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The development of highly producible and interfacial compatible in situ polymerized electrolytes for solid-state lithium metal batteries (SSLMBs) have been plagued by insufficient transport kinetics and uncontrollable dendrite propagation. Herein, we seek to explore a rationally designed nanofiber architecture to balance all the criteria of SSLMBs, in which La0.6Sr0.4CoO3-δ (LSC) enriched with high valence-state Co species and oxygen vacancies is developed as electronically conductive nanofillers embedded within ZnO/Zn3N2-functionalized polyimide (Zn-PI) nanofiber framework for the first time, to establish Li+ transport highways for poly vinylene carbonate (PVC) electrolyte and eliminate nonuniform Li deposits. Revealed by characterization and theoretical calculation under electric field, the positive-negative electrical dipole layer in LSC derived from electron migration between Co and O atoms aids in accelerating Li+ diffusion kinetics through densified electric field around filler particle, featuring a remarkable ionic conductivity of 1.50â mS cm-1 at 25 °C and a high Li+ transference number of 0.91 without the risk of electron leakage. Integrating with the preferential sacrifice of ZnO/Zn3N2 on PI nanofiber upon immediate detection of dendritic Li, which takes part in reconfiguring hierarchical SEI chemistry dominated by LixNy/Li-Zn alloy inner layer and LiF outer layer, SSLMBs are further endowed with prolonged cycling lifespan and exceptional rate capability.
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Employing nanofiber framework for in situ polymerized solid-state lithium metal batteries (SSLMBs) is impeded by the insufficient Li+ transport properties and severe dendritic Li growth. Both critical issues originate from the shortage of Li+ conduction highways and nonuniform Li+ flux, as randomly-scattered nanofiber backbone is highly prone to slippage during battery assembly. Herein, a robust fabric of Li0.33 La0.56 Ce0.06 Ti0.94 O3-δ /polyacrylonitrile framework (p-LLCTO/PAN) with inbuilt Li+ transport channels and high interfacial Li+ flux is reported to manipulate the critical current density of SSLMBs. Upon the merits of defective LLCTO fillers, TFSI- confinement and linear alignment of Li+ conduction pathways are realized inside 1D p-LLCTO/PAN tunnels, enabling remarkable ionic conductivity of 1.21 mS cm-1 (26 °C) and tLi+ of 0.93 for in situ polymerized polyvinylene carbonate (PVC) electrolyte. Specifically, molecular reinforcement protocol on PAN framework further rearranges the Li+ highway distribution on Li metal and alters Li dendrite nucleation pattern, boosting a homogeneous Li deposition behavior with favorable SEI interface chemistry. Accordingly, excellent capacity retention of 76.7% over 1000 cycles at 2 C for Li||LiFePO4 battery and 76.2% over 500 cycles at 1 C for Li||LiNi0.5 Co0.2 Mn0.3 O2 battery are delivered by p-LLCTO/PAN/PVC electrolyte, presenting feasible route in overcoming the bottleneck of dendrite penetration in in situ polymerized SSLMBs.
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In the past decade, in the context of the carbon peaking and carbon neutrality era, the rapid development of new energy vehicles has led to higher requirements for the performance of strike forces such as battery cycle life, energy density, and cost. Lithium-ion batteries have gradually become mainstream in electric vehicle power batteries due to their excellent energy density, rate performance, and cycle life. At present, the most widely used cathode materials for power batteries are lithium iron phosphate (LFP) and LixNiyMnzCo1-y-zO2 cathodes (NCM). However, these materials exhibit bottlenecks that limit the improvement and promotion of power battery performance. In this review, the performance characteristics, cycle life attenuation mechanism (including structural damage, gas generation, and active lithium loss, etc.), and improvement methods (including surface coating and element-doping modification) of LFP and NCM batteries are reviewed. Finally, the development prospects of this field are proposed.
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LiNi0.8Co0.1Mn0.1O2 (LNCMO) cathode materials for lithium-ion batteries (LIBs) were prepared by the hydrothermal synthesis of precursors and high-temperature calcination. The effect of precursor hydrothermal synthesis temperature on the microstructures and electrochemical cycling performances of the Ni-rich LNCMO cathode materials were investigated by SEM, XRD, XPS and electrochemical tests. The results showed that the cathode material prepared using the precursor synthesized at a hydrothermal temperature of 220 °C exhibited the best charge/discharge cycle stability, whose specific capacity retention rate reached 81.94% after 50 cycles. Such enhanced cyclic stability of LNCMO was directly related to the small grain size, high crystallinity and structural stability inherited from the precursor obtained at 220 °C.
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The two-electron oxygen reduction reaction in acid is highly attractive to produce H2O2, a commodity chemical vital in various industry and household scenarios, which is still hindered by the sluggish reaction kinetics. Herein, both density function theory calculation and in-situ characterization demonstrate that in dual-atom CoIn catalyst, O-affinitive In atom triggers the favorable and stable adsorption of hydroxyl, which effectively optimizes the adsorption of OOH on neighboring Co. As a result, the oxygen reduction on Co atoms shifts to two-electron pathway for efficient H2O2 production in acid. The H2O2 partial current density reaches 1.92 mA cm-2 at 0.65 V in the rotating ring-disk electrode test, while the H2O2 production rate is as high as 9.68 mol g-1 h-1 in the three-phase flow cell. Additionally, the CoIn-N-C presents excellent stability during the long-term operation, verifying the practicability of the CoIn-N-C catalyst. This work provides inspiring insights into the rational design of active catalysts for H2O2 production and other catalytic systems.
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As an alternative anode to graphene, molybdenum disulfide (MoS2) has attracted much attention due to its layered structure and high specific capacity. Moreover, MoS2can be synthesized by hydrothermal method with low cost and the size of its layer spacing can be controlled. In this work, the results of experiment and calculation proved that the presence of intercalated Mo atoms, leading to the expansion of MoS2layer spacing and weakening of Mo-S bonding. For the electrochemical properties, the presence of intercalated Mo atoms causes the lower reduction potentials for the Li+intercalation and Li2S formation. In addition, the effective reduction of diffusion resistance and charge transfer resistance in Mo1+xS2leads to the acquisition of high specific capacity for battery applications.
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A novel 3D N- & S-co-doped carbon nanofiber network embedded with ultrafine NiCo oxide nanoparticles is explored by a facile surfactant-assisted electrospinning method. This catalyst has several structural advantages including ultrafine active sites (2-8 nm), hierarchical pores, and abundant defects, allowing for much higher OER/ORR activity compared to commercial IrO2 and Pt/C catalysts. The potential gap (ΔE) of OER and ORR metrics for NSCFs/Ni-Co-NiCo2O is 0.69 V and the Zn-air battery equipped with NSCFs/Ni-Co-NiCo2O as the air cathode delivers a maximum power density of 171.24 mW cm-2 at 268 mA cm-2. Furthermore, the unique structure of the 3D carbon nanofiber network embedded with ultrafine nanoparticles results in superior stability with negligible degradation in activity after 380 h of continuous operation.
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Cellular metals with the large surface/volume ratios and excellent electrical conductivity are widely applicable and have thus been studied extensively. It is highly desirable to develop a facile and cost-effective process for fabrication of porous metallic structures, and yet more so for micro/nanoporous structures. A direct-flame strategy is developed for in situ fabrication of micron-scale cellular architecture on a Ni metal precursor. The flame provides the required heat and also serves as a fuel reformer, which provides a gas mixture of H2 , CO, and O2 for redox treatment of metallic Ni. The redox processes at elevated temperatures allow fast reconstruction of the metal, leading to a cellular structure on Ni wire. This process is simple and clean and avoids the use of sacrificial materials or templates. Furthermore, nanocrystalline MnO2 is coated on the microporous Ni wire (MPNW) to form a supercapacitor electrode. The MnO2 /MPNW electrode and the corresponding fiber-shaped supercapacitor exhibit high specific capacitance and excellent cycling stability. Moreover, this work provides a novel strategy for the fabrication of cellular metals and alloys for a variety of applications, including catalysis, energy storage and conversion, and chemical sensing.
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Capacidad Eléctrica , Conductividad Eléctrica , Incendios/economía , Níquel/química , Análisis Costo-Beneficio , Electrodos , Gases/química , Compuestos de Manganeso/química , Nanopartículas , Oxidación-Reducción , Óxidos/química , PorosidadRESUMEN
For the sake of comparison, a single cell with nanofiber-based LST-GDC composite anode (Cell-1) and a single cell with nanoparticle-based LST-GDC composite anode (Cell-2) are fabricated, respectively. The electrolyte ohmic resistances of the LST-GDC composite anode side half-cells are determined by an AC resistance measurement. Current interrupt is applied to measure the ohmic resistance of the half-cells. Combined with V-I characteristics, the influences of the potential drops caused by electrolyte ohmic resistance, electrode ohmic resistance and electrode electrochemical reaction on the cell kinetics are investigated. Under a current density of 0.6 A cm-2 at 850 °C, for the nanofiber-based LST-GDC composite anode (NF-LST-GDC), the electrode ohmic potential drop is 0.007 V and the potential drop caused by the electrode electrochemical reaction is 0.080 V. While for the nanoparticle-based LST-GDC composite anode (NP-LST-GDC), the corresponding potential drops are 0.159 V and 0.246 V, respectively. Both the potential drops of the former are lower than those of the latter. The kinetics of Cell-1 is greater than Cell-2, i.e., the kinetics of NF-LST-GDC is greater than that of NP-LST-GDC.
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The present paper reports on the preparation of novel bamboo leaf shaped CuO nanorod dispersed hollow carbon fibers (denoted as CuO NR@PCFs). Specially, the new-type hollow carbon fibers (containing abundant micro/meso/macropores and a large specific surface area) were prepared only by simple and fast pyrolysis of the natural product catkins without using any template or surfactant. Meanwhile, a facile method was used to prepare the bamboo leaf shaped CuO nanorod covered PCFs. Thanks to the abundant micro/meso/macropores, large specific surface area, and excellent electrical conduction efficiency of the PCF matrix, the as-prepared CuO NR@PCFs could also afford more catalytic sites, show more excellent reactant transport efficiency, and display more excellent electron transport rates compared with those for the pure CuO balls. Above all, these advantages will result in the excellent oxidation and detection efficiency of the CuO NR@PCF sample to glucose. Electrochemical measurements reveal that the CuO NR@PCF modified electrode can directly catalyze glucose oxidation and display an enhanced current response compared with the pure CuO balls (such as a response time within 4 s, wide linear ranges of 5 × 10(-3)-0.8 mM and 0.8-8.5 mM, good reproducibility, considerable stability, and excellent anti-interference to electroactive molecules and Cl(-)). The superior catalytic activity and selectivity make the CuO NR@PCF catalyst very promising for application in direct detection of glucose.
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Productos Biológicos/química , Biomasa , Carbono/química , Cobre/química , Glucosa/análisis , Nanotubos/química , Plantas/química , Fibra de Carbono , Electroquímica , Glucosa/químicaRESUMEN
Designing and preparing porous transition metal ferrites without using any template, shape-directing agent, and surfactant is a challenge. Herein, heterojunction MFe2O4 (M = Co, Ni, Cu, Mn) nanofiber (NF) based films with three-dimensional configurations were synthesized by electrospinning and the subsequent thermal treatment processes. Characterization results indeed show the 3D net-like textural structures of the electrospun spinel-type MFe2O4 NFs. In particular, the resulting MFe2O4 NFs have lengths up to several dozens of micrometers with an average diameter size of about 150 nm and possess abundant micro/meso/macropores on both the surface and within the films. The hierarchically porous structures and high surface areas of these MFe2O4 NFs (for example, the CoFe2O4 NFs possess a larger BET specific surface area (61.48 m(2) g(-1)) than those of the CoFe2O4 NPs (5.93 m(2) g(-1))) can afford accessible transport channels for effectively decreasing the mass transport resistances, enhancing the electrical conductivity, and increasing the density and reactivity of the exposed catalytic active sites. All these advantages will be responsible for the better electrocatalytic performances of these MFe2O4 NFs compared with their structural isomers (i.e. the MFe2O4 NPs) for the oxygen evolution reaction (OER) and H2O2 reduction in alkaline solution. Meanwhile, both the OER and H2O2 reduction catalytic activities for these MFe2O4 NFs obey the order of CoFe2O4 NFs > CuFe2O4 NFs > NiFe2O4 NFs > MnFe2O4 NFs > Fe2O3 NFs. The CoFe2O4 NFs represent a new class of highly efficient non-noble-metal catalysts for both OER and H2O2 reduction/detection in alkaline media.