N-doped porous carbon nanofibers sheathed pumpkin-like Si/C composites as free-standing anodes for lithium-ion batteries

Dramatic capacity fading and poor rate performance are two main obstacles that severely hamper the widespread application of the Si anode owing to its large volume variation during cycling and low intrinsic electrical conductivity.To mitigate these issues,free-standing N-doped porous carbon nanofibers sheathed pumpkin-like Si/C composites(Si/C-ZIF-8/CNFs)are designed and synthesized by electrospinning and carbonization methods,which present greatly enhanced electrochemical properties for lithium-ion battery anodes.This particular structure alleviates the volume variation,promotes the formation of stable solid electrolyte interphase(SEI)film,and improves the electrical conductivity.As a result,the as-obtained free-standing Si/C-ZIF-8/CNFs electrode delivers a high reversible capacity of 945.5 mAh g^(-1) at 0.2 A g^(-1) with a capacity retention of 64% for 150 cycles,and exhibits a reversible capacity of 538.6 mA h g^(-1) at 0.5 A g^(-1) over 500 cycles.Moreover,the full cell composed of a freestanding Si/C-ZIF-8/CNFs anode and commercial LiNi_(1/3)Co_(1/3)Mn_(1/3)O_(2)(NCM)cathode shows a capacity of 63.4 mA h g^(-1) after 100 cycles at 0.2 C,which corresponds to a capacity retention of 60%.This rational design could provide a new path for the development of high-performance Si-based anodes.

CoN_(x)C active sites-rich three-dimensional porous carbon nanofibers network derived from bacterial cellulose and bimetal-ZIFs as efficient multifunctional electrocatalyst for rechargeable Zn–air batteries

In this work, a CoNxC active sites-rich three-dimensional porous carbon nanofibers network derived from bacterial cellulose and bimetal-ZIFs is prepared via a nucleation growth strategy and a pyrolysis process.The material displays excellent electrocatalytic activity for the oxygen reduction reaction, reaching a high limiting diffusion current density of -7.8 mA cm^(-2), outperforming metal–organic frameworks derived multifunctional electrocatalysts, and oxygen evolution reaction and hydrogen evolution reaction with low overpotentials of 380 and 107 mV, respectively. When the electrochemical properties are further evaluated, the electrocatalyst as an air cathode for Zn-air batteries exhibits a high cycling stability for63 h as well as a maximum power density of 308 mW cm^(-2), which is better than those for most Zn-air batteries reported to date. In addition, a power density of 152 mW cm^(-2) is provided by the solid-state Zn-air batteries, and the cycling stability is outstanding for 24 h. The remarkable electrocatalytic properties are attributed to the synergistic effect of the 3 D porous carbon nanofibers network and abundant inserted CoNxC active sites, which enable the fast transmission of ions and mass and simultaneously provide a large contact area for the electrode/electrolyte.

Integration of Desulfurization and Lithium-Sulfur Batteries Enabled by Amino-Functionalized Porous Carbon Nanofibers

Hydrogen sulfide(H_(2)S)is an industrial exhausted gas that is highly toxic to humans and the environment.Combining desulfurization and fabrication of cathode materials for lithium-sulfur batteries(LSBs)can solve this issue with a double benefit.Herein,the amino-functionalized lotus root-like carbon nanofibers(NH_(2)-PLCNFs)are prepared by the amination of electrospinning carbon nanofibers under dielectric barrier discharge plasma.Selective catalytic oxidation of H_(2)S to elemental sulfur(S)is achieved over the metalfree NH_(2)-PLCNFs catalyst,and the obtained composite S@NH_(2)-PLCNFs is further used as cathode in LSBs.NH_(2)-PLCNFs enable efficient desulfurization(removal capacity as high as 3.46 g H_(2)S g^(−1) catalyst)and strongly covalent stabilization of S on modified carbon nanofibers.LSBs equipped with S@NH_(2)-PLCNFs deliver a high specific capacity of 705.8 mA h g^(−1) at 1 C after 1000 cycles based on the spatial confinement and the covalent stabilization of electroactive materials on amino-functionalized porous carbon matrix.It is revealed that S@NH_(2)-PLCNFs obtained by this kind of chemical vapor deposition leads to a more homogeneous S distribution and superior electrochemical performance to the sample S/NH_(2)-PLCNF-M prepared by the traditional molten infusion.This work opens a new avenue for the combination of environment protection and energy storage.

Fabrication of N,S co-doped porous carbon nanofibers as anode material for sodium-ion batteries with high performance

The N,S co-doped porous carbon nanofibers were fabricated by the carbonization of[Zn_(2)(tdc)_(2)(MA)]n MOFs/polyacrylonitrile nanofibers composite,which was produced by the electrospinning technology.The electrochemical results show that the N,S co-doped porous carbon nanofibers can achieve capacity of 201.2 mAh·g^(-1)at the current density of 0.05 A·g^(-1).Furthermore,the reversible capacity still has 161.3 mAh·g^(-1)even at a high current density of 1 A·g^(-1)after 600 cycles.The superior electrochemical performance shows that the N,S co-doped porous carbon nanofibers electrode material can be used as an ideal anode material for sodium-ion batteries.

Designed preparation of CoS/Co/MoC nanoparticles incorporated in N and S dual-doped porous carbon nanofibers for high-performance Zn-air batteries

The development of low-cost and highly efficient bifunctional electrocatalysts toward oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is of critical importance for clean energy devices such as fuel cells and metal-air batteries.Herein,a sophisticated na nostructure composed of CoS,Co and MoC nanoparticles incorporated in N and S dual-doped porous carbon nanofibers(CoS/Co/MoC-N,SPCNFs)as a high-efficiency bifunctional electrocatalyst is designed and synthesized via an efficient multistep strategy.The as-prepared CoS/Co/MoC-N,S-PCNFs exhibit a positive half-wave potential(E1/2)of0.871 V for ORR and a low overpotential of 289 mV at 10 mA/cm^(2) for OER,outperforming the non-noble metal-based catalysts reported.Furthermore,the assembled Zn-air battery based on CoS/Co/MoC-N,SPCNFs delivers an excellent power density(169.1 mW/cm^(2)),a large specific capacity(819.3 mAh/g)and robust durability,demonstrating the great potential of the as-developed bifunctional electrocatalyst in practical applications.This work is expected to inspire the design of advanced bifunctional nonprecious metal-based electrocatalysts for energy storage.

General synthesis of Pt and Ni co-doped porous carbon nanofibers to boost HER performance in both acidic and alkaline solutions

It is essential to develop efficient electrocatalysts to generate hydrogen from water electrolysis for hydrogen economy. In this work, platinum(Pt) and nickel(Ni) co-doped porous carbon nanofibers(Pt/NiPCNFs) with low Pt content were prepared via an electrospinning, carbonization and galvanic replacement reaction. Because of the high electrical conductivity, abundant electrochemical active sites and synergistic effect between Pt and Ni nanoparticles, the optimized Pt/Ni-PCNFs catalyst shows an excellent HER activity with overpotentials of 20 m V in 0.5 mol/L H_(2)SO_(4) and 46 m V in 1 mol/L KOH at a current density of10 m A/cm^(2). Furthermore, over 35-h long-term stability has been achieved without significant attenuation.This work provides a simple route to prepare highly efficient electrocatalysts for water splitting and has great prospects in the field of renewable energy.

Sulfur-deficient CoNi_(2)S_(4)nanoparticles-anchored porous carbon nanofibers as bifunctional electrocatalyst for overall water splitting

Water electrolysis technology is considered to be one of the most promising means to produce hydrogen.Herein,aiming at the problems of high overpotential and slow kinetics in water splitting,N-doped porous carbon nanofibers-coupled CoNi_(2)S_(4)nanoparticles are prepared as bifunctional electrocatalyst.In the strategy,NaCl is used as the template to prepare porous carbon nanofibers with a large surface area,and sulfur vacancies are created to modulate the electronic structure of CoNi_(2)S_(4).Electron spin resonance confirms the formation of abundant sulfur vacancies,which largely reduce the bandgap of CoNi_(2)S_(4)from 1.68 to 0.52 eV.The narrowed bandgap is conducive to the migration of valence electrons and decreases the charge transfer resistance for electrocatalytic reaction.Moreover,the uniform distribution of CoNi_(2)S_(4)nanoparticles on carbon nanofibers can prevent the aggregation and facilitate the exposure of electrochemical active sites.Therefore,the composite catalyst exhibits low overpotentials of 340 mV@100 mA·cm^(-2)for oxygen evolution reaction and 380 mV@100 mA·cm^(-2)for hydrogen evolution reaction.The assembled electrolyzer requires 1.64 V to achieve 10 mA·cm^(-2)for overall water-splitting with good long-term stability.The excellent performance results from the synergistic effect of porous structures,sulfur deficiency,nitrogen doping,and the well-dispersed active component.

PtZn nanoparticles supported on porous nitrogen-doped carbon nanofibers as highly stable electrocatalysts for oxygen reduction reaction

The oxygen reduction reaction(ORR)electrocatalytic activity of Pt-based catalysts can be significantly improved by supporting Pt and its alloy nanoparticles(NPs)on a porous carbon support with large surface area.However,such catalysts are often obtained by constructing porous carbon support followed by depositing Pt and its alloy NPs inside the pores,in which the migration and agglomeration of Pt NPs are inevitable under harsh operating conditions owing to the relatively weak interaction between NPs and carbon support.Here we develop a facile electrospinning strategy to in-situ prepare small-sized PtZn NPs supported on porous nitrogen-doped carbon nanofibers.Electrochemical results demonstrate that the as-prepared PtZn alloy catalyst exhibits excellent initial ORR activity with a half-wave potential(E_(1/2))of 0.911 V versus reversible hydrogen electrode(vs.RHE)and enhanced durability with only decreasing 11 mV after 30,000 potential cycles,compared to a more significant drop of 24 mV in E_(1/2)of Pt/C catalysts(after 10,000 potential cycling).Such a desirable performance is ascribed to the created triple-phase reaction boundary assisted by the evaporation of Zn and strengthened interaction between nanoparticles and the carbon support,inhibiting the migration and aggregation of NPs during the ORR.

Flexible heteroatom-doped porous carbon nanofiber cages for electrode scaffolds

Porous carbon nanofibers(PCNFs)with rich functionalities and high surface areas are important electrode scaffolds to load active materials,but increasing their pore volumes and strength simultaneously is a challenge.Here,we report a scalable method to fabricate B-F-N triply doped PCNF cages with high porosity of greater than 92.8%and small bending stiffness of 10 mN by electrospinning the mixed sol of poly(tetrafluoroethylene),poly(vinyl alcohol),boric acid,and carbon nanotubes(CNTs)followed by pyrolysis.The macromicro dual-phase separation creates well-controlled macropores(>60 nm)and meso-micropores with large pore volumes(0.55 cm3/g)on carbon nanofibers,while the interior CNTs can cushion the applied stress and render the PCNF films with superior flexibility.Fabricated symmetrical supercapacitors with the PCNF cages exhibit high gravimetric capacitance of 164 F/g at 20 mV/s and 92.5%capacity retention after 20000 cycles at 2 A/g.The reported approach allows the green synthesis of a new PCNF scaffold material with properties appealing for applications.

In situ embedded bismuth nanoparticles among highly porous carbon fibers for efficient carbon dioxide reduction

Electrocatalysis provides an optimal approach for the conversion of carbon dioxide(CO_(2))into high-value chemicals,thereby presenting a promising avenue toward achieve carbon neutrality.However,addressing the selectivity and stability challenges of metal catalysts in electrolytic reduction remains a daunting task.In this study,the electrospinning method is employed to fabricate porous carbon nanofibers loaded with bismuth nanoparticles with the help of in situ pyrolysis.The porous carbon nanofibers as conductive support would facilitate the dispersion of bismuth active sites while inhibiting their aggregation and promoting the mass transfer,thus enhancing their electrocatalytic activity and stability.Additionally,nitrogen doping induces electron delocalization in bismuth atoms through metal-support interactions,thus enabling efficient adsorption of intermediates for improving selectivity based on the theoretical calculation.Consequently,Bi@PCNF-500 exhibits the exceptional selectivity and stability across a wide range of potential windows.Notably,its faradaic efficiency(FE)of formate reaches 92.7%in H-cell and94.9%in flow cell,respectively,with good electrocatalytic stability.The in situ characterization and theoretical calculations elucidate the plausible reaction mechanism to obtain basic rules for designing efficient electrocatalyst.

Zinc-ion hybrid supercapacitors with ultrahigh areal and gravimetric energy densities and long cycling life

Zinc ion hybrid supercapacitor (ZIHSC) with promising energy and power densities is an excellent answer to the ever-growing demand for energy storage devices.The restricted lifespan due to the dendrite formation on metallic zinc (Zn) is one of the main roadblocks.Herein,we investigate the electrochemical capability of oxygen-enriched porous carbon nanofibers (A-CNF) and nitrogen,oxygen-enriched porous carbon nanofibers (N-CNF) cathode materials for structural ZIHSCs.To this end,a series of samples with different chemical compositions (N and O contents) are prepared to present deep insight into the electrochemical mechanism between N/O doping and Zn-ion storage.The as-prepared ZIHSC in the presence of N-CNF cathode and Zn Cl_(2) electrolyte offers a battery-level gravimetric energy density of 143.2 Wh kg^(-1)at a power density of 367.1 W kg^(-1).The free-standing N-CNF electrodes in ZIHSCs enjoy delivering an outstanding areal energy density of 110.4μWh cm^(-2)at 0.24 m W cm^(-2),excellent rate capability,and noticeable cycling stability over 10,000 cycles at 10 A g^(-1)with less than 7%decay.It was also concluded that active pyrrolic N dopants might deliver and facilitate more pseudocapacitance in ZIHSCs than other N configurations,resulting in higher adsorption/desorption and insertion/extraction process of Zn Cl^(+).Taking advantage of the beneficial properties of a free-standing continuous cathode,this novel generation of structural cathode material offers high areal and gravimetric energy densities and mechanical properties in a single zinc-ion-based package.

Lotus root-like porous carbon nanofiber anchored with CoP nanoparticles as all-pH hydrogen evolution electrocatalysts

The development of highly active and cost-effective hydrogen evolution reaction （HER） catalysts is of vital importance to addressing global energy issues. Here, a three-dimensional interconnected porous carbon nanofiber （PCNF） membrane has been developed and utilized as a support for active cobalt phosphide （COP） nanoparticles. This rationally designed self-supported HER catalyst has a lotus root-like multichannel structure, which provides several intrinsic advantages over conventional CNFs. The longitudinal channels can store the electrolyte and ensure fast ion and mass transport within the catalysts. Additionally, mesopores on the outer and inner carbon walls enhance ion and mass migration of the electrolyte to HER active CoP nanoparticles, thus shortening the ion transport distance and increasing the contact area between the electrolyte and the CoP nanoparticles. Moreover, the conductive carbon substrate provides fast electron transfer pathways by forming an integrated conductive network, which further ensures fast HER kinetics. As a result, the CoP/PCNF composites exhibit low onset-potentials （-20, -91, and -84 mV in 0.5 M H2SO4, 1 M PBS, and 1 M KOH, respectively）. These findings show that CoP/PCNF composites are promising self-supporting and high-performance all-pH range HER catalysts.

CHARACTERIZATION AND ADSORPTION PROPERTIES OF POROUS CARBON NANOFIBER GRANULES

The properties of the porous granules produced by agglomeration of catalytically grown carbon nanofibers were investigated in this work. The single pellet crushing strength of the granules is high, e.g., 1.6-2.5 MPa. They have high specific surface areas, averaging 72-141 m^2·g^-1, and the majority of their pores are mesopores or macropores. The adsorption at 298 K of benzene or phenol on the granules is much lower than that on activated carbon and depends not only on the specific surface area of the carbon material but also on the sewing structure of the granules and the morphology of the carbon nanofibers. Treatment in dilute nitric acid appreciably reduces such adsorption.

Improving NiNX and pyridinic N active sites with space-confined pyrolysis for effective CO_(2)electroreduction

Even though various nickel-nitrogen-carbon(Ni-N-C)combinations are prospective low-cost catalysts for the CO_(2)electroreduction reaction(CO_(2)RR),which is one avenue for attaining carbon neutrality,the detailed role of different N species has hardly been investigated.Here,we report a hollow porous N-doped carbon nanofiber with NiNX-pyridinic N active species(denoted as h-Ni-N-C)developed using a facile electrospinning and SiO_(2)space-confined pyrolysis strategy.The NiNX-pyridinic N species are facilely generated during the pyrolysis process,giving rise to enhanced activity and selectivity for the CO_(2)RR.The optimized h-Ni-N-C exhibits a high CO Faradaic efficiency of 91.3%and a large current density of−15.1 mA cm^(−2)at−0.75 V versus reversible hydrogen electrode in an H-cell.Density functional theory(DFT)results show that NiN4-pyridinic N species demonstrate a lower free energy for the catalyst's rate-determining step than isolated NiN4 and pyridinic N species,without affecting the desorption of CO∗intermediate.