result of large volume change upon cycling. Herein, a robust phosphorus anode with long cycle life for sodium‐ion battery via hybridization with functional conductive polymer is presented. To this end, the polyacrylonitrile is first dehydrogenated by sulfur via a facile thermal treatment, forming a conductive main chain embedded with C–S–S moieties. This functional conductive polymer enables the formation of P? S bonds between phosphorus and functional conductive matrix, leading to a robust electrode that can accommodate the large volume change upon substantial volume change in cycling. Consequently, this hybrid anode delivers a high capacity of ≈1300 mAh g?1 at a current density of 520 mA g?1 with high Coulombic efficiency (>99%) and good cycling performance (91% capacity retention after 100 cycles).  相似文献   

19.
High‐capacity lithium‐ion battery anode materials, such as transition metal oxides, Sn and Si, suffer from large volume expansion during lithiation, which causes capacity decay. Introducing sufficient void space to accommodate the volume change is essential to achieve prolonged cycling stability. However, excessive void space may significantly compromise the volumetric energy density. Herein, a method to control the void size in iron oxide@carbon (FeOx@C) yolk–shell structures is developed and the relationship between the void space and electrochemical performance is demonstrated. With an optimized void size, the FeOx@C yolk–shell structure exhibits the best cycling performance. A high reversible capacity of ≈810 mA h g?1 is obtained at 0.2 C, maintaining 790 mA h g?1 after 100 cycles. This contrasts with FeOx@C materials having either smaller or larger void sizes, in which significant capacity fading is observed during cycling. This contribution provides an effective approach to alleviate the volume expansion problem, which can be generally applied to other anode materials to improve their performance in LIBs.  相似文献   

20.
Potassium‐ion batteries (KIBs) are new‐concept of low‐cost secondary batteries, but the sluggish kinetics and huge volume expansion during cycling, both rooted in the size of large K ions, lead to poor electrochemical behavior. Here, a bamboo‐like MoS2/N‐doped‐C hollow tubes are presented with an expanded interlayer distance of 10 Å as a high‐capacity and stable anode material for KIBs. The bamboo‐like structure provides gaps along axial direction in addition to inner cylinder hollow space to mitigate the strains in both radial and vertical directions that ultimately leads to a high structural integrity for stable long‐term cycling. Apart from being a constituent of the interstratified structure the N‐doped‐C layers weave a cage to hold the potassiation products (polysulfide and the Mo nanoparticles) together, thereby effectively hindering the continuing growth of solid electrolyte interphase in the interior of particles. The density functional theory calculations prove that the MoS2/N‐doped‐C atomic interface can provide an additional attraction toward potassium ion. As a result, it delivers a high capacity at a low current density (330 mAh g?1 at 50 mA g?1 after 50 cycles) and a high‐capacity retention at a high current density (151 mAh g?1 at 500 mA g?1 after 1000 cycles).  相似文献   

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