Carbon nanocages bridged with graphene enable fast kinetics for dual-carbon lithium-ion capacitors

Lithium-ion capacitors(LICs) combining the advantages of lithium-ion batteries and supercapacitors are considered a promising nextgeneration energy storage device. However, the sluggish kinetics of battery-type anode cannot match the capacitor-type cathode, restricting the development of LICs. Herein, hierarchical carbon framework(HCF) anode material composed of 0D carbon nanocage bridged with 2D graphene network are developed via a template-confined synthesis process. The HCF with nanocage structure reduces the Li^(+) transport path and benefits the rapid Li^(+) migration, while 2D graphene network can promote the electron interconnecting of carbon nanocages. In addition, the doped N atoms in HCF facilitate to the adsorption of ions and enhance the pseudo contribution, thus accelerate the kinetics of the anode. The HCF anode delivers high specific capacity, remarkable rate capability. The LIC pouch-cell based on HCF anode and active HCF(a-HCF) cathode can provide a high energy density of 162 Wh kg^(-1) and a superior power density of 15.8 kW kg^(-1), as well as a long cycling life exceeding 15,000cycles. This study demonstrates that the well-defined design of hierarchical carbon framework by incorporating 0D carbon nanocages and 2D graphene network is an effective strategy to promote LIC anode kinetics and hence boost the LIC electrochemical performance.

Amine-functionalized hierarchically porous carbon supported Pd nanocatalysts for highly efficient H2 generation from formic acid with fast-diffusion channels

Formic acid(FA)has come to be considered a potential candidate for hydrogen storage,and the development of efficient catalysts for H2releasing is crucial for realizing the sustainable process from FA.Herein,we have developed the ultrafine Pd nanoparticle(NPs)with amine-functionalized carbon as a support,which was found to show an excellent catalytic activity in H_(2)generation from FA dehydrogenation.The synergetic mechanism between amine-group and Pd active site was demonstrated to facilitate H2generation byβ-hydride elimination.Moreover,the texture of support for Pd NPs also plays an important role in determining the reactivity of FA,since the diffusion of gaseous products makes the kinetics of diffusion as a challenge in this high performance Pd catalysts.As a result,the as-prepared Pd/NH_(2)-TPC catalyst with the small sized Pd nanoparticles and the hierarchically porous structures shows a turnover of frequency(TOF)value of 4312 h^(-1)for the additive-free FA dehydrogenation at room temperature,which is comparable to the most promising heterogeneous catalysts.Our results demonstrated that the intrinsic catalytic activities of active site as well as the porous structure of support are both important factors in determining catalytic performances in H2generation from FA dehydrogenation,which is also helpful to develop high-activity catalysts for other advanced gas-liquid-solid reactions systems.

Absorption properties and mechanism of lightweight and broadband electromagnetic wave-absorbing porous carbon by the swelling treatment

Bioderived carbon materials have garnered considerable interest in the fields of microwave absorption and shielding due to their reproducibility and environmental friendliness.In this study,KOH was evenly distributed on biomass Tremella using the swelling induction method,leading to the preparation of a three-dimensional network-structured hierarchical porous carbon(HPC)through carbonization.The achieved microwave absorption intensity is robust at-47.34 dB with a thin thickness of 2.1 mm.Notably,the widest effective absorption bandwidth,reaching 7.0 GHz(11–18 GHz),is attained at a matching thickness of 2.2 mm.The exceptional broadband and reflection loss performance are attributed to the 3D porous networks,interface effects,carbon network defects,and dipole relaxation.HPC has outstanding absorption characteristics due to its excellent impedance matching and high attenuation constant.The uniform pore structures considerably optimize the impedance-matching performance of the material,while the abundance of interfaces and defects enhances the dielectric loss,thereby improving the attenuation constant.Furthermore,the impact of carbonization temperature and swelling rate on microwave absorption performance was systematically investigated.This research presents a strategy for preparing absorbing materials using biomass-derived HPC,showcasing considerable potential in the field of electromagnetic wave absorption.

Advanced Ni-Nx-C single-site catalysts for CO2 electroreduction to CO based on hierarchical carbon nanocages and S-doping

Metal-nitrogen-carbon materials are promising catalysts for CO2 electroreduction to CO. Herein, by taking the unique hierarchical carbon nanocages as the support, an advanced nickel-nitrogen-carbon single-site catalyst is conveniently prepared by pyrolyzing the mixture of NiCl2 and phenanthroline, which exhibits a Faradaic efficiency plateau of > 87% in a wide potential window of −0.6 – −1.0 V. Further S-doping by adding KSCN into the precursor much enhances the CO specific current density by 68%, up to 37.5 A·g−1 at −0.8 V, along with an improved CO Faradaic efficiency plateau of > 90%. Such an enhancement can be ascribed to the facilitated CO pathway and suppressed hydrogen evolution from thermodynamic viewpoint as well as the increased electroactive surface area and improved charge transfer fromkinetic viewpoint due to the S-doping. This study demonstrates a simple and effective approach to advanced electrocatalysts by synergetic modification of the porous carbon-based support and electronic structure of the active sites.

Preparation and performance of hierarchically porous carbons as oxygen electrodes for lithium oxygen batteries

The hierarchically porous carbons （HPCs） were prepared by sol-gel selassembly technology in different surfactant concentrations and were used as the potential electrode for lithium oxygen batteries. The physical and electrochemical properties of the as-prepared HPCs were investigated by filed emission scanning electron microscopy （FE-SEM）, transmission electron microscopy （TEM）, nitrogen adsorption-desorption isotherm and galvanostatic charge/discharge. The results indicate that all of the HPCs mainly possess mesoporous structure with nearly similar pore size distribution. Using the HPCs as the electrode, a high discharge capacity for lithium oxygen battery can be achieved, and the discharge capacity increases with the specific surface area. Especially, the HPCs-3 oxygen electrode with CTAB concentration of 0.27 mol/L exhibits good capacity retention through controlling discharge depth to 800 mA·h/g and the highest discharge capacity of 2050 mA·h/g at a rate of 0.1 mA/cm2.

Hierarchical carbon nanocages as high-rate anodes for Li-and Na-ion batteries

Novel hierarchical carbon nanocages （hCNCs） are proposed as high-rate anodes for Li- and Na-ion batteries. The unique structure of the porous network for hCNCs greatly favors electrolyte penetration, ion diffusion, electron conduction, and structural stability, resulting in high rate capability and excellent cyclability. For lithium storage, the corresponding electrode stores a steady reversible capacity of 970 mAh·g^-1 at a rate of 0.1 A·g^-1 after 10 cycles, and stabilizes at 229 mAh·g^-1 after 10,000 cycles at a high rate of 25 A·g^-1（33 s for full-charging） while delivering a large specific power of 37 kW·kgelectrode^-1 and specific energy of 339 Wh·kgelectrode^-1. For sodium storage, the hCNC reaches a high discharge capacity of -50 mAh·g^-1 even at a high rate of 10 A·g^-1.

Defect-induced deposition of manganese oxides on hierarchical carbon nanocages for high-performance lithium-oxygen batteries

The cathode of lithium-oxygen(Li-O_(2))batteries should have large space for high Li_(2)O_(2) uptake and superior electrocatalytic activity to oxygen evolution/reduction for long lifespan.Herein,a high-performance MnO_(x)/hCNC cathode was constructed by the defect-induced deposition of manganese oxide(MnOx)nanoparticles on hierarchical carbon nanocages(hCNC).The corresponding Li-O2 battery(MnOx/hCNC@Li-O_(2))exhibited excellent electrocatalytic activity with the low overpotential of 0.73-0.99 V in the current density range of 0.1-1.0 A·g^(-1).The full discharge capacity and cycling life of MnO_(x)/hCNC@Li-O_(2) were increased by~86.7%and~91%,respectively,compared with the hCNC@Li-O_(2) counterpart.The superior performance of MnO_(x)/hCNC cathode was ascribed to(i)the highly dispersed MnO_(x) nanoparticles for boosting the reversibility of oxygen evolution/reduction reactions,(ii)the interconnecting pore structure for increasing Li_(2)O_(2) accommodation and facilitating charge/mass transfer,and(iii)the concealed surface defects of hCNC for suppressing side reactions.This study demonstrated an effective strategy to improve the performance of Li-O_(2) batteries by constructing cathodes with highly dispersed catalytic sites and hierarchical porous structure.

Enlarging ion-transfer micropore channels of hierarchical carbon nanocages for ultrahigh energy and power densities

Increasing the energy density of supercapacitor without sacrificing its high power is an everlasting pursuit in energy storage.Using ionic liquid electrolyte with high operating voltage can increase the energy density but usually at the expense of power density due to the large ion size,low ionic conductivity and high viscosity.Herein we demonstrate a simultaneous increase of the energy and power densities with ionic liquid electrolyte(EMIMBF4)mainly by enlarging the ion-transfer micropore channels of the electrode material,i.e.,the unique hierarchical carbon nanocages(hCNC).Boudouard reaction is adopted to tune the micropore size while remaining the hierarchical framework of hCNC.Meanwhile,the specific surface area,pore volume and conductivity are also increased under optimal activation temperature.Such a unique modification boosts the large-sized ion transfer,leading to the obvious decrease of equivalent series resistance and the dramatic increase of supercapacitive performance thereof.The optimized product exhibits an energy density up to 153.8 W h kg^(-1) at the power density of 1.8 kW kg^(-1),and maintains 54.0 W h kg^(-1) even at an ultrahigh power density of 480.1 kW kg^(-1).This study demonstrates an effective way to explore advanced electrode materials by the fine regulation of micropores and related properties.

Hierarchically mesoporous carbon spheres coated with a single atomic Fe-N-C layer for balancing activity and mass transfer in fuel cells

Novel cost-effective fuel cells have become more attractive due to the demands for rare and expensive platinum-group metal(PGM)catalysts for mitigating the sluggish kinetics of the oxygen reduction reaction(ORR).The high-cost PGM catalyst in fuel cells can be replaced by earth-abundant transition-metalbased catalysts,that is,an Fe-N-C catalyst,which is considered one of the most promising alternatives.However,the performance of the Fe-N-C catalyst is hindered by the low catalytic activity and poor stability,which is caused by insufficient active sites and the lack of optimization of the triple-phase interface for mass transportation.Herein,a novel Fe–N–C catalyst consisting of mono-dispersed hierarchically mesoporous carbon sphere cores and single Fe atom-dispersed functional shells are presented.The synergistic effect between highly dispersed Fe-active sites and well-organized porous structures yields the combination of high ORR activity and high mass transfer performance.The half-wave potential of the catalyst in 0.1M H_(2)SO_(4) is 0.82 V versus reversible hydrogen electrode,and the peak power density is 812 mW·cm^(−2) in H_(2)–O_(2) fuel cells.Furthermore,it shows superior methanol tolerance,which is almost immune to methanol poisoning and generates up to 162 mW·cm^(−2) power density in direct methanol fuel cells.

Status and perspectives of hierarchical porous carbon materials in terms of high-performance lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries,although a promising candidate of next-generation energy storage devices,are hindered by some bottlenecks in their roadmap toward commercialization.The key challenges include solving the issues such as low utilization of active materials,poor cyclic stability,poor rate performance,and unsatisfactory Coulombic efficiency due to the inherent poor electrical and ionic conductivity of sulfur and its discharged products(e.g.,Li2S2 and Li_(2)S),dissolution and migration of polysulfide ions in the electrolyte,unstable solid electrolyte interphase and dendritic growth on an odes,and volume change in both cathodes and anodes.Owing to the high specific surface area,pore volume,low density,good chemical stability,and particularly multimodal pore sizes,hierarchical porous carbon(HPC)mate rials have received considerable attention for circumventing the above pro blems in Li-S batteries.Herein,recent progress made in the synthetic methods and deployment of HPC materials for various components including sulfur cathodes,separators and interlayers,and lithium anodes in Li-S batteries is presented and summarized.More importantly,the correlation between the structures(pore volume,specific surface area,degree of pores,and heteroatom-doping)of HPC and the electrochemical performances of Li-S batteries is elaborated.Finally,a discussion on the challenges and future perspectives associated with HPCs for Li-S batteries is provided.

Lignin derived hierarchical porous carbon with extremely suppressed polyselenide shuttling for high-capacity and long-cycle-life lithium-selenium batteries

Lithium-selenium(Li-Se)batteries have attracted considerable attentions for next-generation energy storage systems owing to high volumetric capacity of 3265 m Ah cm^(-3) and excellent electronic conductivity(~10^(-5)S cm^(-1))of selenium.However,the shuttling effect and capacity fading prevent their wide applications.Herein we report a low-cost strategy for scalable fabrication of lignin derived hierarchical porous carbon(LHPC)as a new high-loading Se host for high-capacity and long-term cycling Li-Se batteries in carbonate electrolyte.The resulting LHPC exhibits three-dimensional(3D)hierarchically porous structure,high specific surface area of 1696 m^(2) g^(-1),and hetero-atom doping(O,S),which can effectively confine the Se particles into the micropores,and meanwhile,offer effective chemical binding sites for selenides from hetero-atoms(O,S).As a result,our Li-Se batteries based on Se@LHPC demonstrate high capacity of 450 m Ah g^(-1) at 0.5 C after 500 cycles,with a low capacity fading rate of only 0.027%.The theoretical simulation confirmed the strong affinity of selenides on the O and S sites of LHPC effectively mitigating the Se losing.Therefore,our strategy of using lignin as the low-cost precursor of hierarchically porous carbon for high-loading Se host offers new opportunities for high-capacity and long-life Li-Se batteries.

Anti-aggregation growth and hierarchical porous carbon encapsulation enables the C@VO_(2) cathode with superior storage capability for aqueous zinc-ion batteries

Self-aggregation and sluggish transport kinetics of cathode materials would usually lead to the poor electrochemical performance for aqueous zinc-ion batteries(AZIBs).In this work,we report the construction of C@VO_(2) composite via anti-aggregation growth and hierarchical porous carbon encapsulation.Both of the morphology of composite and pore structure of carbon layer can be regulated by tuning the adding amount of glucose.When acting as cathode applied for AZIBs,the C@VO_(2)-3:3 composite can deliver a high capacity of 281 m Ah g^(-1) at 0.2 A g^(-1).Moreover,such cathode also exhibits a remarkably rate capability and cyclic stability,which can release a specific capacity of 195 m Ah g^(-1) at 5 A g^(-1) with the capacity retention of 95.4%after 1000 cycles.Besides that,the evolution including the crystal structure,valence state and transport kinetics upon cycling were also deeply investigated.In conclusion,benefited from the synergistic effect of anti-aggregation morphology and hierarchical porous carbon encapsulation,the building of such C@VO_(2) composite can be highly expected to enhance the ion accessible site,boost the transport kinetics and thus performing a superior storage performance.Such design concept can be applied for other kinds of electrode materials and accelerating the development of highperformance AZIBs.

CO2-hierarchical activated carbon prepared from coal gasification residue: Adsorption equilibrium, isotherm, kinetic and thermodynamic studies for methylene blue removal

Mineral matter in a residue(RC G)from coal gasification(CG)was removed by two-stage acid leaching.Hierarchical activated carbon(HAC)was prepared by activating RC Gwith CO2.The performance of HAC on removing methylene blue(MB)from an aqueous solution was investigated.HAC was characterized by N2 adsorption–desorption isotherm,Fourier transform infrared spectroscopy,and scanning electron microscopy.The results show that HAC exhibits hierarchical pore structure with high specific surface area(862.76 m2·g-1)and total pore volume(0.684 cm3·g-1),and abundant organic functional groups.The adsorption equilibrium data of MB on HAC are best fitted to the Redlich-Peterson.The kinetic data show that the pseudo-first-order model is more suitable at low MB concentration,while the advantages of the pseudo-second-orderand the Elovich models are more obvious as the concentration increases.According to the thermodynamic parameters,the HAC-MB adsorption process is spontaneous and endothermic.

Nitrogen-doped hierarchical few-layered porous carbon for efficient electrochemical energy storage

Large surface area,high conductivity,and rich active site of carbon electrode materials are necessary characteristics for energy storage devices.However,high conductivity and high nitrogen doping of carbon electrode materials are difficult to coordinate.Here,a facile method via the carbonization of nitrogen-containing Schiff base polymer has been developed to prepare high conductivity and high nitrogen-doped hierarchical porous carbon.The organic components with a benzene ring structure in the polymer promote the formation of more sp^(2)-graphitized carbon,which is beneficial for the improvement of electrical conductivity.Nitrogen-doped hierarchical porous carbon calcined at 900℃ under the NH3 atmosphere possesses high nitrogen content of 7.48 at%,a large specific surface area of 1613.2m2/g,and high electrical conductivity of 2.7 S/cm.As electrode materials in an aqueous-based supercapacitor,nitrogen-doped hierarchical porous carbon exhibits superior specific capacitance of 385 F/g at 1 A/g as well as excellent rate performance(242 and 215 F/g at a current density of 100 and 200 A/g,respectively).In addition,the specific capacitance of electrode measured in a two-electrode system is 335 F/g at 1 A/g,and the long-term cycling stability can be achieved with more than 94%initial capacitance after 10000 cycles.The constructed symmetric supercapacitor delivers high energy density and high power density.The outstanding electrochemical performances combined with the novel and scalable synthetic approach make the nitrogen‐doped hierarchical porous carbon potential electrode material for electrochemical devices.

Hierarchical porous nitrogen,oxygen,and phosphorus ternary doped hollow biomass carbon spheres for high-speed and long-life potassium storage

Limited lithium resources have promoted the exploration of new battery technologies.Among them,potassium-ion batteries are considered as promising alternatives.At present,commercial graphite and other carbon-based materials have shown good prospects as anodes for potassium-ion batteries.However,the volume expansion and structural collapse caused by periodic K+insertion/extraction have severely restricted further development and application of potassium-ion batteries.A hollow biomass carbon ball(NOP-PB)ternarily doped with N,O,and P was synthesized and used as the negative electrode of a potassium-ion battery.X-ray photoelectron spectroscopy,Fourier‐transform infrared spectroscopy,and transmission electron microscopy confirmed that the hollow biomass carbon spheres were successfully doped with N,O,and P.Further analysis proved that N,O,and P ternary doping expands the interlayer distance of the graphite surface and introduces more defect sites.DFT calculations simultaneously proved that the K adsorption energy of the doped structure is greatly improved.The solid hollow hierarchical porous structure buffers the volume expansion of the potassium insertion process,maintains the original structure after a long cycle and promotes the transfer of potassium ions and electrons.Therefore,the NOP‐PB negative electrode shows extremely enhanced electrochemical performance,including high specific capacity,excellent long‐term stability,and good rate stability.

Dual template approach for the synthesis of hierarchically mesocellular carbon foams

We demonstrated a simple and effective dual-templating approach for the synthesis of hierarchically mesocellular carbon foams by using nonionic surfactant of sorbitan monooleate and silica colloid particles as sacrificial templates, and resorcinol/ formaldehyde as carbon source. The representative carbon foam has dual mesopore sizes of 4 and 10 nm, and possesses the specific surface area of 580 m^2/g and the total pore volume of 0.80 cm^3/g.

A novel one-step reaction sodium-sulfur battery with high areal sulfur loading on hierarchical porous carbon fiber

Room temperature sodium-sulfur(RT Na-S)batteries are gaining extensive attention as attractive alternatives for large-scale energy storage,due to low cost and high abundancy of sodium and sulfur in nature.However,the dilemmas regarding soluble polysulfides(Na_(2)Sn,4<n<8)and the inferior reaction kinetics limit their practical application.To address these issues,we report the activated porous carbon fibers(APCF)with small sulfur molecules(S2-4)confined in ultramicropores,to achieve a reversible single-step reaction in RT Na-S batteries.The mechanism is investigated by the in situ UV/vis spectroscopy,which demonstrates Na2S is the only product during the whole discharge process.Moreover,the hierarchical carbon structure can enhance areal sulfur loading without sacrificing the capacity due to thorough contact between electrolyte and sulfur electrode.As a consequence,the APCF electrode with 38 wt%sulfur(APCF-38S)delivers a high initial reversible specific capacity of 1412 mAh g^(-1) and 10.6mAh cm^(-2)(avg.areal sulfur loading:7.5 mg cm^(-2))at 0.1 C(1C=1675 mA g^(-1)),revealing high degree of sulfur utilization.This study provides a new strategy for the development of high areal capacity RT Na-S batteries.

Seaweed-Derived Hierarchically Porous Carbon for Highly Efficient Removal of Tetracycline

Herein we present a facile approach for the preparation of a novel hierarchically porous carbon,in which seaweeds serve as carbon source and KOH as activator.The fabricated KOH-activated seaweed carbon(KSC)displays strong affinity towards tetracycline with maximum uptake quantity of 853.3 mg/g,significantly higher than other tetracycline adsorbents.The superior adsorption capacity ascribes to large specific surface area(2614 m^(2)/g)and hierarchically porous structure of K-SC,along with strongπ-πinteractions between tetracycline and KSC.In addition,the as-prepared K-SC exhibits fast adsorption kinetics,capable of removing99%of tetracycline in 30 min.Meanwhile,the exhausted K-SC can be regenerated for four cycling adsorption without an obvious degradation in capacities.More importantly,p H and ionic strengths barely affect the adsorption performance of K-SC,implying electrostatic interactions hardly play any role in tetracycline adsorption process.Furthermore,the K-SC packed fixed-bed column(0.1 g of adsorbents)can continually treat 2780 m L solution spiked with 5.0 mg/g tetracycline before reaching the breakthrough point.All in all,the fabricated K-SC equips with high adsorption capacity,fast adsorption rate,glorious anti-interference capability and good reusability,which make it hold great feasibilities for treating tetracycline contamination in real applications.

Rambutan-like hierarchically porous carbon microsphere as electrodematerial for high-performance supercapacitors

Used as high-performance electrodes,both structural and compositional alterations of carbon materials play very important roles in energy conversion/storage devices.Especially in supercapacitors,hierarchical pores and heteroatom doping in carbon materials are indispensable.Here the rambutan-like hierarchically porous carbon microspheres(PCMs)have been constructed via a hydrothermal treatment,followed by carbonization/activation.The hierarchically porous microstructure is composed of three-dimensional porous carbon networks,which give rise to a large surface area.Moreover,N and O functional groups are introduced in the as-prepared samples,which could generate the extra pseudocapacitance.Benefitting from the interconnected hierarchical and open structure,PCM exhibits outstanding capacitive performance,for example,superior specific capacitance and rate capability(397 and 288 F g^(−1) at 0.5 and 20A g^(−1),respectively),as well as long cycling stability(about 95%capacitance retention after 10,000 cycles).These encouraging results may pave an efficient way to fabricate advanced supercapacitors in the future.

Facile Fabrication of Hierarchical Porous N/O Functionalized Carbon Derived from Blighted Grains Towards Electrochemical Capacitors

The hierarchical porous N/O co-functionalized carbon(HPNOC)was scalably prepared by using the lowcost and renewable blighted grains as the raw material coupled with mild KHCO_3 activation for electrochemical capacitors(ECs).The elemental N was in situ doped in the obtained HPNOC without any N-containing additives.Remarkably,the obtained HPNOC was endowed with a large specific surface area(about 2 624m^2·g^(-1)),high pore volume(about 1.35cm^3·g^(-1)),as well as high-content N/O functionalization(about 1.9%(in atom)N and about 10.2%(in atom)O.Furthermore,the as-resulted HPNOC electrode with a high mass loading of 5mg·cm^(-2 )exhibited competitive gravimetric capacitances of about 373.6F·g^(-1 )at 0.5A·g^(-1),and even about 260.4F·g^(-1 )at a high rate of 10A·g^(-1);superior capacitance retention of about 98.8%at 1A·g^(-1 )over 10 000consecutive cycles;and high specific energy of about 9.6W·h·kg^(-1 )at a power of 500W·kg^(-1),when evaluated as a promising electrode in 6mol KOH for advanced electrochemical supercapacitors.More encouragingly,the green synthetic strategy we developed holds a huge promise in generalizing for other biomass-derived carbon materials for versatile energy-related applications.