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1.
The mechanism of Li–O2 batteries is based on the reactions of lithium ions and oxygen, which hold a theoretical higher energy density of approximately 3500 W h kg−1. In order to improve the practical specific capacity and cycling performance of Li–O2 batteries, a catalytically active mechanically robust air cathode is required. In this work, we synthesized a freestanding catalytic cathode with RuO2 decorated 3D web Co3O4 nanowires on nickel foam. When the specific capacity was limited at 500 mA h g−1, the RuO2–Co3O4/NiF had a stable cycling life of up to 122 times. The outstanding performance can be primarily attributed to the robust freestanding Co3O4 nanowires with RuO2 loading. The unique 3D web nanowire structure provides a large surface for Li2O2 growth and RuO2 nanoparticle loading, and the RuO2 nanoparticles help to promote the round trip deposition and decomposition of Li2O2, therefore enhancing the cycling behavior. This result indicates the superiority of RuO2–Co3O4/NiF as a freestanding highly efficient catalytic cathode for Li–O2 batteries.

Freestanding RuO2–Co3O4 nanowires on Ni foam were synthesized and applied as a cathode in Li–O2 battery. This cathode can deliver a high capacity of 9620 mA h g−1 and stable long-term operation exceeding 122 cycles at 100 mA g−1.  相似文献   

2.
A layered nanosphere structured NiO catalyst was successfully synthesized by a simple and efficient hydrothermal method as a cathode material for lithium–oxygen (Li–O2) batteries. Cyclic voltammetry (CV), dual electrode voltammetry (DECV) and chronoamperometry (CA) by rotating ring-disk electrode (RRDE) were carried out to investigate the catalytic activity of this catalyst for the oxygen evolution reaction (OER). The results revealed that the layered nanosphere NiO exhibited excellent electrochemical performance, stability and a typical four-electron reaction as a cathode electrocatalyst for rechargeable nonaqueous Li–O2 batteries. The overpotential of the NiO is only up to 0.61 V. X-ray photoelectron spectroscopy (XPS) characterization shows that the Li2O2 and Li2CO3 formed during the discharge process and decomposed after charging. Moreover, the cut-off voltage of discharging is about 2.0 V in the NiO-based Li–O2 batteries, while the specific capacity is up to 3040 mA h g−1. There is no obvious performance decline of the battery after 50 cycles at a current density of 0.1 mA cm−2 with a superior limited specific capacity of 800 mA h g−1. Herein, the layered nanosphere structured NiO catalyst is considered a promising cathode electrocatalyst for Li–O2 batteries.

A layered nanosphere structured NiO catalyst was synthesized by a simple and efficient hydrothermal method as a cathode material for lithium–oxygen (Li–O2) batteries.  相似文献   

3.
Herein, hollow porous CuO–CuCo2O4 dodecahedrons are synthesized by using a simple self-sacrificial metal–organic framework (MOF) template, which resulted in dodecahedron morphology with hierarchically porous architecture. When evaluated as a cathodic electrocatalyst in lithium–oxygen batteries, the CuO–CuCo2O4 composite exhibits a significantly enhanced electrochemical performance, delivering an initial capacity of 6844 mA h g−1 with a remarkably decreased discharge/charge overpotential to 1.15 V (vs. Li/Li+) at a current density of 100 mA g−1 and showing excellent cyclic stability up to 111 charge/discharge cycles under a cut-off capacity of 1000 mA h g−1 at 400 mA g−1. The outstanding electrochemical performance of CuO–CuCo2O4 composite can be owing to the intrinsic catalytic activity, unique porous structure and the presence of substantial electrocatalytic sites. The ex situ XRD and SEM are also carried out to reveal the charge/discharge behavior and demonstrate the excellent reversibility of the CuO–CuCo2O4 based electrode.

Metal–organic framework derived porous CuO–CuCo2O4 dodecahedrons as a cathode catalyst for Li–O2 batteries with significantly enhanced rate and cyclic performance.  相似文献   

4.
Lithium–sulfur (Li–S) batteries are the most promising energy storage systems owing to their high energy density. However, shuttling of polysulfides detracts the electrochemical performance of Li–S batteries and thus prevents the commercialization of Li–S batteries. Here, TiO2@porous carbon nanofibers (TiO2@PCNFs) are fabricated via combining electrospinning and electrospraying techniques and the resultant TiO2@PCNFs are evaluated for use as an interlayer in Li–S batteries. TiO2 nanoparticles on PCNFs are observed from SEM and TEM images. A high initial discharge capacity of 1510 mA h g−1 is achieved owing to the novel approach of electrospinning the carbon precursor and electrospraying TiO2 nanoparticles simultaneously. In this approach TiO2 nanoparticles capture polysulfides with strong interaction and the PCNFs with high conductivity recycle and re-use the adsorbed polysulfides, thus leading to high reversible capacity and stable cycling performance. A high reversible capacity of 967 mA h g−1 is reached after 200 cycles at 0.2C. The cell with the TiO2@PCNF interlayer also delivers a reversible capacity of around 1100 mA h g−1 at 1C, while the cell without the interlayer exhibits a lower capacity of 400 mA h g−1. Therefore, this work presents a novel approach for designing interlayer materials with exceptional electrochemical performance for high performance Li–S batteries.

Lithium–sulfur (Li–S) batteries are the most promising energy storage systems owing to their high energy density.  相似文献   

5.
Suitable catalysts and reasonable structures for oxygen electrodes can effectively improve the electrochemical performance of lithium–oxygen batteries. In this work, ruthenium oxide modified boron-doped hierarchically porous reduced graphene aerogels (RuO2-B-HRG) are prepared by a sol–gel and subsequent low temperature annealing method and used as oxygen electrodes. The RuO2 nanoparticles (5–10 nm) are uniformly anchored in the three-dimensional B-HRG continuous electric network. The RuO2-B-HRG aerogel possesses a large specific surface area (287.211 m2 g−1) and numerous mesopores and micropores. The pores facilitate electrolyte impregnation and oxygen diffusion, and they provide greatly increased accommodation space for the discharge products. Electrochemical tests show that the RuO2-B-HRG/KB enables the electrode overpotential to decrease, and the rate capability and the cycling stability are enhanced compared with pure HRG. The enhanced performance is ascribed to the bifunctional catalytic activity of RuO2-B-HRG and its unique three-dimensional porous architecture. The method is proved to be an effective strategy to combine porous carbon materials and nanoscale catalysts as electrodes for Li–O2 batteries.

Hierarchically porous RuO2-B-HRG is a great bifunctional catalyst and effectively improve the performance of non-aqueous Li–O2 batteries.  相似文献   

6.
Electrochemical water splitting technology is considered to be the most reliable method for converting renewable energy such as wind and solar energy into hydrogen. Here, a nanostructured RuO2/Co3O4–RuCo-EO electrode is designed via magnetron sputtering combined with electrochemical oxidation for the oxygen evolution reaction (OER) in an alkaline medium. The optimized RuO2/Co3O4–RuCo-EO electrode with a Ru loading of 0.064 mg cm−2 exhibits excellent electrocatalytic performance with a low overpotential of 220 mV at the current density of 10 mA cm−2 and a low Tafel slope of 59.9 mV dec−1 for the OER. Compared with RuO2 prepared by thermal decomposition, its overpotential is reduced by 82 mV. Meanwhile, compared with RuO2 prepared by magnetron sputtering, the overpotential is also reduced by 74 mV. Furthermore, compared with the RuO2/Ru with core–shell structure (η = 244 mV), the overpotential is still decreased by 24 mV. Therefore, the RuO2/Co3O4–RuCo-EO electrode has excellent OER activity. There are two reasons for the improvement of the OER activity. On the one hand, the core–shell structure is conducive to electron transport, and on the other hand, the addition of Co adjusts the electronic structure of Ru.

The optimized RuO2/Co3O4–RuCo-EO electrode with Ru loading of 0.064 mg cm−2 exhibits the excellent oxygen evolution activity with an overpotential of 220 mV at the current density of 10 mA cm−2 and a Tafel slope of 59.9 mV dec−1.  相似文献   

7.
Anode material Li2TiO3–coke was prepared and tested for lithium-ion batteries. The as-prepared material exhibits excellent cycling stability and outstanding rate performance. Charge/discharge capacities of 266 mA h g−1 at 0.100 A g−1 and 200 mA h g−1 at 1.000 A g−1 are reached for Li2TiO3–coke. A cycling life-time test shows that Li2TiO3–coke gives a specific capacity of 264 mA h g−1 at 0.300 A g−1 and a capacity retention of 92% after 1000 cycles of charge/discharge.

Anode material Li2TiO3–coke was prepared and tested for lithium-ion batteries. The as-prepared material exhibits excellent cycling stability and outstanding rate performance.  相似文献   

8.
Developing large-scale and high-performance OER (oxygen evolution reaction) and ORR (oxygen reduction reaction) catalysts have been a challenge for commercializing secondary zinc–air batteries. In this work, transition metal-doped cobalt–nickel sulfide spinels are directly produced via a continuous hydrothermal flow synthesis (CHFS) approach. The nanosized cobalt–nickel sulfides are doped with Ag, Fe, Mn, Cr, V, and Ti and evaluated as bifunctional OER and ORR catalyst for Zn–air battery application. Among the doped spinel catalysts, Mn-doped cobalt–nickel sulfides (Ni1.29Co1.49Mn0.22S4) exhibit the most promising OER and ORR performance, showing an ORR onset potential of 0.9 V vs. RHE and an OER overpotential of 348 mV measured at 10 mA cm−2, which is attributed to their high surface area, electronic structure of the dopant species, and the synergistic coupling of the dopant species with the active host cations. The dopant ions primarily alter the host cation composition, with the Mn(iii) cation linked to the introduction of active sites by its favourable electronic structure. A power density of 75 mW cm−2 is achieved at a current density of 140 mA cm−2 for the zinc–air battery using the manganese-doped catalyst, a 12% improvement over the undoped cobalt–nickel sulfide and superior to that of the battery with a commercial RuO2 catalyst.

Transition metal-doped cobalt–nickel sulfide spinel (Ni1.29Co1.49Mn0.22S4) nanocatalysts for secondary Zn–air batteries with an efficient and stable electrochemical performance.  相似文献   

9.
A bagasse-based 3D carbon matrix (BC) with high specific surface area and high conductivity was obtained by carbonization and pore-forming processes with bagasse as the carbon precursor and K2FeO4 as the pore-former. The microporous structure and nitrogenous functional groups were determined in the prepared carbon matrix, which could allow high sulfur loading and improve the polysulfide absorption capacity during cycling. After sulfur infusion, the S/BC composite with 68.8% sulfur content was obtained. The lithium–sulfur (Li–S) battery with the S/BC cathode shows high specific capacity and good cycling performance. It delivers a specific capacity of 1360 mA h g−1 at 0.2C and remains at 790 mA h g−1 after 200 cycles. At 1C, the Li–S with this composite cathode exhibits 601 mA h g−1 after 150 cycles. This work offers a new kind of green material and a new method for Li–S batteries.

Bagasse-based carbon matrix with microporous structure and nitrogenous functional groups could have high sulfur loading and excellent polysulfide absorption capacity.  相似文献   

10.
Lithium–sulfur (Li–S) batteries are regarded as one of the most promising energy storage technologies, however, their practical application is greatly limited by a series of sulfur cathode challenges such as the notorious “shuttle effect”, low conductivity and large volume change. Here, we develop a facile hydrothermal method for the large scale synthesis of sulfur hosts consisting of three-dimensional graphene aerogel with tiny TiO2 nanoparticles (5–10 nm) uniformly dispersed on the graphene sheet (GA–TiO2). The obtained GA–TiO2 composites have a high surface area of ∼360 m2 g−1 and a hierarchical porous structure, which facilitates the encapsulation of sulfur in the carbon matrix. The resultant GA–TiO2/S composites exhibit a high initial discharge capacity of 810 mA h g−1 with an ultralow capacity fading of 0.054% per cycle over 700 cycles at 2C, and a high rate (5C) performance (396 mA h g−1). Such architecture design paves a new way to synthesize well-defined sulfur hosts to tackle the challenges for high performance Li–S batteries.

GA–TiO2 composites as a cathode material realize an excellent electrochemical performance in Li–S batteries.  相似文献   

11.
Lithium–sulfur (Li–S) batteries are promising candidates for next generation rechargeable batteries because of their high energy density of 2600 W h kg−1. However, the insulating nature of sulfur and Li2S, the “shuttle effect” of lithium polysulfides (LiPSs), and the volumetric change of sulfur electrodes limit the practical application of Li–S batteries. Here, lychee-like TiO2@TiN hollow spheres (LTTHS) have been developed that combine the advantages of high adsorption TiO2 and high conductivity TiN to achieve smooth adsorption/spread/conversion of LiPSs and use them as a sulfur host material in Li–S batteries for the first time. The cathode exhibits an initial specific capacity of 1254 mA h g−1 and a reversible capacity of 533 mA h g−1 after 500 cycles at 0.2C, which corresponds to an average coulombic efficiency up to 99%. The cell with the LTTHS@S cathode achieved an extended lifespan of over 1000 cycles. Such good performance can be assigned to the good adsorption and catalysis of the dual-function TiO2@TiN composite. This work proved that the TiO2@TiN composite can be an attractive matrix for sulfur cathodes.

Lithium–sulfur (Li–S) batteries are promising candidates for next generation rechargeable batteries because of their high energy density of 2600 W h kg−1.  相似文献   

12.
Thermal batteries with molten salt electrolytes are used for many military applications, primarily as power sources for guided missiles. The Li–B/CoS2 couple is designed for high-power, high-voltage thermal batteries. However, their capacity and safe properties are influenced by acute self-discharge that results from the dissolved lithium anode in molten salt electrolytes. To solve those problems, in this paper, carbon coated CoS2 was prepared by pyrolysis reaction of sucrose at 400 °C. The carbon coating as a physical barrier can protect CoS2 particles from damage by dissolved lithium and reduce the self-discharge reaction. Therefore, both the discharge efficiency and safety of Li–B/CoS2 thermal batteries are increased remarkably. Discharge results show that the specific capacity of the first discharge plateau of carbon-coated CoS2 is 243 mA h g−1 which is 50 mA h g−1 higher than that of pristine CoS2 at a current density of 100 mA cm−2. The specific capacity of the first discharge plateau at 500 mA cm−2 for carbon-coated CoS2 and pristine CoS2 are 283 mA h g−1 and 258 mA h g−1 respectively. The characterizations by XRD and DSC indicate that the carbonization process has no noticeable influence on the intrinsic crystal structure and thermal stability of pristine CoS2.

Suppressing self-discharge of Li–B/CoS2 thermal batteries through modifying the CoS2 cathode with a protective carbon coating layer.  相似文献   

13.
14.
The intrinsic polysulfide shuttle in lithium–sulfur (Li–S) batteries have significantly limited their practical applications. Conductive carbon materials with heteroatom doping and rich porosity is the most common strategy for the effective prevention of polysulfide shuttle, but are usually obtained with high costs and tedious procedures. Herein, we managed to obtain highly porous N, S-codoped carbon materials (NS-C) through treating waste plastic of polyvinylchloride (PVC) with KOH. The resulting NS-C was revealed to be highly efficient hosts for sulfur cathode, achieving large reversible capacities of 1205 mA h g−1 and 836 mA h g−1 at 0.1C and 1.0C, respectively, and remaining at 550 mA h g−1 after 500 cycles at 1C rate, showing an outstanding cycling stability. The significantly enhanced cycling performance was mainly ascribed to both the hierarchically porous structure and heavy N, S co-dopants, which respectively provided physical blocks and chemical affinity for the efficient immobilization of intermediate lithium polysulfides. The results provide an effective paradigm in the surface chemistry and sulfur cathode materials design for high-performance Li–S batteries and a new application for recycled plastic waste.

The intrinsic polysulfide shuttle in lithium–sulfur (Li–S) batteries have significantly limited their practical applications.  相似文献   

15.
Limiting the shuttle effect of polysulfides is an important means to realizing high energy density lithium–sulfur batteries (Li–S). In this study, an efficient electrocatalyst (CNFs@Ni3FeN) is synthesized by anchoring Ni3FeN in the carbon nanofibers (CNFs). The CNFs@Ni3FeN shows electrocatalytic activity and enhances the conversion of polysulfides. After assembling a battery, a high initial capacity (1452 mA h g−1) and favorable long-time cycling stability (100 cycles) with a capacity retention rate of 83% are obtained by the electrocatalysis of Ni3FeN. Compared with unmodified CNFs, the cycling stability of CNFs@Ni3FeN can be greatly improved. The catalytic mechanism is further deduced by X-ray photoelectron spectroscopy (XPS). Our work will inspire the rational design of CNFs@support hybrids for various electrocatalysis applications.

Limiting the shuttle effect of polysulfides is an important means to realizing high energy density lithium–sulfur batteries (Li–S).  相似文献   

16.
The design of stable and high performance metal free bifunctional electrocatalysts is a necessity in alkaline zinc–air batteries for oxygen reduction and evolution reaction. In the present work co-doped carbon materials have been developed from polymeric precursors with abundant active sites to achieve bifunctional activity. A 3-dimensional microporous nitrogen–carbon (NC) and co-doped nitrogen–sulfur–carbon (NSC) and nitrogen–phosphorus–carbon (NPC) were synthesized using poly(2,5-benzimidazole) as an N containing precursor. The obtained sheet like structure shows outstanding ORR and OER performance in alkaline systems with excellent stability compared to Pt/C catalyst. The doped heteroatom in the carbon is expected to have redistributed the charge around heteroatom dopants lowering the ORR potential and modifying the oxygen chemisorption mode thereby weakening the O–O bonding and improving the ORR activity and overall catalytic performance. The bifunctional activity (ΔE = Ej=10E1/2) of an air electrode for NPC, NSC, NC and Pt/C is 0.82 V, 0.87 V, 1.06 V and 1.03 V respectively, and the NPC value is smaller than most of the reported metal and non-metal based electrocatalysts. The ORR (from onset potential) and OER (10 mA cm−2) overpotential for NPC, NSC, and NC is (290 mV, 410 mV), (310 mV, 450 mV) and (340 mV, 600 mV) respectively. In the prepared catalyst the NPC exhibited higher ORR and OER activity (NPC > NSC > NC). The doping of P in NPC is found to have a great influence on the microstructure and therefore on the ORR and OER activity.

Metal free bifunctional catalysts based on co-doped carbon materials synthesized from polymeric precursors via a simple pyrolysis route with high cyclic stability and low polarization for Zn–air batteries.  相似文献   

17.
Lithium–oxygen (Li–O2) batteries as promising energy storage devices possess high gravimetric energy density and low emission. However, poor reversibility of electrochemical reactions at the cathode significantly affects the electrochemical properties of nonaqueous Li–O2 batteries, and low charge–discharge efficiency also results in short cycle-life. In this work, functional air cathodes containing mesoporous tungsten carbide nanoparticles for improving the reversibility of positive reactions in Li–O2 cells are designed. Mesoporous tungsten carbides are synthesized with mesoporous carbon nitride as the reactive template and carbon source. And mesoporous tungsten carbides in cathode materials display better electrochemical performance in Li–O2 cells in comparison with mesoporous carbon nitride and hard carbon. Tungsten carbide-1 (WC-1) with larger specific surface area promotes reversible formation and decomposition of Li2O2 at the cathode and lower charge overpotential (about 0.93 V) at 100 mA g−1, which allows the Li–O2 cell to run up to 100 cycles. In addition, synergistic interaction between WC-1 and LiI could further decrease the charging overpotentials of Li–O2 cells and improve the charge–discharge performances of the Li–O2 cells. These results indicate that mesoporous electrocatalysts can be utilized as promising functional materials for Li–O2 cells to decrease overpotentials.

Tungsten carbide with large specific surface area catalyzes reversible formation/decomposition of Li2O2 with low overpotential in a Li–O2 cell.  相似文献   

18.
ZnMnO3 has attracted enormous attention as a novel anode material for rechargeable lithium-ion batteries due to its high theoretical capacity. However, it suffers from capacity fading because of the large volumetric change during cycling. Here, porous ZnMnO3 yolk–shell microspheres are developed through a facile and scalable synthesis approach. This ZnMnO3 can effectively accommodate the large volume change upon cycling, leading to an excellent cycling stability. When applying this ZnMnO3 as the anode in lithium-ion batteries, it shows a remarkable reversible capacity (400 mA h g−1 at a current density of 400 mA g−1 and 200 mA h g−1 at 6400 mA g−1) and excellent cycling performance (540 mA h g−1 after 300 cycles at 400 mA g−1) due to its unique structure. Furthermore, a novel conversion reaction mechanism of the ZnMnO3 is revealed: ZnMnO3 is first converted into intermediate phases of ZnO and MnO, after which MnO is further reduced to metallic Mn while ZnO remains stable, avoiding the serious pulverization of the electrode brought about by lithiation of ZnO.

ZnMnO3 has attracted enormous attention as a novel anode material for rechargeable lithium-ion batteries due to its high theoretical capacity.  相似文献   

19.
Even after a decade of research and rapid development of lithium–sulfur (Li–S) batteries, the infamous shuttle effect of lithium polysulfide is still the major challenge hindering the commercialization of Li–S batteries. In order to further address this issue, a functionalized PP separator is obtained through selective single-sided chemical tailoring, and then organosiloxane fumigation grafting. During the charge–discharge process, the grafted functional groups can effectively block the transportation of the dissolved polysulfides through strong chemical anchoring, inhibit the shuttle effect and greatly enhance the cycle stability of the Li–S battery. Interestingly, the specially designed single-sided enlarged channel structure formed by chemical tailoring can well accommodate the deposition with intermediate polysulfides on the separator surface toward the cathode chamber, resulting in enhanced initial discharge capacity and rate performance. Compared to the battery assembled with PP, the Li–S battery employing the separator grafted with a 3-ureidopropyltrimethoxysilane (PP–Ox–U) displays better electrochemical performance. Even at 2C, it can still deliver a high capacity of 786 mA h g−1, and retain a capacity of 410 mA h g−1 with a low capacity fading of 0.095% per cycle over 500 cycles. This work provides a very promising and feasible strategy for the development of a special functionalization PP separator for Li–S batteries with high electrochemical performance.

Even after a decade of research and rapid development of lithium–sulfur (Li–S) batteries, the infamous shuttle effect of lithium polysulfide is still the major challenge hindering the commercialization of Li–S batteries.  相似文献   

20.
Although there have been many studies addressing the dendrite growth issue of lithium (Li)–metal batteries (LMBs), the Li–metal anode has not yet been implemented in today''s rechargeable batteries. There is a need to accelerate the practical use of LMBs by considering their cost-effectiveness, ecofriendliness, and scalability. Herein, a cost-effective and uniform protection layer was developed by simple heat treatment of a Post-it note. The carbonized Post-it protection layer, which consisted of electrochemically active carbon fibers and electrochemically inert CaCO3 particles, significantly contributed to stable plating and stripping behaviors. The resulting protected Li anode exhibited excellent electrochemical performance: extremely low polarization during cycling (<40 mV at a current density of 1 mA cm−2) and long lifespan (5000 cycles at 10 mA cm−2) of the symmetric cell, as well as excellent rate performance at 2C (125 mA h g−1) and long cyclability (cycling retention of 62.6% after 200 cycles) of the LiFePO4‖Li full cell. The paper-derived Li protection layer offer a facile and scalable approach to enhance LMB electrochemical performance.

A low-cost, ecofriendly, and scalable paper-derived protective layer is designed to achieve excellent electrochemical performance.  相似文献   

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