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1.
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   

2.
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   

3.
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   

4.
Although abundant germanium (Ge)‐based anode materials have been explored to obtain high specific capacity, high rate performance, and long charge/discharge lifespans for lithium‐ion batteries (LIBs), their performances are still far from satisfactory due to the intrinsic defects of Ge and the relatively intricate anode structure. To work out these issues, a 3D ordered porous N‐doped carbon framework with Ge quantum dots uniformly embedded (3DOP Ge@N? C) as a binder‐free anode for LIBs via a facile polystyrene colloidal nanospheres template‐confined strategy is proposed. This unique structure not only facilitates Li‐ion diffusion and electron transport that can guarantee rapid de/alloying reaction, but also alleviates the huge volume changes during reactions and improves cycling stability. Notably, the resulting anode delivers a high specific reversible capacity (≈1160 mA h g?1 at 1 A g?1), superior rate properties (exceeding 500 mA h g?1 at 40 A g?1), and excellent cycling stability (over 90% capacity retention after 1200 cycles even at 5 A g?1). Furthermore, both the 3DOP Ge@N? C anode with high areal mass loading (up to 8 mg cm?2) and the full cell coupled with LiFePO4 cathode display high capacity and cycling stability, further indicative of the favorable real‐life application prospects for high‐energy LIBs.  相似文献   

5.
As an anode material for lithium‐ion batteries, titanium dioxide (TiO2) shows good gravimetric performance (336 mAh g?1 for LiTiO2) and excellent cyclability. To address the poor rate behavior, slow lithium‐ion (Li+) diffusion, and high irreversible capacity decay, TiO2 nanomaterials with tuned phase compositions and morphologies are being investigated. Here, a promising material is prepared that comprises a mesoporous “yolk–shell” spherical morphology in which the core is anatase TiO2 and the shell is TiO2(B). The preparation employs a NaCl‐assisted solvothermal process and the electrochemical results indicate that the mesoporous yolk–shell microspheres have high specific reversible capacity at moderate current (330.0 mAh g?1 at C/5), excellent rate performance (181.8 mAh g?1 at 40C), and impressive cyclability (98% capacity retention after 500 cycles). The superior properties are attributed to the TiO2(B) nanosheet shell, which provides additional active area to stabilize the pseudocapacity. In addition, the open mesoporous morphology improves diffusion of electrolyte throughout the electrode, thereby contributing directly to greatly improved rate capacity.  相似文献   

6.
A unique watermelon‐like structured SiOx–TiO2@C nanocomposite is synthesized by a scalable sol–gel method combined with carbon coating process. Ultrafine TiO2 nanocrystals are uniformly embedded inside SiOx particles, forming SiOx–TiO2 dual‐phase cores, which are coated with outer carbon shells. The incorporation of TiO2 component can effectively enhance the electronic and lithium ionic conductivities inside the SiOx particles, release the structure stress caused by alloying/dealloying of Si component and maximize the capacity utilization by modifying the Si–O bond feature and decreasing the O/Si ratio (x‐value). The synergetic combination of these advantages enables the synthesized SiOx–TiO2@C nanocomposite to have excellent electrochemical performances, including high specific capacity, excellent rate capability, and stable long‐term cycleability. A stable specific capacity of ≈910 mAh g?1 is achieved after 200 cycles at the current density of 0.1 A g?1 and ≈700 mAh g?1 at 1 A g?1 for over 600 cycles. These results suggest a great promise of the proposed particle architecture, which may have potential applications in the improvement of various energy storage materials.  相似文献   

7.
The fabrication of mesoporous black titanium dioxide (TiO2?x ) with a chiral nematic organization of core–shell nanorods is reported. Chiral templating of TiO2 nanoparticles onto gelatin‐functionalized cellulose nanocrystals (CNCs) followed by calcination yields carbonized TiO2/CNC helical materials that recover white TiO2 replicas after carbon removal. The hydrothermal surface reduction of the traditional white TiO2 by ascorbic acid affords freestanding chiral nematic black TiO2?x. The black TiO2?x is a visible light active semiconducting mesoporous structure constructed by chiral nematic crystalline–amorphous TiO2 core–shell nanorods. The chiral black TiO2?x nanoparticles supported on mesoporous nanocarbon networks are evaluated as lithium‐ion battery anode electrodes. Beyond the current efforts, these black TiO2?x materials and their composites may be useful in the fields of energy storage and catalysis.  相似文献   

8.
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   

9.
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   

10.
Metal sulfides are an important class of functional materials possessing exceptional electrochemical performance and thus hold great promise for rechargeable secondary batteries. In this work, we deposited gallium sulfide (GaSx, x = 1.2) thin films by atomic layer deposition (ALD) onto single‐walled carbon nanotube (SWCNT) powders. The ALD GaSx was performed at 150 °C, and produced uniform and conformal amorphous films. The resulting core‐shell, nanostructured SWCNT‐GaSx composite exhibited excellent electrochemical performance as an anode material for lithium‐ion batteries (LIBs), yielding a stable capacity of ≈575 mA g–1 at a current density of 120 mA g–1 in the voltage window of 0.01–2 V, and an exceptional columbic efficiency of >99.7%. The GaSx component of the composite produced a specific capacity of 766 mA g–1, a value two times that of conventional graphite anodes. We attribute the excellent electrochemical performance of the composite to four synergistic effects: 1) the uniform and conformal ALD GaSx coating offers short electronic and Li‐ion pathways during cycling; 2) the amorphous structure of the ALD GaSx accommodates stress during lithiation‐delithiation processes; 3) the mechanically robust SWCNT framework also accommodates stress from cycling; 4) the SWCNT matrix provides a continuous, high conductivity network.  相似文献   

11.
Fe3O4 nanocrystals confined in mesocellular carbon foam (MSU‐F‐C) are synthesized by a “ host–guest ” approach and tested as an anode material for lithium‐ion batteries (LIBs). Briefly, an iron oxide precursor, Fe(NO3)3·9H2O, is impregnated in MSU‐F‐C having uniform cellular pores ~30 nm in dia­meter, followed by heat‐treatment at 400 °C for 4 h under Ar. Magnetite Fe3O4 nanocrystals with sizes between 13–27 nm are then successfully fabricated inside the pores of the MSU‐F‐C, as confirmed by transmission electron microscopy (TEM), dark‐field scanning transmission electron microscopy (STEM), energy dispersive X‐ray spectroscopy (EDS), X‐ray diffraction (XRD), and nitrogen sorption isotherms. The presence of the carbon most likely allows for reduction of some of the Fe3+ ions to Fe2+ ions via a carbothermoreduction process. A Fe3O4/MSU‐F‐C nanocomposite with 45 wt% Fe3O4 exhibited a first charge capacity of 1007 mA h g?1 (Li+ extraction) at 0.1 A g?1 (~0.1 C rate) with 111% capacity retention at the 150th cycle, and retained 37% capacity at 7 A g?1 (~7 C rate). Because the three dimensionally interconnected open pores are larger than the average nanosized Fe3O4 particles, the large volume expansion of Fe3O4 upon Li‐insertion is easily accommodated inside the pores, resulting in excellent electrochemical performance as a LIB anode. Furthermore, when an ultrathin Al2O3 layer (<4 Å) was deposited on the composite anode using atomic layer deposition (ALD), the durability, rate capability and undesirable side reactions are significantly improved.  相似文献   

12.
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   

13.
The construction of bifunctional electrode materials for hydrogen evolution reaction (HER) and lithium‐ion batteries (LIBs) has been a hot topic of research. Herein, metal–organic frameworks (MOFs) derived micro‐/nanostructured Ni2P/Ni hybrids with a porous carbon coating (denoted as Ni2P/Ni@C) are prepared using a feasible pyrolysis–phosphidation strategy. On the one hand, the optimal Ni2P/Ni@C catalyst exhibits superior HER performance with a low overpotential of 149 mV versus a reversible hydrogen electrode (RHE) at 10 mA cm?2 and excellent durability. The density functional theory computations verify that the strong synergistic effect between Ni2P and Ni could optimize the electronic structure, thus rendering the enhanced electrocatalytic performance. On the other hand, the Ni2P/Ni@C electrode displays a reversible capacity of 597 mAh g?1 after 1000 cycles at 1000 mA g?1 and improved rate capability as an anode for LIBs, owing to the well‐organized micro‐/nanostructure and conductive Ni core. In addition, the electrochemical reaction mechanism of the Ni2P/Ni@C electrode upon lithiation/delithiation is investigated in detail via ex situ X‐ray powder diffraction and X‐ray photoelectron spectroscopy methods. It is expected that the facile and controllable approach can be extended to fabricate other MOF‐based metal phosphides/metal hybrids for electrochemical energy storage and conversion systems.  相似文献   

14.
Sodium‐ion hybrid capacitors (SIHCs) can potentially combine the virtues of high‐energy density of batteries and high‐power output as well as long cycle life of capacitors in one device. The key point of constructing a high‐performance SIHC is to couple appropriate anode and cathode materials, which can well match in capacity and kinetics behavior simultaneously. In this work, a novel SIHC, coupling a titanium dioxide/carbon nanocomposite (TiO2/C) anode with a 3D nanoporous carbon cathode, which are both prepared from metal–organic frameworks (MOFs, MIL‐125 (Ti) and ZIF‐8, respectively), is designed and fabricated. The robust architecture and extrinsic pseudocapacitance of TiO2/C nanocomposite contribute to the excellent cyclic stability and rate capability in half‐cell. Hierarchical 3D nanoporous carbon displays superior capacity and rate performance. Benefiting from the merits of structures and performances of anode and cathode materials, the as‐built SIHC achieves a high energy density of 142.7 W h kg?1 and a high power output of 25 kW kg?1 within 1–4 V, as well as an outstanding life span of 10 000 cycles with over 90% of the capacity retention. The results make it competitive in high energy and power–required electricity storage applications.  相似文献   

15.
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   

16.
Nonmetallic plasmonic heterostructure TiO2‐mesocrystals/WO3?x‐nanowires (TiO2‐MCs/WO3?x‐NWs) are constructed by coupling mesoporous crystal TiO2 and plasmonic WO3?x through a solvothermal procedure. The continuous photoelectron injection from TiO2 stabilizes the free carrier density and leads to strong surface plasmon resonance (SPR) of WO3?x, resulting in strong light absorption in the visible and near‐infrared region. Photocatalytic hydrogen generation of TiO2‐MCs/WO3?x‐NWs is attributed to plasmonic hot electrons excited on WO3?x‐NWs under visible light irradiation. However, utilization of injected photoelectrons on WO3?x‐NWs has low efficiency for hydrogen generation and a co‐catalyst (Pt) is necessary. TiO2‐MCs/WO3?x‐NWs are used as co‐catalyst free plasmonic photocatalysts for CO2 reduction, which exhibit much higher activity (16.3 µmol g?1 h?1) and selectivity (83%) than TiO2‐MCs (3.5 µmol g?1 h?1, 42%) and WO3?x‐NWs (8.0 µmol g?1 h?1, 64%) for methane generation under UV–vis light irradiation. A photoluminescence study demonstrates the photoelectron injection from TiO2 to WO3?x, and the nonmetallic SPR of WO3?x plays a great role in the highly selective methane generation during CO2 photoreduction.  相似文献   

17.
Developing earth‐abundant, active, and robust electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) remains a vital challenge for efficient conversion of sustainable energy sources. Herein, metal–semiconductor hybrids are reported with metallic nanoalloys on various defective oxide nanowire arrays (Cu/CuOx, Co/CoOx, and CuCo/CuCoOx) as typical Mott–Schottky electrocatalysts. To build the highway of continuous electron transport between metals and semiconductors, nitrogen‐doped carbon (NC) has been implanted on metal–semiconductor nanowire array as core–shell conductive architecture. As expected, NC/CuCo/CuCoOx nanowires arrays, as integrated Mott–Schottky electrocatalysts, present an overpotential of 112 mV at 10 mA cm?2 and a low Tafel slope of 55 mV dec?1 for HER, simultaneously delivering an overpotential of 190 mV at 10 mA cm?2 for OER. Most importantly, NC/CuCo/CuCoOx architectures, as both the anode and the cathode for overall water splitting, exhibit a current density of 10 mA cm?2 at a cell voltage of 1.53 V with excellent stability due to high conductivity, large active surface area, abundant active sites, and the continuous electron transport from prominent synergetic effect among metal, semiconductor, and nitrogen‐doped carbon. This work represents an avenue to design and develop efficient and stable Mott–Schottky bifunctional electrocatalysts for promising energy conversion.  相似文献   

18.
Designed as a high‐capacity, high‐rate, and long‐cycle life anode for sodium‐ion batteries, ultrasmall Sn nanoparticles (≈8 nm) homogeneously embedded in spherical carbon network (denoted as 8‐Sn@C) is prepared using an aerosol spray pyrolysis method. Instrumental analyses show that 8‐Sn@C nanocomposite with 46 wt% Sn and a BET surface area of 150.43 m2 g?1 delivers an initial reversible capacity of ≈493.6 mA h g?1 at the current density of 200 mA g?1, a high‐rate capacity of 349 mA h g?1 even at 4000 mA g?1, and a stable capacity of ≈415 mA h g?1 after 500 cycles at 1000 mA g?1. The remarkable electrochemical performance of 8‐Sn@C is owing to the synergetic effects between the well‐dispersed ultrasmall Sn nanoparticles and the conductive carbon network. This unique structure of very‐fine Sn nanoparticles embedded in the porous carbon network can effectively suppress the volume fluctuation and particle aggregation of tin during prolonged sodiation/desodiation process, thus solving the major problems of pulverization, loss of electrical contact and low utilization rate facing Sn anode.  相似文献   

19.
Maricite NaFePO4 nanodots with minimized sizes (≈1.6 nm) uniformly embedded in porous N‐doped carbon nanofibers (designated as NaFePO4@C) are first prepared by electrospinning for maximized Na‐storage performance. The obtained flexible NaFePO4@C fiber membrane adherent on aluminum foil is directly used as binder‐free cathode for sodium‐ion batteries, revealing that the ultrasmall nanosize effect as well as a high‐potential desodiation process can transform the generally perceived electrochemically inactive maricite NaFePO4 into a highly active amorphous phase; meanwhile, remarkable electrochemical performance in terms of high reversible capacity (145 mA h g?1 at 0.2 C), high rate capability (61 mA h g?1 at 50 C), and unprecedentedly high cyclic stability (≈89% capacity retention over 6300 cycles) is achieved. Furthermore, the soft package Na‐ion full battery constructed by the NaFePO4@C nanofibers cathode and the pure carbon nanofibers anode displays a promising energy density of 168.1 Wh kg?1 and a notable capacity retention of 87% after 200 cycles. The distinctive 3D network structure of very fine NaFePO4 nanoparticles homogeneously encapsulated in interconnected porous N‐doped carbon nanofibers, can effectively improve the active materials' utilization rate, facilitate the electrons/Na+ ions transport, and strengthen the electrode stability upon prolonged cycling, leading to the fascinating Na‐storage performance.  相似文献   

20.
Silicon nanowires (Si NWs) have been identified as an excellent candidate material for the replacement of graphite in anodes, allowing for a significant boost in the capacity of lithium‐ion batteries (LIBs). Herein, high‐density Si NWs are grown on a novel 3D interconnected network of binary‐phase Cu‐silicide nanofoam (3D CuxSiy NF) substrate. The nanofoam facilitates the uniform distribution of well‐segregated and small‐sized catalyst seeds, leading to high‐density/single‐phase Si NW growth with an areal‐loading in excess of 1.0 mg cm?2 and a stable areal capacity of ≈2.0 mAh cm?2 after 550 cycles. The use of the 3D CuxSiy NF as a substrate is further extended for Al, Bi, Cu, In, Mn, Ni, Sb, Sn, and Zn mediated Si NW growth, demonstrating the general applicability of the anode architecture.  相似文献   

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