The chemical activation of various precursors is effective for creating additional closed pores in hard carbons for sodium storage.However,the formation mechanism of closed pores under the influence of pore-forming ag...The chemical activation of various precursors is effective for creating additional closed pores in hard carbons for sodium storage.However,the formation mechanism of closed pores under the influence of pore-forming agents is not well understood.Herein,an effective chemical activation followed by a high-temperature self-healing strategy is employed to generate interconnected closed pores in lignin-derived hard carbon(HCs).By systematic experimental design combined with electron paramagnetic res-onance spectroscopy,it can be found that the content of free radicals in the carbon matrix influences the closure of open pores at high temperatures.Excessively high activation temperature(>700 C)leads to a low free radical concentration,making it difficult to achieve self-healing of open pores at high tempera-tures.By activation at 700°C,a balance between pore making and self-healing is achieved in the final hard carbon.A large number of free radicals triggers rapid growth and aggregation of carbon microcrys-tals,blocking pre-formed open micropores and creating additional interconnected closed pores in as-obtained hard carbons.As a result,the optimized carbon anode(LK-700-1300)delivers a high reversible capacity of 330.8 mA h g^(-1) at 0.03 A g^(-1),which is an increase of 86 mA h g^(-1) compared to the pristine lignin-derived carbon anode(L-700-1300),and exhibits a good rate performance(202.1 mA h g^(-1) at 1 A g^(-1)).This work provides a universal and effective guidance for tuning closed pores of hard carbons from otherprecursors.展开更多
Nitrogen doping has been widely used to improve the performance of carbon electrodes in supercapacitors,particularly in terms of their high-frequency response.However,the charge storage and electrolyte ion response me...Nitrogen doping has been widely used to improve the performance of carbon electrodes in supercapacitors,particularly in terms of their high-frequency response.However,the charge storage and electrolyte ion response mechanisms of different nitrogen dopants at high frequencies are still unclear.In this study,melamine foam carbons with different configurations of surfacedoped N were formed by gradient carbonization,and the effects of the configurations on the high-frequency response behavior of the supercapacitors were analyzed.Using a combination of experiments and first-principle calculations,we found that pyrrolic N,characterized by a higher adsorption energy,increases the charge storage capacity of the electrode at high frequencies.On the other hand,graphitic N,with a lower adsorption energy,increases the speed of ion response.We propose the use of adsorption energy as a practical descriptor for electrode/electrolyte design in high-frequency applications,offering a more universal approach for improving the performance of N-doped carbon materials in supercapacitors.展开更多
Transition-metal phosphides(TMPs)with high catalytic activity are widely used in the design of electrodes for water splitting.However,a major challenge is how to achieve the trade-off between activity and stability of...Transition-metal phosphides(TMPs)with high catalytic activity are widely used in the design of electrodes for water splitting.However,a major challenge is how to achieve the trade-off between activity and stability of TMPs.Herein,a novel method for synthesizing CoP nanoparticles encapsu-lated in a rich-defect carbon shell(CoP/DCS)is developed through the self-assembly of modified polycyclic aromatic molecules.The graft and removal of high-activity C-N bonds of aromatic molecules render the controllable design of crystallite defects of carbon shell.The density functional theory calculation indicates that the carbon defects with unpaired electrons could effectively tailor the band structure of CoP.Benefiting from the improved activity and corrosion resistance,the CoP/DCS delivers outstanding difunctional hydrogen evolution reaction(88 mV)and oxygen evolution reaction(251 mV)performances at 10 mA cm^(−2)current density.Furthermore,the coupled water electrolyzer with CoP/DCS as both the cathode and anode presents ultralow cell voltages of 1.49 V to achieve 10 mA cm^(−2)with long-time stability.This strategy to improve TMPs electrocatalyst with rich-DCS and heterogeneous structure will inspire the design of other transition metal compound electrocatalysts for water splitting.展开更多
N-doped porous carbon has been extensively investigated for broad electrochemical applications.The performance is significantly impacted by the electrochemical double layer(EDL),which is material dependent and hard to...N-doped porous carbon has been extensively investigated for broad electrochemical applications.The performance is significantly impacted by the electrochemical double layer(EDL),which is material dependent and hard to characterize.Limited understanding of doping-derived EDL structure hinders insight into the structure-performance relations and the rational design of high-performance materials.Thus,we analyzed the mass and chemical composition variation of EDL within electrochemical operation by electrochemical quartz crystal microbalance,in-situ X-ray photoelectron spectroscopy,and time-offlight secondary ion mass spectrometry.We found that N-doping triggers specifically adsorbed propylene carbonate solvent in the inner Helmholtz plane(IHP),which prevents ion rearrangement and enhances the migration of cations.However,this specific adsorption accelerated solvent decomposition,rendering rapid performance degradation in practical devices.This work reveals that the surface chemistry of electrodes can cause specific adsorption of solvents and change the EDL structure,which complements the classical EDL theory and provide guidance for practical applications.展开更多
Metal-ion capacitors(including Li^(+),Na^(+),and K^(+))effectively combine a battery negative electrode capable of reversibly intercalating metal cations,together with an electrical double-layer positive electrode.How...Metal-ion capacitors(including Li^(+),Na^(+),and K^(+))effectively combine a battery negative electrode capable of reversibly intercalating metal cations,together with an electrical double-layer positive electrode.However,such novel cell design has a birth defect,namely kinetics mismatch between sluggish negative electrode and fast positive electrode,thus limiting the energy-power performance.Herein,we design a MoS_(2)-carbon composite anode with the ordered macroporous architecture and interlayer-expanded feature,exhibiting the fast and reversible Na^(+)redox processes.This kinetically favored anode is coupled with a homemade activated carbon cathode that allows for the excellent electrochemical performance of sodiumion capacitor with respect to large specific capacity,high-rate capability,and robust cycling.Through quantification of the potential swings of anode and cathode via a three-electrode Swagelok cell,we for the first time observe the abnormal variation law of potential swings and thus directly providing the evidence that the kinetics gap has been filled up by this kinetically favored anode.Our results represent a crucial step toward understanding the key issues of kinetics mismatch for hybrid cell,thus propelling the development of design of kinetically favored anode materials for high-performance metalion capacitors.展开更多
The state-of-the-art lithium-ion capacitors (LICs),consisting of high-capacity battery-type anode and high-rate capacitor-type cathode,can deliver high energy density and large power density when comparing with tradit...The state-of-the-art lithium-ion capacitors (LICs),consisting of high-capacity battery-type anode and high-rate capacitor-type cathode,can deliver high energy density and large power density when comparing with traditional supercapacitors and lithium-ion batteries,respectively.However,the ion kinetics mismatch between cathode and anode leads to unsatisfied cycling lifetime and anode degradation.Tremendous efforts have been devoted to solving the abovementioned issue.One promising strategy is altering high conductive hard carbon anode with excellent structural stability to match with activated carbon cathode,assembling dual-carbon LIC.In this contribution,one-pot in-situ expansion and heteroatom doping strategy was adopted to prepare sheet-like hard carbon,while activated carbon was obtained involving activation.Ammonium persulfate was used as expanding and doping agent simultaneously.While furfural residues (FR) were served as carbon precursor.The resulting hard carbon (FRNS-HC) and activated carbon (FRNS-AC)show excellent electrochemical performance as negative and positive electrodes in a lithium-ion battery (LIB).To be specific,374.2 m Ah g^(-1)and 123.1 m Ah g^(-1)can be achieved at 0.1 A g^(-1)and 5 A g^(-1)when FRNS-HC was tested as anode.When combined with a highly porous carbon cathode (S_(BET)=2961 m^(2)g^(-1)) synthesized from the same precursor,the LIC showed high specific energy of147.67 Wh kg^(-1)at approximately 199.93 W kg^(-1),and outstanding cycling life with negligible capacitance fading over 1000 cycles.This study could lead the way for the development of heteroatom-doped porous carbon nanomaterials applied to Li-based energy storage applications.展开更多
The presence of oxygen functional groups is detrimental to the capacitive performance of porous carbon electrode in organic electrolyte. In this regards, hydrogen thermal reduction has been demonstrated effective appr...The presence of oxygen functional groups is detrimental to the capacitive performance of porous carbon electrode in organic electrolyte. In this regards, hydrogen thermal reduction has been demonstrated effective approach in removing the unstable surface oxygen while maintaining the high porosity of carbon matrix. However, the exact evolution mechanism of various oxygen species during this process, as well as the correlation with electrochemical properties, is still under development. Herein, biomass-based porous carbon is adopted as the model material to trace its structure evolution of oxygen removal under hydrogen thermal reduction process with the temperature range of 400–800 °C. The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700°C. XPS, TPRMS and Boehm titration results indicate that the oxygen elimination undergoes three distinctive stages(intermolecular dehydration, hydrogenation and decomposition reactions). The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700 °C. Benefiting from the stable electrochemical interface and the optimized porous structure, the as-obtained HAC-700 exhibit significantly suppressed self-discharge and leak current, with improved cycling stability, which is attributable to the stabilization of electrochemical interface between carbon surface and electrolyte. The result provides insights for rational design of surface chemistry for high-performance carbon electrode towards advanced energy storage.展开更多
Starch,as a typical polysaccharide with natural spherical morphology,is not only a preferred precursor for preparing carbon materials but also a model polymer for investigating thermochemical evolution mechanisms.Howe...Starch,as a typical polysaccharide with natural spherical morphology,is not only a preferred precursor for preparing carbon materials but also a model polymer for investigating thermochemical evolution mechanisms.However,starch usually suffers from severe foaming and low carbon yield during direct pyrolysis.Herein,we report a simple and eco-friendly dry strategy,by maleic anhydride initiating the esterification of starch,to design carbon microspheres against the starch foaming.Moreover,the infuence of ester grafting on the pyrolytic behavior of starch is also focused.The formation of ester groups in precursor guarantees the structural stability of starch-based intermediate because it can promote the accumulation of unsaturated species and accelerate the water elimination during pyrolysis.Meanwhile,the esterification and dehydration reactions greatly deplete the primary hydroxyl groups in the starch molecules and thus the rapid levoglucosan release is inhibited,which well keeps the spherical morphology of starch and ensures the high carbon yield.In further exploration as anode materials for Lithium-ion batteries,the obtained carbon microspheres exhibit good cyclability and rate performance with a reversible capacity of 444 m Ah g^(-1)at 50 m A g^(-1).This work provides theoretical fundamentals for the controllable thermal transformation of biomass towards wide applications.展开更多
Hard carbons are widely investigated as potential anodes for lithium and sodium ion batteries owing to their internally well-tailored textures(closed pores and defects) and large microcrystalline interlayer spacing. T...Hard carbons are widely investigated as potential anodes for lithium and sodium ion batteries owing to their internally well-tailored textures(closed pores and defects) and large microcrystalline interlayer spacing. The renewable biomass is a green and economically attractive carbon source to produce hard carbons. However, the chemical and structural complexity of biomass has plagued the understanding of evolution mechanism from organic precursors to hard carbons and the structure-property relationship.This makes it difficult to finely tune the microstructure of biomass-derived hard carbons, thus greatly restricting their high-performance applications. Most recently, the optimal utilization and controllable conversion of biomass-derived biopolymers(such as starch, cellulose and lignin) at the molecular level have become a burgeoning area of research to develop hard carbons for advanced batteries.Considering the principal source of carbonaceous materials is from biomass pyrolysis, we firstly overview the chemical structures and pyrolysis behaviors of three main biopolymers. Then, the controllable preparation of hard carbons using various physicochemical properties of biopolymers at the molecular level is systematically discussed. Furthermore, we highlight present challenges and further opportunities in this field. The Review will guide future research works on the design of sustainable hard carbons and the optimization of battery performance.展开更多
In this work, a series of carbon aerogel microspheres（CAMs） with tailored pore structures were successfully prepared via a sol-gel method and subsequent heat-treatment at various temperatures from 600 to 1600 ℃. Th...In this work, a series of carbon aerogel microspheres（CAMs） with tailored pore structures were successfully prepared via a sol-gel method and subsequent heat-treatment at various temperatures from 600 to 1600 ℃. The effects of heat-treatment temperature（HTT） on the CAM microstructure were systematically investigated by physical and chemical characterization. The electrical conductivity increased by up to 250 S/cm and mesopores with high electrolyte accessibility developed in the CAM with increasing HTT. However, the specific surface area（SSA） decreased for HTTs from 1000 to 1600 ℃. The results show that these two factors should be finely balanced for further applications in high power supercapacitors.The CAMs carbonized at 1000 ℃ had the highest SSA（1454 m^2/g）, large mesoporous content（20%） and favorable conductivity（71 S/cm）. They delivered a high energy density of 38.4 Wh/kg at a power density of 0.17 kW/kg. They retained an energy density of 25.5 Wh/kg even at a high power density of 10.2 kW/kg,and a good rate capability of 84% after 10,000 cycles. This performance is superior to, or at least comparable to, those of most reported carbon materials.展开更多
Sustainable development based on the value-added utilization of furfural residues(FRs)is an effective way to achieve a profitable circular economy.This comprehensive work highlights the potential of FRs as precursor t...Sustainable development based on the value-added utilization of furfural residues(FRs)is an effective way to achieve a profitable circular economy.This comprehensive work highlights the potential of FRs as precursor to prepare porous carbons for high performance supercapacitors(SCs).To improve the electrochemical performance of FR-based carbon materials,a facile route based on methanol pretreatment coupled with pre-carbonization and followed KOH activation is proposed.More defects could be obtained after methanol treatment,which is incline to optimize textural structure.The activated methanol treated FR-based carbon materials(AFRMs)possess high specific surface area(1753.5 m^(2) g^(-1)),large pore volume(0.85 cm^(3) g^(-1)),interconnected micro/mesoporous structure,which endow the AFRMs with good electrochemical performance in half-cell(326.1 F g^(-1) at 0.1 Ag^(-1),189.4 Fg^(-1) at 50 A g^(-1) in 6 mol L^(-1) KOH).The constructed symmetric SCs based on KOH,KOH–K_(3)Fe(CN)_(6) and KOH-KI electrolyte deliver energy density up to 8.9,9.9 and 10.6 Wh kg^(-1) with a capacitance retention of over 86%after 10,000 cycles.Furthermore,the self-discharge can be restrained by the addition of K_(3)Fe(CN)_(6) and KI in KOH electrolyte.This study provides an effective approach for high-valued utilization of FR waste.展开更多
The Li-ion capacitors(LICs)develop rapidly due to their double-high features of high-energy density and high-power density.However,the relative low capacity of cathode and sluggish kinetics of anode seriously impede t...The Li-ion capacitors(LICs)develop rapidly due to their double-high features of high-energy density and high-power density.However,the relative low capacity of cathode and sluggish kinetics of anode seriously impede the development of LICs.Herein,the precisely pore-engineered and heteroatomtailored defective hierarchical porous carbons(DHPCs)as large-capacity cathode and high-rate anode to construct high-performance dual-carbon LICs have been developed.The DHPCs are prepared based on triple-activation mechanisms by direct pyrolysis of sustainable lignin with urea to generate the interconnected hierarchical porous structure and plentiful heteroatominduced defects.Benefiting from these advanced merits,DHPCs show the well-matched high capacity and fast kinetics of both cathode and anode,exhibiting large capacities,superior rate capability and long-term lifespan.Both experimental and computational results demonstrate the strong synergistic effect of pore and dopants for Li storage.Consequently,the assembled dual-carbon LIC exhibits high voltage of 4.5 V,high-energy density of 208 Wh kg^(−1),ultrahigh power density of 53.4 kW kg^(−1)and almost zerodecrement cycling lifetime.Impressively,the full device with high mass loading of 9.4 mg cm^(−2)on cathode still outputs high-energy density of 187 Wh kg^(−1),demonstrative of their potential as electrode materials for high-performance electrochemical devices.展开更多
The development of advanced bifunctional oxygen electrocatalysts for oxygen reduction and evolution reactions(ORR and OER) is critical to the practical application of zinc-air batteries(ZABs). Herein, a silica-assiste...The development of advanced bifunctional oxygen electrocatalysts for oxygen reduction and evolution reactions(ORR and OER) is critical to the practical application of zinc-air batteries(ZABs). Herein, a silica-assisted method is reported to integrate numerous accessible edge Fe-Nx sites into porous graphitic carbon(named Fe-N-G) for achieving highly active and robust oxygen electrocatalysis. Silica facilitates the formation of edge Fe-Nx sites and dense graphitic domains in carbon by inhibiting iron aggregation.The purification process creates a well-developed mass transfer channel for Fe-N-G. Consequently,Fe-N-G delivers a half-wave potential of 0.859 V in ORR and an overpotential of 344 m V at10 m A cm^(-2)in OER. During long-term operation, the graphitic layers protect edge Fe-Nx sites from demetallation in ORR and synergize with Fe OOH species endowing Fe-N-G with enhanced OER activity.Density functional theory calculations reveal that the edge Fe-Nx site is superior to the in-plane Fe-Nx site in terms of OH* dissociation in ORR and OOH* formation in OER. The constructed ZAB based on Fe-N-G cathode shows a higher peak power density of 133 m W cm^(-2)and more stable cycling performance than Pt/C + RuO2counterparts. This work provides a novel strategy to obtain high-efficiency bifunctional oxygen electrocatalysts through space mediation.展开更多
Closed pores formed in hard carbons play an essential role in sodium storage at plateau region.However,the effect of different structural features on the diffusion of sodium ions into closed pores remains unclear.Here...Closed pores formed in hard carbons play an essential role in sodium storage at plateau region.However,the effect of different structural features on the diffusion of sodium ions into closed pores remains unclear.Herein,a precursor reconstruction strategy is conducted to regulate carbon microstructures including interlayer spacing,defect concentration,and closed pore volume by changing the ratio of aromatic and polysaccharide components.Aromatic structure parts tend to develop disordered carbons with fewer defects,larger interlayer spacing,and smaller closed pore volume,while polysaccharide components prefer to form disordered carbons with more defects,smaller interlayer spacing,and larger closed pore volume.Through the correlation analysis of microstructure features and the sodium storage capacity below 0.1 V.It finds that the intercalation capacity is proportional to the ratio of pseudo-graphitic domains,whereas the pore filling capacity appeared at lower potential gradually decreases with the increasing defect concentration due to homo-ionic repulsion effect,without linear correlation with shortrange microcrystalline and closed pore volume.The optimized sample with suitable interlayer spacing and defect concentration exhibits a high plateau capacity of 241.7 m Ah/g.This work provides insights into the exploitation of closed pore sodium storage performance.展开更多
The burgeoning global economy during the past decades gives rise to the continuous increase in fossil fuels consumption and rapid growth of CO_(2) emission,which demands an urgent exploration into green and sustainabl...The burgeoning global economy during the past decades gives rise to the continuous increase in fossil fuels consumption and rapid growth of CO_(2) emission,which demands an urgent exploration into green and sustainable devices for energy storage and power management.Supercapacitors based on activated carbon electrodes are promising systems for highly efficient energy harvesting and power supply,but their promotion is hindered by the moderate energy density compared with batteries.Therefore,scalable conversion of CO_(2) into novel carbon nanostructures offers a powerful alternative to tackle both issues:mitigating the greenhouse effect caused by redundant atmospheric CO_(2) and providing carbon materials with enhanced electrochemical performances.In this tutorial review,the techniques,opportunities and barriers in the design and fabrication of advanced carbon materials using CO_(2) as feedstock as well as their impact on the energy-storage performances of supercapacitors are critically examined.In particular,the chemical aspects of various Cv2 conversion reactions are highlighted to establish a detailed understanding for the science and technology involved in the microstructural evolution,surface engineering and porosity control of CO_(2)-converted carbon nanostructures.Finally,the prospects and challenges associated with the industrialization of CO_(2) conversion and their practical application in supercapacitors are also discussed.展开更多
Lithium-sulfur battery(LSB) has high energy density but is limited by the polysulfides shuttle and dendrite growth during cycling. Herein, a free-standing cellulose nanofiber(CNF) separator is designed and fabricated ...Lithium-sulfur battery(LSB) has high energy density but is limited by the polysulfides shuttle and dendrite growth during cycling. Herein, a free-standing cellulose nanofiber(CNF) separator is designed and fabricated in isopropanol/water suspension through vacuum filtration progress. CNFs with abundant polar oxygen-containing functional groups can chemically immobilize the polysulfides, and suppress the formation of the dendrites by controlling the surface morphology of the SEI on lithium metal in LSB. The isopropanol content in a suspension can fine-tune the pore structure of the membrane to achieve optimal electrochemical performance. The prepared separator displays integrated advantages of an ultrathin thickness(19 μm), lightweight(0.87 mg cm^(-2)), extremely high porosity(98.05%), and decent electrolyte affinity. As a result, the discharge capacity of the LSB with CNF separator at the first and 100 th cycle is 1.4 and 1.3 times that of PP separator, respectively. Our research provides an environmentalfriendly and facile strategy for the preparation of multifunctional separators for LSBs.展开更多
Aqueous zinc ion hybrid capacitors(ZIHCs)hold great potential for large-scale energy storage applications owing to their high safety and low cost,but suffer from low capacity and energy density.Herein,pyridinic nitrog...Aqueous zinc ion hybrid capacitors(ZIHCs)hold great potential for large-scale energy storage applications owing to their high safety and low cost,but suffer from low capacity and energy density.Herein,pyridinic nitrogen enriched porous carbon(nPC)was successfully synthesized via the growth,subsequent annealing and acid etching of bimetal organic frameworks for high capacity and safe ZIHCs with exceptional rate capability.Benefiting from the mesopores for easy ion diffusion,high electrical conductivity enabled by in-situ grown carbon nanotubes matrix and residual metal Co nanoparticles for fast electron transfer,sufficient micropores and high N content(8.9 at%)with dominated pyridinic N(54%)for enhanced zinc ion storage,the resulting nPC cathodes for ZIHCs achieved high capacities of 302 and137 m Ah g^(-1) at 1 and 18 A g^(-1),outperforming most reported carbon based cathodes.Theoretical results further disclosed that pyridinic N possessed larger binding energy of-4.99 eV to chemically coordinate with Zn2+than other N species.Moreover,quasi-solid-state ZIHCs with gelatin based gel electrolytes exhibited high energy density of 157.6 Wh kg^(-1) at 0.69 kW kg^(-1),high safety and mechanical flexibility to withstand mechanical deformation and drilling.This strategy of developing pyridinic nitrogen enriched porous carbon will pave a new avenue to construct safe ZIHCs with high energy densities.展开更多
A facile hydrolysis method was applied to fabricate high-performance Co-layered double hydroxide（LDH）nanocages/graphene composites for supercapacitors. The materials exhibit enhanced rate capability than the counter...A facile hydrolysis method was applied to fabricate high-performance Co-layered double hydroxide（LDH）nanocages/graphene composites for supercapacitors. The materials exhibit enhanced rate capability than the counterpart electrode free of graphene while maintaining a high specific capacitance. In addition,such Co-LDH nanocages/graphene composites display an excellent cycling stability; the capacitance retention of Co-LDH nanocages/graphene composite electrode remains 90.4% after 10000 cycles at a current density of 2 A g（-1）. The integration of high capacity of double hydroxide and outstanding conductivity of graphene makes the delicately-designed composites promising candidates for electrode materials for supercapacitors.展开更多
Recently, binary metal oxides have been considerably researched for energy storage since it can provide higher electrical conductivity and electrochemical activity than single components. Besides, rational arrays stru...Recently, binary metal oxides have been considerably researched for energy storage since it can provide higher electrical conductivity and electrochemical activity than single components. Besides, rational arrays structure design can effectively enhance the utilization of active material. In this article, we synthesis a porous NiCo_2O_4 nanowires arrays, which were intimate contact with flexible carbon cloth（CC）by a facile hydrothermal reaction and calcination treatment. The rational array structures of NiCo_2O_4 facilitate the diffusion of electrolyte and effectively increase the utilization of active material. The asobtained NiCo_2O_4@CC electrode exhibits a high capacitance of 1183 mF cm^（-2） and an outstanding capacitance retention of 90.4% after 3000 cycles. Furthermore, a flexible asymmetric supercapacitor（ASC）using NiCo_2O_4@CC as positive electrode and activated carbon cloth（ACC） as negative electrode was fabricated, which delivers a large capacitance of 750 mF cm^（-2）（12.5 F cm^（-3））, a high energy density of 0.24 mWh cm^（-2）（3.91 mWh cm^（-3））, as well as excellent cycle stability under different bending states.These remarkable results suggest that as-assembled NiCo_2O_4@CC//ACC ASC is a promising candidate in flexible energy storage applications.展开更多
A new approach is provided to resolve the large-scale applications of coal tar pitch. Carbon foams with uniform pore size are prepared at the foaming pressure of normal pressure using coal tar pitch as raw materials. ...A new approach is provided to resolve the large-scale applications of coal tar pitch. Carbon foams with uniform pore size are prepared at the foaming pressure of normal pressure using coal tar pitch as raw materials. The physical and chemical performance of high softening point pitch(HSPP) can be regulated by vacuumizing owing to the cooperation of vacuumizing and polycondensation. Results indicate that the optimum softening point and weight ratio of quinoline insoluble are about 292℃ and 65.7%, respectively. And the optimum viscosity of HSPP during the foaming process is distributed in the range of 1000-10000 Pa·s. The resultant carbon foam exhibits excellent performance, such as uniform pore structure, high compressive strength(4.7 MPa), low thermal conductivity(0.07 W·m^(-1) ·K^(-1)), specially, it cannot be fired under the high temperature of 1200 ℃.Thus, this kind of carbon foam is a potential candidate for thermal insulation material applied in energy saving building.展开更多
基金supported by the National Natural Science Foundation of China (22379157,22179139)the Key Research and Development (R&D) Projects of Shanxi Province(202102040201003)+1 种基金the Research Program of Shanxi Province(202203021211203)the ICC CAS (SCJC-XCL-2023-10 and SCJC-XCL-2023-13)
文摘The chemical activation of various precursors is effective for creating additional closed pores in hard carbons for sodium storage.However,the formation mechanism of closed pores under the influence of pore-forming agents is not well understood.Herein,an effective chemical activation followed by a high-temperature self-healing strategy is employed to generate interconnected closed pores in lignin-derived hard carbon(HCs).By systematic experimental design combined with electron paramagnetic res-onance spectroscopy,it can be found that the content of free radicals in the carbon matrix influences the closure of open pores at high temperatures.Excessively high activation temperature(>700 C)leads to a low free radical concentration,making it difficult to achieve self-healing of open pores at high tempera-tures.By activation at 700°C,a balance between pore making and self-healing is achieved in the final hard carbon.A large number of free radicals triggers rapid growth and aggregation of carbon microcrys-tals,blocking pre-formed open micropores and creating additional interconnected closed pores in as-obtained hard carbons.As a result,the optimized carbon anode(LK-700-1300)delivers a high reversible capacity of 330.8 mA h g^(-1) at 0.03 A g^(-1),which is an increase of 86 mA h g^(-1) compared to the pristine lignin-derived carbon anode(L-700-1300),and exhibits a good rate performance(202.1 mA h g^(-1) at 1 A g^(-1)).This work provides a universal and effective guidance for tuning closed pores of hard carbons from otherprecursors.
文摘Nitrogen doping has been widely used to improve the performance of carbon electrodes in supercapacitors,particularly in terms of their high-frequency response.However,the charge storage and electrolyte ion response mechanisms of different nitrogen dopants at high frequencies are still unclear.In this study,melamine foam carbons with different configurations of surfacedoped N were formed by gradient carbonization,and the effects of the configurations on the high-frequency response behavior of the supercapacitors were analyzed.Using a combination of experiments and first-principle calculations,we found that pyrrolic N,characterized by a higher adsorption energy,increases the charge storage capacity of the electrode at high frequencies.On the other hand,graphitic N,with a lower adsorption energy,increases the speed of ion response.We propose the use of adsorption energy as a practical descriptor for electrode/electrolyte design in high-frequency applications,offering a more universal approach for improving the performance of N-doped carbon materials in supercapacitors.
基金Youth Innovation Promotion Association of the Chinese Academy of Sciences,Grant/Award Number:2021174National Natural Science Foundation of China,Grant/Award Number:51902326Natural Science Foundation of Shanxi Province,Grant/Award Numbers:201901D211588,20210302124421。
文摘Transition-metal phosphides(TMPs)with high catalytic activity are widely used in the design of electrodes for water splitting.However,a major challenge is how to achieve the trade-off between activity and stability of TMPs.Herein,a novel method for synthesizing CoP nanoparticles encapsu-lated in a rich-defect carbon shell(CoP/DCS)is developed through the self-assembly of modified polycyclic aromatic molecules.The graft and removal of high-activity C-N bonds of aromatic molecules render the controllable design of crystallite defects of carbon shell.The density functional theory calculation indicates that the carbon defects with unpaired electrons could effectively tailor the band structure of CoP.Benefiting from the improved activity and corrosion resistance,the CoP/DCS delivers outstanding difunctional hydrogen evolution reaction(88 mV)and oxygen evolution reaction(251 mV)performances at 10 mA cm^(−2)current density.Furthermore,the coupled water electrolyzer with CoP/DCS as both the cathode and anode presents ultralow cell voltages of 1.49 V to achieve 10 mA cm^(−2)with long-time stability.This strategy to improve TMPs electrocatalyst with rich-DCS and heterogeneous structure will inspire the design of other transition metal compound electrocatalysts for water splitting.
基金the National Science Foundation for Excellent Young Scholars of China(21922815)the National Natural Science Foundation of China(22179139)+2 种基金the National Key Research and Development Program of China(2020YFB1505800)the Youth Innovation Promotion Association of CAS(2019178)the“Transformational Technologies for Clean Energy and Demonstration”Strategic Priority Research Program of the CAS(XDA21000000)。
文摘N-doped porous carbon has been extensively investigated for broad electrochemical applications.The performance is significantly impacted by the electrochemical double layer(EDL),which is material dependent and hard to characterize.Limited understanding of doping-derived EDL structure hinders insight into the structure-performance relations and the rational design of high-performance materials.Thus,we analyzed the mass and chemical composition variation of EDL within electrochemical operation by electrochemical quartz crystal microbalance,in-situ X-ray photoelectron spectroscopy,and time-offlight secondary ion mass spectrometry.We found that N-doping triggers specifically adsorbed propylene carbonate solvent in the inner Helmholtz plane(IHP),which prevents ion rearrangement and enhances the migration of cations.However,this specific adsorption accelerated solvent decomposition,rendering rapid performance degradation in practical devices.This work reveals that the surface chemistry of electrodes can cause specific adsorption of solvents and change the EDL structure,which complements the classical EDL theory and provide guidance for practical applications.
基金supported by National Natural Science Foundation of China(No.51902188)Natural Science Foundation of Jiangsu Province(No.BK20190207)+1 种基金Natural Science Doctoral Foundation of Shandong Province(No.ZR2019BB057)the CAS Key Laboratory of Carbon Materials(No.KLCMKFJJ2006).
文摘Metal-ion capacitors(including Li^(+),Na^(+),and K^(+))effectively combine a battery negative electrode capable of reversibly intercalating metal cations,together with an electrical double-layer positive electrode.However,such novel cell design has a birth defect,namely kinetics mismatch between sluggish negative electrode and fast positive electrode,thus limiting the energy-power performance.Herein,we design a MoS_(2)-carbon composite anode with the ordered macroporous architecture and interlayer-expanded feature,exhibiting the fast and reversible Na^(+)redox processes.This kinetically favored anode is coupled with a homemade activated carbon cathode that allows for the excellent electrochemical performance of sodiumion capacitor with respect to large specific capacity,high-rate capability,and robust cycling.Through quantification of the potential swings of anode and cathode via a three-electrode Swagelok cell,we for the first time observe the abnormal variation law of potential swings and thus directly providing the evidence that the kinetics gap has been filled up by this kinetically favored anode.Our results represent a crucial step toward understanding the key issues of kinetics mismatch for hybrid cell,thus propelling the development of design of kinetically favored anode materials for high-performance metalion capacitors.
基金financially supported by the National Natural Science Foundation of China (22075308, 22209197)Natural Science Foundation of Shanxi Province (20210302 1224439, 202203021211002)Shanxi Province Science Foundation for Youths (No: SQ2019001)。
文摘The state-of-the-art lithium-ion capacitors (LICs),consisting of high-capacity battery-type anode and high-rate capacitor-type cathode,can deliver high energy density and large power density when comparing with traditional supercapacitors and lithium-ion batteries,respectively.However,the ion kinetics mismatch between cathode and anode leads to unsatisfied cycling lifetime and anode degradation.Tremendous efforts have been devoted to solving the abovementioned issue.One promising strategy is altering high conductive hard carbon anode with excellent structural stability to match with activated carbon cathode,assembling dual-carbon LIC.In this contribution,one-pot in-situ expansion and heteroatom doping strategy was adopted to prepare sheet-like hard carbon,while activated carbon was obtained involving activation.Ammonium persulfate was used as expanding and doping agent simultaneously.While furfural residues (FR) were served as carbon precursor.The resulting hard carbon (FRNS-HC) and activated carbon (FRNS-AC)show excellent electrochemical performance as negative and positive electrodes in a lithium-ion battery (LIB).To be specific,374.2 m Ah g^(-1)and 123.1 m Ah g^(-1)can be achieved at 0.1 A g^(-1)and 5 A g^(-1)when FRNS-HC was tested as anode.When combined with a highly porous carbon cathode (S_(BET)=2961 m^(2)g^(-1)) synthesized from the same precursor,the LIC showed high specific energy of147.67 Wh kg^(-1)at approximately 199.93 W kg^(-1),and outstanding cycling life with negligible capacitance fading over 1000 cycles.This study could lead the way for the development of heteroatom-doped porous carbon nanomaterials applied to Li-based energy storage applications.
基金National Science Foundation for Excellent Young Scholars of China (21922815)Key Research and Development (R&D) Projects of Shanxi Province (201903D121007)+3 种基金Natural Science Foundations of Shanxi Province (201801D221156)DNL Cooperation Fund of CAS (DNL180308)Science and Technology Service Network Initiative of CAS (KFJ-STS-ZDTP-068)Youth Innovation Promotion Association of CAS。
文摘The presence of oxygen functional groups is detrimental to the capacitive performance of porous carbon electrode in organic electrolyte. In this regards, hydrogen thermal reduction has been demonstrated effective approach in removing the unstable surface oxygen while maintaining the high porosity of carbon matrix. However, the exact evolution mechanism of various oxygen species during this process, as well as the correlation with electrochemical properties, is still under development. Herein, biomass-based porous carbon is adopted as the model material to trace its structure evolution of oxygen removal under hydrogen thermal reduction process with the temperature range of 400–800 °C. The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700°C. XPS, TPRMS and Boehm titration results indicate that the oxygen elimination undergoes three distinctive stages(intermolecular dehydration, hydrogenation and decomposition reactions). The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700 °C. Benefiting from the stable electrochemical interface and the optimized porous structure, the as-obtained HAC-700 exhibit significantly suppressed self-discharge and leak current, with improved cycling stability, which is attributable to the stabilization of electrochemical interface between carbon surface and electrolyte. The result provides insights for rational design of surface chemistry for high-performance carbon electrode towards advanced energy storage.
基金supported by the National Science Foundation for Excellent Young Scholars of China(21922815)the Key Research and Development(R&D)Projects of Shanxi Province(201903D121180)the National Key Research and Development(R&D)Program of China。
文摘Starch,as a typical polysaccharide with natural spherical morphology,is not only a preferred precursor for preparing carbon materials but also a model polymer for investigating thermochemical evolution mechanisms.However,starch usually suffers from severe foaming and low carbon yield during direct pyrolysis.Herein,we report a simple and eco-friendly dry strategy,by maleic anhydride initiating the esterification of starch,to design carbon microspheres against the starch foaming.Moreover,the infuence of ester grafting on the pyrolytic behavior of starch is also focused.The formation of ester groups in precursor guarantees the structural stability of starch-based intermediate because it can promote the accumulation of unsaturated species and accelerate the water elimination during pyrolysis.Meanwhile,the esterification and dehydration reactions greatly deplete the primary hydroxyl groups in the starch molecules and thus the rapid levoglucosan release is inhibited,which well keeps the spherical morphology of starch and ensures the high carbon yield.In further exploration as anode materials for Lithium-ion batteries,the obtained carbon microspheres exhibit good cyclability and rate performance with a reversible capacity of 444 m Ah g^(-1)at 50 m A g^(-1).This work provides theoretical fundamentals for the controllable thermal transformation of biomass towards wide applications.
基金the support of this work by the Fundamental Research Program of Shanxi Province(20210302123008,20210302124101)the Youth Innovation Promotion Association of CAS(2019178)+1 种基金the National Science Foundation for Excellent Young Scholars of China(21922815)the National Natural Science Foundation of China(21975275,22179139)。
文摘Hard carbons are widely investigated as potential anodes for lithium and sodium ion batteries owing to their internally well-tailored textures(closed pores and defects) and large microcrystalline interlayer spacing. The renewable biomass is a green and economically attractive carbon source to produce hard carbons. However, the chemical and structural complexity of biomass has plagued the understanding of evolution mechanism from organic precursors to hard carbons and the structure-property relationship.This makes it difficult to finely tune the microstructure of biomass-derived hard carbons, thus greatly restricting their high-performance applications. Most recently, the optimal utilization and controllable conversion of biomass-derived biopolymers(such as starch, cellulose and lignin) at the molecular level have become a burgeoning area of research to develop hard carbons for advanced batteries.Considering the principal source of carbonaceous materials is from biomass pyrolysis, we firstly overview the chemical structures and pyrolysis behaviors of three main biopolymers. Then, the controllable preparation of hard carbons using various physicochemical properties of biopolymers at the molecular level is systematically discussed. Furthermore, we highlight present challenges and further opportunities in this field. The Review will guide future research works on the design of sustainable hard carbons and the optimization of battery performance.
基金supported by the National Natural Science Foundation of China (51402324, 51002166 and 51402325)
文摘In this work, a series of carbon aerogel microspheres（CAMs） with tailored pore structures were successfully prepared via a sol-gel method and subsequent heat-treatment at various temperatures from 600 to 1600 ℃. The effects of heat-treatment temperature（HTT） on the CAM microstructure were systematically investigated by physical and chemical characterization. The electrical conductivity increased by up to 250 S/cm and mesopores with high electrolyte accessibility developed in the CAM with increasing HTT. However, the specific surface area（SSA） decreased for HTTs from 1000 to 1600 ℃. The results show that these two factors should be finely balanced for further applications in high power supercapacitors.The CAMs carbonized at 1000 ℃ had the highest SSA（1454 m^2/g）, large mesoporous content（20%） and favorable conductivity（71 S/cm）. They delivered a high energy density of 38.4 Wh/kg at a power density of 0.17 kW/kg. They retained an energy density of 25.5 Wh/kg even at a high power density of 10.2 kW/kg,and a good rate capability of 84% after 10,000 cycles. This performance is superior to, or at least comparable to, those of most reported carbon materials.
基金financially supported by the National Natural Science Foundation of China(22075308,U1710106,U1810111)Natural Science Foundation of Shanxi Province(No:201801D221371)Shanxi Province Science Foundation for Youths(No:SQ2019001).
文摘Sustainable development based on the value-added utilization of furfural residues(FRs)is an effective way to achieve a profitable circular economy.This comprehensive work highlights the potential of FRs as precursor to prepare porous carbons for high performance supercapacitors(SCs).To improve the electrochemical performance of FR-based carbon materials,a facile route based on methanol pretreatment coupled with pre-carbonization and followed KOH activation is proposed.More defects could be obtained after methanol treatment,which is incline to optimize textural structure.The activated methanol treated FR-based carbon materials(AFRMs)possess high specific surface area(1753.5 m^(2) g^(-1)),large pore volume(0.85 cm^(3) g^(-1)),interconnected micro/mesoporous structure,which endow the AFRMs with good electrochemical performance in half-cell(326.1 F g^(-1) at 0.1 Ag^(-1),189.4 Fg^(-1) at 50 A g^(-1) in 6 mol L^(-1) KOH).The constructed symmetric SCs based on KOH,KOH–K_(3)Fe(CN)_(6) and KOH-KI electrolyte deliver energy density up to 8.9,9.9 and 10.6 Wh kg^(-1) with a capacitance retention of over 86%after 10,000 cycles.Furthermore,the self-discharge can be restrained by the addition of K_(3)Fe(CN)_(6) and KI in KOH electrolyte.This study provides an effective approach for high-valued utilization of FR waste.
基金financialy supported by National Natural Science Foundation of China(Grants 22005298,22125903,51872283,22075279,22279137)Dalian Innovation Support Plan for High Level Talents(2019RT09)+3 种基金Dalian National Laboratory For Clean Energy(DNL),CAS,DNL Cooperation Fund,CAS(DNL201912,DNL201915,DNL202016,DNL202019),DICP(DICP I2020032)The Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy(YLUDNL Fund 2021002,YLU-DNL Fund 2021009)Suzhou University Scientific Research Platform(2021XJPT07)China Postdoctoral Science Foundation(2019 M661141)
文摘The Li-ion capacitors(LICs)develop rapidly due to their double-high features of high-energy density and high-power density.However,the relative low capacity of cathode and sluggish kinetics of anode seriously impede the development of LICs.Herein,the precisely pore-engineered and heteroatomtailored defective hierarchical porous carbons(DHPCs)as large-capacity cathode and high-rate anode to construct high-performance dual-carbon LICs have been developed.The DHPCs are prepared based on triple-activation mechanisms by direct pyrolysis of sustainable lignin with urea to generate the interconnected hierarchical porous structure and plentiful heteroatominduced defects.Benefiting from these advanced merits,DHPCs show the well-matched high capacity and fast kinetics of both cathode and anode,exhibiting large capacities,superior rate capability and long-term lifespan.Both experimental and computational results demonstrate the strong synergistic effect of pore and dopants for Li storage.Consequently,the assembled dual-carbon LIC exhibits high voltage of 4.5 V,high-energy density of 208 Wh kg^(−1),ultrahigh power density of 53.4 kW kg^(−1)and almost zerodecrement cycling lifetime.Impressively,the full device with high mass loading of 9.4 mg cm^(−2)on cathode still outputs high-energy density of 187 Wh kg^(−1),demonstrative of their potential as electrode materials for high-performance electrochemical devices.
基金financial support from the National Key Research and Development Project (2017YFB0308200)the CAS Key Laboratory of Carbon Materials (KLCMKFJJ2011)。
文摘The development of advanced bifunctional oxygen electrocatalysts for oxygen reduction and evolution reactions(ORR and OER) is critical to the practical application of zinc-air batteries(ZABs). Herein, a silica-assisted method is reported to integrate numerous accessible edge Fe-Nx sites into porous graphitic carbon(named Fe-N-G) for achieving highly active and robust oxygen electrocatalysis. Silica facilitates the formation of edge Fe-Nx sites and dense graphitic domains in carbon by inhibiting iron aggregation.The purification process creates a well-developed mass transfer channel for Fe-N-G. Consequently,Fe-N-G delivers a half-wave potential of 0.859 V in ORR and an overpotential of 344 m V at10 m A cm^(-2)in OER. During long-term operation, the graphitic layers protect edge Fe-Nx sites from demetallation in ORR and synergize with Fe OOH species endowing Fe-N-G with enhanced OER activity.Density functional theory calculations reveal that the edge Fe-Nx site is superior to the in-plane Fe-Nx site in terms of OH* dissociation in ORR and OOH* formation in OER. The constructed ZAB based on Fe-N-G cathode shows a higher peak power density of 133 m W cm^(-2)and more stable cycling performance than Pt/C + RuO2counterparts. This work provides a novel strategy to obtain high-efficiency bifunctional oxygen electrocatalysts through space mediation.
基金supported by the National Key Research and Development(R&D)Program of China(No.2020YFB1505803)the Youth Innovation Promotion Association of CAS(No.2019178)the Innovation Fund for Basic Research Program supported by ICC CAS(Nos.SCJC-XCL-2023-10,SCJC-XCL-2023-13)。
文摘Closed pores formed in hard carbons play an essential role in sodium storage at plateau region.However,the effect of different structural features on the diffusion of sodium ions into closed pores remains unclear.Herein,a precursor reconstruction strategy is conducted to regulate carbon microstructures including interlayer spacing,defect concentration,and closed pore volume by changing the ratio of aromatic and polysaccharide components.Aromatic structure parts tend to develop disordered carbons with fewer defects,larger interlayer spacing,and smaller closed pore volume,while polysaccharide components prefer to form disordered carbons with more defects,smaller interlayer spacing,and larger closed pore volume.Through the correlation analysis of microstructure features and the sodium storage capacity below 0.1 V.It finds that the intercalation capacity is proportional to the ratio of pseudo-graphitic domains,whereas the pore filling capacity appeared at lower potential gradually decreases with the increasing defect concentration due to homo-ionic repulsion effect,without linear correlation with shortrange microcrystalline and closed pore volume.The optimized sample with suitable interlayer spacing and defect concentration exhibits a high plateau capacity of 241.7 m Ah/g.This work provides insights into the exploitation of closed pore sodium storage performance.
基金financially supported by the National Natural Science Foundation of China(No.51907193 and No.51677182)the Dalian National Laboratory(DNL)for Clean Energy Cooperation Fund,CAS(No.DNL201915 and No.DNL201912)+2 种基金the Beijing Municipal Science and Technology Commission(No.Z181100000118006)the Key Research Program of Frontier Sciences,CAS(No.ZDBS-LY-JSC047)the Youth Innovation Promotion Association,CAS(No.2020000022)。
文摘The burgeoning global economy during the past decades gives rise to the continuous increase in fossil fuels consumption and rapid growth of CO_(2) emission,which demands an urgent exploration into green and sustainable devices for energy storage and power management.Supercapacitors based on activated carbon electrodes are promising systems for highly efficient energy harvesting and power supply,but their promotion is hindered by the moderate energy density compared with batteries.Therefore,scalable conversion of CO_(2) into novel carbon nanostructures offers a powerful alternative to tackle both issues:mitigating the greenhouse effect caused by redundant atmospheric CO_(2) and providing carbon materials with enhanced electrochemical performances.In this tutorial review,the techniques,opportunities and barriers in the design and fabrication of advanced carbon materials using CO_(2) as feedstock as well as their impact on the energy-storage performances of supercapacitors are critically examined.In particular,the chemical aspects of various Cv2 conversion reactions are highlighted to establish a detailed understanding for the science and technology involved in the microstructural evolution,surface engineering and porosity control of CO_(2)-converted carbon nanostructures.Finally,the prospects and challenges associated with the industrialization of CO_(2) conversion and their practical application in supercapacitors are also discussed.
基金supported by the National Key Research and Development Program(2018YFB1501500)the National Science Foundation for Excellent Young Scholars of China(21922815)+2 种基金the National Key Research and Development(R&D)Program of China(2020YFB1505800)the Research and Development Project of Key Core and Common Technology of Shanxi Province(2020XXX014)the Fundamental Research Program of Shanxi Province(20210302123008,20210302124101)。
文摘Lithium-sulfur battery(LSB) has high energy density but is limited by the polysulfides shuttle and dendrite growth during cycling. Herein, a free-standing cellulose nanofiber(CNF) separator is designed and fabricated in isopropanol/water suspension through vacuum filtration progress. CNFs with abundant polar oxygen-containing functional groups can chemically immobilize the polysulfides, and suppress the formation of the dendrites by controlling the surface morphology of the SEI on lithium metal in LSB. The isopropanol content in a suspension can fine-tune the pore structure of the membrane to achieve optimal electrochemical performance. The prepared separator displays integrated advantages of an ultrathin thickness(19 μm), lightweight(0.87 mg cm^(-2)), extremely high porosity(98.05%), and decent electrolyte affinity. As a result, the discharge capacity of the LSB with CNF separator at the first and 100 th cycle is 1.4 and 1.3 times that of PP separator, respectively. Our research provides an environmentalfriendly and facile strategy for the preparation of multifunctional separators for LSBs.
基金financially supported by the National Key R@D Program of China(Grants 2016YBF0100100 and 2016YFA0200200)National Natural Science Foundation of China(Grants 51872283,and 21805273)+8 种基金Liaoning BaiQianWan Talents Program,LiaoNing Revitalization Talents Program(Grant XLYC1807153)Natural Science Foundation of Liaoning Province(2020-MS-095)Joint Research Fund Liaoning-Shenyang National Laboratory for Materials Science(Grants 20180510038)DICP(DICP ZZBS201708,DICP ZZBS201802,and DICP I202032)DICP&QIBEBT(Grant No.DICP&QIBEBT UN201702)Dalian National Laboratory For Clean Energy(DNL),CAS,DNL Cooperation Fund,CAS(DNL180310,DNL180308,DNL201912,and DNL201915)the Fundamental Research Funds for the Central Universities of China(N180503012)the State Key Laboratory of Fine Chemicals(KF1911)the CAS Key Laboratory of Carbon Materials(KLCMKFJJ2004)。
文摘Aqueous zinc ion hybrid capacitors(ZIHCs)hold great potential for large-scale energy storage applications owing to their high safety and low cost,but suffer from low capacity and energy density.Herein,pyridinic nitrogen enriched porous carbon(nPC)was successfully synthesized via the growth,subsequent annealing and acid etching of bimetal organic frameworks for high capacity and safe ZIHCs with exceptional rate capability.Benefiting from the mesopores for easy ion diffusion,high electrical conductivity enabled by in-situ grown carbon nanotubes matrix and residual metal Co nanoparticles for fast electron transfer,sufficient micropores and high N content(8.9 at%)with dominated pyridinic N(54%)for enhanced zinc ion storage,the resulting nPC cathodes for ZIHCs achieved high capacities of 302 and137 m Ah g^(-1) at 1 and 18 A g^(-1),outperforming most reported carbon based cathodes.Theoretical results further disclosed that pyridinic N possessed larger binding energy of-4.99 eV to chemically coordinate with Zn2+than other N species.Moreover,quasi-solid-state ZIHCs with gelatin based gel electrolytes exhibited high energy density of 157.6 Wh kg^(-1) at 0.69 kW kg^(-1),high safety and mechanical flexibility to withstand mechanical deformation and drilling.This strategy of developing pyridinic nitrogen enriched porous carbon will pave a new avenue to construct safe ZIHCs with high energy densities.
基金Supports by the Jilin Province/Jilin University co-Construction Project-Funds for New Materials (SXGJSF2017-3, Branch2/440050316A36)the National Key R&D Program of China (2016YFA0200400)+2 种基金the NSFC (51372095), the Program for JLU Science and Technology Innovative Research Team (JLUSTIRT)“Double-First Class” Discipline for Materials Science & Engineeringthe Special Funding for Academic Leaders
文摘A facile hydrolysis method was applied to fabricate high-performance Co-layered double hydroxide（LDH）nanocages/graphene composites for supercapacitors. The materials exhibit enhanced rate capability than the counterpart electrode free of graphene while maintaining a high specific capacitance. In addition,such Co-LDH nanocages/graphene composites display an excellent cycling stability; the capacitance retention of Co-LDH nanocages/graphene composite electrode remains 90.4% after 10000 cycles at a current density of 2 A g（-1）. The integration of high capacity of double hydroxide and outstanding conductivity of graphene makes the delicately-designed composites promising candidates for electrode materials for supercapacitors.
基金supported by the National Natural Science Foundation of China(Grant nos.51402324,51402325,51302281)
文摘Recently, binary metal oxides have been considerably researched for energy storage since it can provide higher electrical conductivity and electrochemical activity than single components. Besides, rational arrays structure design can effectively enhance the utilization of active material. In this article, we synthesis a porous NiCo_2O_4 nanowires arrays, which were intimate contact with flexible carbon cloth（CC）by a facile hydrothermal reaction and calcination treatment. The rational array structures of NiCo_2O_4 facilitate the diffusion of electrolyte and effectively increase the utilization of active material. The asobtained NiCo_2O_4@CC electrode exhibits a high capacitance of 1183 mF cm^（-2） and an outstanding capacitance retention of 90.4% after 3000 cycles. Furthermore, a flexible asymmetric supercapacitor（ASC）using NiCo_2O_4@CC as positive electrode and activated carbon cloth（ACC） as negative electrode was fabricated, which delivers a large capacitance of 750 mF cm^（-2）（12.5 F cm^（-3））, a high energy density of 0.24 mWh cm^（-2）（3.91 mWh cm^（-3））, as well as excellent cycle stability under different bending states.These remarkable results suggest that as-assembled NiCo_2O_4@CC//ACC ASC is a promising candidate in flexible energy storage applications.
基金Supported by the National Natural Science Foundation of China(51472086,51002051)CAS Key Laboratory of Carbon Materials(No KLCMKFJJ1703)
文摘A new approach is provided to resolve the large-scale applications of coal tar pitch. Carbon foams with uniform pore size are prepared at the foaming pressure of normal pressure using coal tar pitch as raw materials. The physical and chemical performance of high softening point pitch(HSPP) can be regulated by vacuumizing owing to the cooperation of vacuumizing and polycondensation. Results indicate that the optimum softening point and weight ratio of quinoline insoluble are about 292℃ and 65.7%, respectively. And the optimum viscosity of HSPP during the foaming process is distributed in the range of 1000-10000 Pa·s. The resultant carbon foam exhibits excellent performance, such as uniform pore structure, high compressive strength(4.7 MPa), low thermal conductivity(0.07 W·m^(-1) ·K^(-1)), specially, it cannot be fired under the high temperature of 1200 ℃.Thus, this kind of carbon foam is a potential candidate for thermal insulation material applied in energy saving building.
