A new MEEKC method assisted with pressure-driven mobile phase was presented for the separation of felted explosives. Microemulsion solution was composed of 80 mmol/L heptane -120 mmol/L SDS (sodium dodecyl sulphate) -...A new MEEKC method assisted with pressure-driven mobile phase was presented for the separation of felted explosives. Microemulsion solution was composed of 80 mmol/L heptane -120 mmol/L SDS (sodium dodecyl sulphate) - 900 mmol/L butanol - 10 mmol/L borate at pH 9.4 and a pressure-driven flow of 0.020 mL/min under 1.3 MPa was employed to manipulate the separation. Explosives HMX (1, 3, 5, 7-tetranitro-l, 3, 5, 7-tetrazacyclooctane) and TATB (triamino-trinitrobenzene), which were felted on fluorine rubber F2311 (polytrifluorochlorethylene and polyvinylidene fluoride 1/1 co-polymerization) and F2314 (polytrifluorochlorethylene and polyvinylidene fluoride 4/1 co-polymerization) were well separated with very good peak shapes.展开更多
MXene,a transition metal carbide/nitride,has been prominent as an ideal electrochemical active material for supercapacitors.However,the low MXene load limits its practical applications.As environmental concerns and su...MXene,a transition metal carbide/nitride,has been prominent as an ideal electrochemical active material for supercapacitors.However,the low MXene load limits its practical applications.As environmental concerns and sustainable development become more widely recognized,it is necessary to explore a greener and cleaner technology to recycle textile by-products such as cotton.The present study proposes an effective 3D fabrication method that uses MXene to fabricate waste denim felt into ultralight and flexible supercapacitors through needling and carbonization.The 3D structure provided more sites for loading MXene onto Z-directional fiber bundles,resulting in more efficient ion exchange between the electrolyte and electrodes.Furthermore,the carbonization process removed the specific adverse groups in MXenes,further improving the specific capacitance,energy density,power density and electrical conductivity of supercapacitors.The electrodes achieve a maximum specific capacitance of 1748.5 mF cm-2 and demonstrate remarkable cycling stability maintaining more than 94%after 15,000 galvanostatic charge/discharge cycles.Besides,the obtained supercapacitors present a maximum specific capacitance of 577.5 mF cm^(-2),energy density of 80.2μWh cm^(-2)and power density of 3 mW cm^(-2),respectively.The resulting supercapacitors can be used to develop smart wearable power devices such as smartwatches,laying the foundation for a novel strategy of utilizing waste cotton in a high-quality manner.展开更多
The scarcity of wettability,insufficient active sites,and low surface area of graphite felt(GF)have long been suppressing the performance of vanadium redox flow batteries(VRFBs).Herein,an ultra-homogeneous multipledim...The scarcity of wettability,insufficient active sites,and low surface area of graphite felt(GF)have long been suppressing the performance of vanadium redox flow batteries(VRFBs).Herein,an ultra-homogeneous multipledimensioned defect,including nano-scale etching and atomic-scale N,O codoping,was used to modify GF by the molten salt system.NH_(4)Cl and KClO_(3) were added simultaneously to the system to obtain porous N/O co-doped electrode(GF/ON),where KClO_(3) was used to ultra-homogeneously etch,and O-functionalize electrode,and NH4Cl was used as N dopant,respectively.GF/ON presents better electrochemical catalysis for VO_(2)+/VO_(2)+ and V3+/V2+ reactions than only O-functionalized electrodes(GF/O)and GF.The enhanced electrochemical properties are attributed to an increase in active sites,surface area,and wettability,as well as the synergistic effect of N and O,which is also supported by the density functional theory calculations.Further,the cell using GF/ON shows higher discharge capacity,energy efficiency,and stability for cycling performance than the pristine cell at 140 mA cm^(−2) for 200 cycles.Moreover,the energy efficiency of the modified cell is increased by 9.7% from 55.2% for the pristine cell at 260 mA cm^(−2).Such an ultra-homogeneous etching with N and O co-doping through“boiling”molten salt medium provides an effective and practical application potential way to prepare superior electrodes for VRFB.展开更多
Hydrogen peroxide synthesis by electro-reduction of O_(2) to substitute the current anthraquinone process has attracted a great deal of attention. Low oxygen utilization rate and low hydrogen peroxide production remai...Hydrogen peroxide synthesis by electro-reduction of O_(2) to substitute the current anthraquinone process has attracted a great deal of attention. Low oxygen utilization rate and low hydrogen peroxide production remain obstacles to electro-Fenton application. In situ H_(2)O_(2) generated by electrochemical reaction depends on the electrochemical performance of the cathode and the structure of the reactor. Here, novel graphite felt(GF) modified by La-doped CeO_(2)(La-CeO_(2)) was developed as a cathode. A new double chamber electro-Fenton reactor was proposed, where an organic ultrafiltration membrane was used to prevent H_(2)O_(2) from spreading to the anode. The effects of hydrothermal temperature, time and urea concentration on the electrochemical properties of graphite felt were investigated. The accumulated concentration of H_(2)O_(2) on the modified cathode reached 218.4 mg·L^(-1)in 1 h when the optimal conditions of hydrothermal temperature 120 ℃ and urea concentration 0.55%(mass) in 24 h. The degradation rate of methyl orange reached 98.29%. The new electro-Fenton reactor can efficiently produce hydrogen peroxide to degrade various organic substances and has a high potential for treating wastewater in the chemical industry.展开更多
Fabrication, characterization and performance of a porous metal-fiber sintered felt （PMFSF） based on multi-tooth cutting and solid-phase sintering were studied. The PMFSF was used as the anodic methanol barrier in a...Fabrication, characterization and performance of a porous metal-fiber sintered felt （PMFSF） based on multi-tooth cutting and solid-phase sintering were studied. The PMFSF was used as the anodic methanol barrier in a passive air-breathing direct methanol fuel cell to mitigate the effects of methanol crossover. Compared with the commercial SUS316L felt made of bundle-drawn fibers, this self-made PMFSF has larger pore diameter, polarized pore distribution, irregular fiber shape, rougher surface, lower mass flow resistance and evident hydrophobicity. The results reveal that the use of a PMFSF significantly enhances the cell performance since it helps to maintain a balance between the reactant and product management while depressing methanol crossover. The PMFSF with a porosity of 70% yields the highest cell performance at a methanol concentration of 4 mol/L.展开更多
Electro-oxidation of Ce （ Ⅲ ） to Ce （ Ⅳ ） in parallel plate flow type electrolyzer divided with cation exchange membrane was carried out in nitric acid media at carbon felt anode under galvanostatic conditions. ...Electro-oxidation of Ce （ Ⅲ ） to Ce （ Ⅳ ） in parallel plate flow type electrolyzer divided with cation exchange membrane was carried out in nitric acid media at carbon felt anode under galvanostatic conditions. Carbon felt was used as an anode for its high specific surface area and high oxygen evolution overpotential. Pt coated Ti plates were used as cathode and anode current feeder. The oxidation of 1 mol· L^-1 Ce（ Ⅲ ） solution in 2 mol· L^- 1 HNO3 was proceeding with a high current efficiency （92%） until about 80% of Ce（ Ⅲ ） was oxidized. Then, oxygen evolution, accompanied by terminal voltage jump, took place, lowering current efficiency. Ce（ Ⅲ ） was oxidized up to 90% with current efficiency of 62%. In this mode, strong carbon felt anode oxidation was observed. The wear out of carbon felt was 46% in six consequent runs （6 h of operation）. After each run, carbon felt surface had to be renewed with slightly alkaline solution to remove carbon oxidation products and ensure regular operational conditions. When anode surface was blocked, oxygen evolution took place from the beginning of electrolysis due to higher actual current density. The wear out of carbon felt anode could be minimized by means of oxygen evolution prevention. In the case when electrolysis had been stopped before oxygen evolution started （at Ce（ Ⅳ ） conversion of about 80% ）, the wear out of anode was less than 2% during 6 consequent runs （4 h of operation）.展开更多
Surface electropositivity and low internal resistance are important factors to improve the anode performance in microbial fuel cells (MFCs). Nitrogen doping is an effective way for the modification of traditional carb...Surface electropositivity and low internal resistance are important factors to improve the anode performance in microbial fuel cells (MFCs). Nitrogen doping is an effective way for the modification of traditional carbon materials. In this work, heat treatment and melamine were used to modify carbon felts to enhance electrogenesis capacity of MFCs. The modified carbon felts were characterized using X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), atomic force microscopy (AFM) and malvern zeta potentiometer. Results show that the maximum power densities under heat treatment increase from 276.1 to 423.4 mW/m(2) (700 degrees C) and 461.5 mW/m(2) (1200 degrees C) and further increase to 472.5 mW/m(2) (700 degrees C) and 515.4 mW/m(2) (1200 degrees C) with the co-carbonization modification of melamine. The heat treatment reduces the material resistivity, improves the zeta potential which is beneficial to microbial adsorption and electron transfer. The addition of melamine leads to the higher content of surface pyridinic and quaternary nitrogen and higher zeta potential. It is related to higher MFCs performance. Generally, the melamine modification at high temperature increases the feasibility of carbon felt as MFCs's anode materials. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.展开更多
Fabricating of high performance electrodes by a sustainable and cost effective method is essential to the development of vanadium redox flow batteries(VRFBs).In this work,an effective strategy is proposed to deposit c...Fabricating of high performance electrodes by a sustainable and cost effective method is essential to the development of vanadium redox flow batteries(VRFBs).In this work,an effective strategy is proposed to deposit carbon nanoparticles on graphite felts by hydrothermal carbonization method.This in-situ method minimizes the drop off and aggregation of carbon nanoparticles during electrochemical testing.Such integration of felts and hydrothermal carbons(HTC)produces a new electrode that combines the outstanding electrical conductivity of felts with the effective redox active sites provided by the HTC coating layer.The presence of the amorphous carbon layers on the felts is found to be able to promote the mass/charge transfer,and create oxygenated/nitrogenated active sites and hence enhances wettability.Consequently,the most optimized electrode based on a rational approach delivers an impressive electrochemical performance toward VRFBs in wide range of current densities from 200 to 500 mAcm^-2.The voltage efficiency(VE)of GFs-HTC is much higher than the VEs of the pristine GFs,especially at high current densities.It exhibits a 4.18 times increase in discharge capacity over the pristine graphite felt respectively,at a high current density of 400 mAcm^-2.The enhanced performance is attributed to the abundant active sites from amorphous hydrothermal carbon,which facilitates the fast electrochemical kinetics of vanadium redox reactions.This work evidences that the glucose-derived hydrothermal carbons as energy storage booster hold great promise in practical VRFBs application.展开更多
Electrode materials with good redox kinetics,excellent mass transfer characteristics and ultra-high stability play a crucial role in reducing the life-cycle cost and prolonging the maintenance-free time of the vanadiu...Electrode materials with good redox kinetics,excellent mass transfer characteristics and ultra-high stability play a crucial role in reducing the life-cycle cost and prolonging the maintenance-free time of the vanadium flow batteries(VFB).Herein,a nitrogen-doped porous graphite felt electrode(N-PGF)is proposed by growing ZIF-67 nanoparticles on carbon fibers and then calcinating and acid etching.The multi-scale structure of“carbon fiber gap(electrolyte flow),micro/nano pore(active species diffusion)and Nitrogen active center(reaction site)”in N-PGF electrode effectively increases the catalytic sites and promotes mass transfer characteristics.Reasonable electrode design makes the battery show excellent rate performance and ultra-high cycling stability.The peak power density of the battery reaches 1006 mW cm^(-2).During 1000 cycles at 150 mA cm^(-2),the average discharge capacity and average discharge energy of N-PGF increase substantially by 11.6%and 23.4%compared with the benchmark thermal activated graphite felt,respectively.More excitingly,after ultra-long term(5000 cycles)operation at an ultra-high current density(300 mA cm^(-2)),N-PGF exhibits an unprecedented energy efficiency retention(99.79%)and electrochemical performance stability.展开更多
Vanadium flow battery （VFB） is a fast going and promising system for large-scale stationary energy stor- age. However, drawbacks such as low power density and narrow temperature window caused by poor catalytic activ...Vanadium flow battery （VFB） is a fast going and promising system for large-scale stationary energy stor- age. However, drawbacks such as low power density and narrow temperature window caused by poor catalytic activity of graphite felt （GF） electrodes limit its worldwide application. In this paper, bismuth, as a low-cost, no-toxic and high-activity electrocatalyst, is used to modify the thermal activated GF （TGF） via a facile hydrothermal method. Bismuth can effectively inhibit the side reaction of hydrogen evolution in wide temperature range, while promoting the V2＋/V3＋ redox reaction. As a result, the VFB assembled with Bi/TGF as negative electrode demonstrates outstanding rate performance under the current density up to 400 mAcm-2, as well as a long-term stability over 600 charging/discharging cycles at a high cur- rent density of 150mA cm-2. Moreover, it also shows excellent temperature adaptability from -10 ℃ to 50 ℃ and high durability for life test at the temperature of 50 ℃.展开更多
Vanadium redox flow batteries(VRFBs)are one of the most promising energy storage systems owing to their safety,efficiency,flexibility and scalability.However,the commercial viability of VRFBs is still hindered by the ...Vanadium redox flow batteries(VRFBs)are one of the most promising energy storage systems owing to their safety,efficiency,flexibility and scalability.However,the commercial viability of VRFBs is still hindered by the low electrochemical performance of the available carbon-based electrodes.Defect engineering is a powerful strategy to enhance the redox catalytic activity of carbon-based electrodes for VRFBs.In this paper,uniform carbon defects are introduced on the surfaces of carbon felt(CF)electrode by Ar plasma etching.Together with a higher specific surface area,the Ar plasma treated CF offers additional catalytic sites,allowing faster and more reversible oxidation/reduction reactions of vanadium ions.As a result,the VRFB using plasma treated electrode shows a power density of 1018.3 mW/cm^(2),an energy efficiency(EE)of 84.5%,and the EE remains stable over 1000 cycles.展开更多
The cerium-based redox flow battery(RFB)is regarded as a compelling gridscale energy storage technology to revolutionize the utilization of renewable energy by storing the energy in liquid electrolytes.However,its wid...The cerium-based redox flow battery(RFB)is regarded as a compelling gridscale energy storage technology to revolutionize the utilization of renewable energy by storing the energy in liquid electrolytes.However,its widespread implementation is impeded by the cerium redox reactions that exhibit slow kinetics on commercial graphite felt(GF)electrodes.Surface functionalization may be an available activation strategy to achieve a significant boost in the electrochemical performance of GFs.However,conventional chemical and/or electrochemical routes for the surface functionalization of GFs suffer from the issues of complication,and the deterioration of the resulting modified electrode surface over long-term cycle processes leads to catalytic activity decline.Here,we develop a facile and general strategy for introducing the functional groups to the electrode through the addition of L-cysteine into electrolytes.The-COOH,-NH_(2),and-SH groups in L-cysteine can induce oxygen/nitrogen/sulfur trifunctional doping on GF surfaces with lower deterioration rates,which enables the activated GFs to demonstrate a promising electrocatalytic activity toward cerium redox reactions and excellent durability when used as a cerium-based RFB electrode.This study proposes a rational strategy to overcome the intrinsic limitations of existing modification techniques for GFs and provides a potential pathway toward high-performance RFBs.展开更多
A phosphorous-doped graphite felt(PGF) is fabricated and examined as electrode for vanadium flow battery(VFB). P doping improves the electrolyte wettability of GF and induces more defect sites on its surface, resultin...A phosphorous-doped graphite felt(PGF) is fabricated and examined as electrode for vanadium flow battery(VFB). P doping improves the electrolyte wettability of GF and induces more defect sites on its surface, resulting in significantly enhanced activity and reversibility towards VO2^+/VO2^+ and V^2+/V3^+couples. VFB with PGF electrode demonstrates outstanding performance such as high-rate capability under 50–400 mA cm^-2, wide-temperature tolerance at-20 °C–60 °C, and excellent durability over 1000 charge–discharge cycles. These merits enable PGF a promising electrode for the next-generation VFB,which can operate at high-power and all-climate conditions.展开更多
Redox flow batteries offer a potential solution to an increase in renewable energy generation on the grid by offering long-term, large-scale storage and regulation of power. However, they are currently un- derutilised...Redox flow batteries offer a potential solution to an increase in renewable energy generation on the grid by offering long-term, large-scale storage and regulation of power. However, they are currently un- derutilised due to cost and performance issues, many of which are linked to the microstructure of the porous carbon electrodes used. Here, for the first time, we offer a detailed study of the in situ effects of compression on a commercially available carbon felt electrode. Visualisation of electrode structure us- ing X-ray computed tomography shows the non-linear way that these materials compress and various metrics are used to elucidate the changes in porosity, pore size distribution and tortuosity factor under compressions from 0%-90%.展开更多
Nickel hexacyanoferrate (NiHCF) film was synthesized on porous three-dimensional carbon felt (PTCF) substrate by repetitious batch chemical depositions, and the NiHCF/PTCF electrode was used as electrochemically switc...Nickel hexacyanoferrate (NiHCF) film was synthesized on porous three-dimensional carbon felt (PTCF) substrate by repetitious batch chemical depositions, and the NiHCF/PTCF electrode was used as electrochemically switched ion exchange (ESIX) electrode in a packed bed for continuous separation for cesium ions. The morphologies of the prepared electrodes were characterized by scanning electron microscopy and the effects of solution concentration on the ion-exchange capacity of the electrodes were investigated by cyclic voltammetry technique. Cycling stability and long-term storage stability of NiHCF/PTCF electrodes were also studied. The NiHCF/PTCF electrodes with excellent ion-exchange ability were used to assemble a diaphragm-isolated ESIX reactor for cesium separation. Continuous separation of cesium and regeneration of NiHCF/PTCF electrode based on the diaphragm-isolated reactor were performed in a laboratory-scale two-electrode system.展开更多
This paper addresses the damaging role of the parasitic hydrogen evolution reaction (HER) in the negative half-cell of a vanadium redox flow battery (VRFB) on state-of-the-art carbon felt electrodes at different tempe...This paper addresses the damaging role of the parasitic hydrogen evolution reaction (HER) in the negative half-cell of a vanadium redox flow battery (VRFB) on state-of-the-art carbon felt electrodes at different temperatures. It was found that increasing the temperature resulted in a better catalytic performance for both the positive and negative half-cell reactions. In addition, increasing the temperature significantly enhanced the undesired HER at the negative side. Operating the VRFB cell at higher temperature led to a decrease in the coulombic efficiency attributed to the higher hydrogen production. More pronounced hydrogen production caused an oxidation on the surface of the carb on fibers and a degradation of the electrode as indicated from scanning electron microscopy and X-ray photoelectron spectroscopy measurements. This observed degradation results in fading of the overall performance of the vanadium redox flow battery over time.展开更多
Prussian blue (PB) modified carbon felt electrodes were prepared. The electrochemical behavior was investigated by cyclic voltammetry, electrochemical impedance spectroscopy and charge-discharge experiments. In order ...Prussian blue (PB) modified carbon felt electrodes were prepared. The electrochemical behavior was investigated by cyclic voltammetry, electrochemical impedance spectroscopy and charge-discharge experiments. In order to distinguish the mechanism of the PB modified carbon felt electrode, the electrochemical quartz crystal microbalance (EQCM) was employed. The results of cyclic voltammetry show that the modification can improve the reversibility and the suitable PB deposition is the amount of 10 circles deposition. PB modified carbon felt electrode can effectively decrease the charge transfer resistance. The voltage efficiency of VRB employing PB modified carbon felt electrode can be increased by 12%. The mass change of the PB modified Pt crystal electrode in the process of the potential scan is obvious. The reaction of substitution of VO2+ for high-spin Fe ion in PB is probable to happen and the possible reaction equation is given. The preliminary exploration shows that PB modified carbon felt is electrochemically promising for redox flow battery.展开更多
PAN-based graphite felt （PGF） treated in 98% sulphuric acid for 5 h and then kept at 450 ℃ for 2 h was evaluated for their electrochemical performance as electrodes of vanadium redox battery （VRB）. Structure and ...PAN-based graphite felt （PGF） treated in 98% sulphuric acid for 5 h and then kept at 450 ℃ for 2 h was evaluated for their electrochemical performance as electrodes of vanadium redox battery （VRB）. Structure and characteristic of treated PAN-based graphite felt （TPGF） were determined by means of Fourier Transform Infi-ared Spectroscopy, Scanning Electron Microscopy, Brunauer-Emmett-Teller surface area analysis and VRB test system. The results show that the acid and heat synergistic effect increase the number of --COOH functional groups on the PGF surface, and the PGF is eroded by sulphuric acid oxidation, resulting in the surface area increases from 0.31 m^2/g to 0.45 m^2/g. The V（ Ⅱ ）/V（Ⅲ） redox reaction is electrochemically reversible on the TPGF electrode, while the V（Ⅳ）/V（Ⅴ） couple is a quasi reversible process. The diffusion coefficients of the oxidation for V（Ⅳ）/V（Ⅴ） obtained from the scope of peak current Ip vs scan rate v^1/2 is 4.4×10^-5 cm^2/s. The improvement of electrochemical activity for the electrode is mainly ascribed to the increase of the number of ---COOH groups on the TPGF, which behaves as active sites catalyzing the vanadium species reactions and accelerating electron transfer reaction and oxygen transfer.展开更多
The electrode is one of the main components in redox flow batteries(RFBs), as it provides the reactions sites for redox couples and can influence the cell performance through its effect on cell voltage losses associat...The electrode is one of the main components in redox flow batteries(RFBs), as it provides the reactions sites for redox couples and can influence the cell performance through its effect on cell voltage losses associated with activation overpotential, concentration overpotential and ohmic losses. Extensive research has thus been carried out on material selection, structural design and modification of electrodes as well as electrocatalysis for redox reactions. This review provides an historical overview of the screening and modification of electrode materials together with recent progress in novel electrode architectures, electrode modification and electrocatalysis methods. RFB systems such as iron/chromium, polysulfide/bromine and all vanadium batteries are discussed in detail.展开更多
文摘A new MEEKC method assisted with pressure-driven mobile phase was presented for the separation of felted explosives. Microemulsion solution was composed of 80 mmol/L heptane -120 mmol/L SDS (sodium dodecyl sulphate) - 900 mmol/L butanol - 10 mmol/L borate at pH 9.4 and a pressure-driven flow of 0.020 mL/min under 1.3 MPa was employed to manipulate the separation. Explosives HMX (1, 3, 5, 7-tetranitro-l, 3, 5, 7-tetrazacyclooctane) and TATB (triamino-trinitrobenzene), which were felted on fluorine rubber F2311 (polytrifluorochlorethylene and polyvinylidene fluoride 1/1 co-polymerization) and F2314 (polytrifluorochlorethylene and polyvinylidene fluoride 4/1 co-polymerization) were well separated with very good peak shapes.
基金The authors acknowledge the financial support from the National Natural Science Foundation of China(Nos.52073224,32201491)the Textile Vision Basic Research Program of China(No.J202110)+3 种基金the Scientific Research Project of Shaanxi Provincial Education Department,China(No.22JC035)the Advanced Manufacturing Technology Program of Xi’an Science and Technology Bureau,China(No.21XJZZ0019)the Research Fund for the Doctoral Program of Xi’an Polytechnic University(No.BS202053)the Youth Innovation Team of Shaanxi Universities and Institute of Flexible electronics and Intelligent Textile.
文摘MXene,a transition metal carbide/nitride,has been prominent as an ideal electrochemical active material for supercapacitors.However,the low MXene load limits its practical applications.As environmental concerns and sustainable development become more widely recognized,it is necessary to explore a greener and cleaner technology to recycle textile by-products such as cotton.The present study proposes an effective 3D fabrication method that uses MXene to fabricate waste denim felt into ultralight and flexible supercapacitors through needling and carbonization.The 3D structure provided more sites for loading MXene onto Z-directional fiber bundles,resulting in more efficient ion exchange between the electrolyte and electrodes.Furthermore,the carbonization process removed the specific adverse groups in MXenes,further improving the specific capacitance,energy density,power density and electrical conductivity of supercapacitors.The electrodes achieve a maximum specific capacitance of 1748.5 mF cm-2 and demonstrate remarkable cycling stability maintaining more than 94%after 15,000 galvanostatic charge/discharge cycles.Besides,the obtained supercapacitors present a maximum specific capacitance of 577.5 mF cm^(-2),energy density of 80.2μWh cm^(-2)and power density of 3 mW cm^(-2),respectively.The resulting supercapacitors can be used to develop smart wearable power devices such as smartwatches,laying the foundation for a novel strategy of utilizing waste cotton in a high-quality manner.
基金supported by the National Natural Science Foundation of China(No.51872090)Natural Science Foundation of Hebei Province(No.E2019209433,E2022209158)Colleges and Universities in Hebei Province Science and Technology Research Project(No.JZX2024026).
文摘The scarcity of wettability,insufficient active sites,and low surface area of graphite felt(GF)have long been suppressing the performance of vanadium redox flow batteries(VRFBs).Herein,an ultra-homogeneous multipledimensioned defect,including nano-scale etching and atomic-scale N,O codoping,was used to modify GF by the molten salt system.NH_(4)Cl and KClO_(3) were added simultaneously to the system to obtain porous N/O co-doped electrode(GF/ON),where KClO_(3) was used to ultra-homogeneously etch,and O-functionalize electrode,and NH4Cl was used as N dopant,respectively.GF/ON presents better electrochemical catalysis for VO_(2)+/VO_(2)+ and V3+/V2+ reactions than only O-functionalized electrodes(GF/O)and GF.The enhanced electrochemical properties are attributed to an increase in active sites,surface area,and wettability,as well as the synergistic effect of N and O,which is also supported by the density functional theory calculations.Further,the cell using GF/ON shows higher discharge capacity,energy efficiency,and stability for cycling performance than the pristine cell at 140 mA cm^(−2) for 200 cycles.Moreover,the energy efficiency of the modified cell is increased by 9.7% from 55.2% for the pristine cell at 260 mA cm^(−2).Such an ultra-homogeneous etching with N and O co-doping through“boiling”molten salt medium provides an effective and practical application potential way to prepare superior electrodes for VRFB.
基金supported by the Tianjin Synthetic Biotechnology Innovation Capacity Improvement Project (TSBICIP-KJGG003)Qinglan Plan of the Jiangsu Education Department。
文摘Hydrogen peroxide synthesis by electro-reduction of O_(2) to substitute the current anthraquinone process has attracted a great deal of attention. Low oxygen utilization rate and low hydrogen peroxide production remain obstacles to electro-Fenton application. In situ H_(2)O_(2) generated by electrochemical reaction depends on the electrochemical performance of the cathode and the structure of the reactor. Here, novel graphite felt(GF) modified by La-doped CeO_(2)(La-CeO_(2)) was developed as a cathode. A new double chamber electro-Fenton reactor was proposed, where an organic ultrafiltration membrane was used to prevent H_(2)O_(2) from spreading to the anode. The effects of hydrothermal temperature, time and urea concentration on the electrochemical properties of graphite felt were investigated. The accumulated concentration of H_(2)O_(2) on the modified cathode reached 218.4 mg·L^(-1)in 1 h when the optimal conditions of hydrothermal temperature 120 ℃ and urea concentration 0.55%(mass) in 24 h. The degradation rate of methyl orange reached 98.29%. The new electro-Fenton reactor can efficiently produce hydrogen peroxide to degrade various organic substances and has a high potential for treating wastewater in the chemical industry.
基金Projects(50930005,51075155)supported by the National Natural Science Foundation of ChinaProject(20100172110001)supported by PhD Programs Foundation of Ministry of Education of China
文摘Fabrication, characterization and performance of a porous metal-fiber sintered felt （PMFSF） based on multi-tooth cutting and solid-phase sintering were studied. The PMFSF was used as the anodic methanol barrier in a passive air-breathing direct methanol fuel cell to mitigate the effects of methanol crossover. Compared with the commercial SUS316L felt made of bundle-drawn fibers, this self-made PMFSF has larger pore diameter, polarized pore distribution, irregular fiber shape, rougher surface, lower mass flow resistance and evident hydrophobicity. The results reveal that the use of a PMFSF significantly enhances the cell performance since it helps to maintain a balance between the reactant and product management while depressing methanol crossover. The PMFSF with a porosity of 70% yields the highest cell performance at a methanol concentration of 4 mol/L.
文摘Electro-oxidation of Ce （ Ⅲ ） to Ce （ Ⅳ ） in parallel plate flow type electrolyzer divided with cation exchange membrane was carried out in nitric acid media at carbon felt anode under galvanostatic conditions. Carbon felt was used as an anode for its high specific surface area and high oxygen evolution overpotential. Pt coated Ti plates were used as cathode and anode current feeder. The oxidation of 1 mol· L^-1 Ce（ Ⅲ ） solution in 2 mol· L^- 1 HNO3 was proceeding with a high current efficiency （92%） until about 80% of Ce（ Ⅲ ） was oxidized. Then, oxygen evolution, accompanied by terminal voltage jump, took place, lowering current efficiency. Ce（ Ⅲ ） was oxidized up to 90% with current efficiency of 62%. In this mode, strong carbon felt anode oxidation was observed. The wear out of carbon felt was 46% in six consequent runs （6 h of operation）. After each run, carbon felt surface had to be renewed with slightly alkaline solution to remove carbon oxidation products and ensure regular operational conditions. When anode surface was blocked, oxygen evolution took place from the beginning of electrolysis due to higher actual current density. The wear out of carbon felt anode could be minimized by means of oxygen evolution prevention. In the case when electrolysis had been stopped before oxygen evolution started （at Ce（ Ⅳ ） conversion of about 80% ）, the wear out of anode was less than 2% during 6 consequent runs （4 h of operation）.
文摘Surface electropositivity and low internal resistance are important factors to improve the anode performance in microbial fuel cells (MFCs). Nitrogen doping is an effective way for the modification of traditional carbon materials. In this work, heat treatment and melamine were used to modify carbon felts to enhance electrogenesis capacity of MFCs. The modified carbon felts were characterized using X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), atomic force microscopy (AFM) and malvern zeta potentiometer. Results show that the maximum power densities under heat treatment increase from 276.1 to 423.4 mW/m(2) (700 degrees C) and 461.5 mW/m(2) (1200 degrees C) and further increase to 472.5 mW/m(2) (700 degrees C) and 515.4 mW/m(2) (1200 degrees C) with the co-carbonization modification of melamine. The heat treatment reduces the material resistivity, improves the zeta potential which is beneficial to microbial adsorption and electron transfer. The addition of melamine leads to the higher content of surface pyridinic and quaternary nitrogen and higher zeta potential. It is related to higher MFCs performance. Generally, the melamine modification at high temperature increases the feasibility of carbon felt as MFCs's anode materials. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.
基金supported by the Award Program for Fujian Minjiang Scholar Professorshipthe National Natural Science Foundation of China(21571035)。
文摘Fabricating of high performance electrodes by a sustainable and cost effective method is essential to the development of vanadium redox flow batteries(VRFBs).In this work,an effective strategy is proposed to deposit carbon nanoparticles on graphite felts by hydrothermal carbonization method.This in-situ method minimizes the drop off and aggregation of carbon nanoparticles during electrochemical testing.Such integration of felts and hydrothermal carbons(HTC)produces a new electrode that combines the outstanding electrical conductivity of felts with the effective redox active sites provided by the HTC coating layer.The presence of the amorphous carbon layers on the felts is found to be able to promote the mass/charge transfer,and create oxygenated/nitrogenated active sites and hence enhances wettability.Consequently,the most optimized electrode based on a rational approach delivers an impressive electrochemical performance toward VRFBs in wide range of current densities from 200 to 500 mAcm^-2.The voltage efficiency(VE)of GFs-HTC is much higher than the VEs of the pristine GFs,especially at high current densities.It exhibits a 4.18 times increase in discharge capacity over the pristine graphite felt respectively,at a high current density of 400 mAcm^-2.The enhanced performance is attributed to the abundant active sites from amorphous hydrothermal carbon,which facilitates the fast electrochemical kinetics of vanadium redox reactions.This work evidences that the glucose-derived hydrothermal carbons as energy storage booster hold great promise in practical VRFBs application.
基金supported by the National Natural Science Foundation of China(21576154)the Natural Science Foundation of Guangdong Province(2022A1515011999 and 2019A1515011955)the Shenzhen Basic Research Project(20200829101039001 and GXWD20201231165806004)。
文摘Electrode materials with good redox kinetics,excellent mass transfer characteristics and ultra-high stability play a crucial role in reducing the life-cycle cost and prolonging the maintenance-free time of the vanadium flow batteries(VFB).Herein,a nitrogen-doped porous graphite felt electrode(N-PGF)is proposed by growing ZIF-67 nanoparticles on carbon fibers and then calcinating and acid etching.The multi-scale structure of“carbon fiber gap(electrolyte flow),micro/nano pore(active species diffusion)and Nitrogen active center(reaction site)”in N-PGF electrode effectively increases the catalytic sites and promotes mass transfer characteristics.Reasonable electrode design makes the battery show excellent rate performance and ultra-high cycling stability.The peak power density of the battery reaches 1006 mW cm^(-2).During 1000 cycles at 150 mA cm^(-2),the average discharge capacity and average discharge energy of N-PGF increase substantially by 11.6%and 23.4%compared with the benchmark thermal activated graphite felt,respectively.More excitingly,after ultra-long term(5000 cycles)operation at an ultra-high current density(300 mA cm^(-2)),N-PGF exhibits an unprecedented energy efficiency retention(99.79%)and electrochemical performance stability.
基金financial support from the National Natural Science Foundation of China (No. 21576154)the Open Fund of The State Key Laboratory of Refractories and Metallurgy (No. G201809)the Shenzhen Basic Research Project (Nos. JCYJ20170412170756603 and JCYJ20170307152754218)
文摘Vanadium flow battery （VFB） is a fast going and promising system for large-scale stationary energy stor- age. However, drawbacks such as low power density and narrow temperature window caused by poor catalytic activity of graphite felt （GF） electrodes limit its worldwide application. In this paper, bismuth, as a low-cost, no-toxic and high-activity electrocatalyst, is used to modify the thermal activated GF （TGF） via a facile hydrothermal method. Bismuth can effectively inhibit the side reaction of hydrogen evolution in wide temperature range, while promoting the V2＋/V3＋ redox reaction. As a result, the VFB assembled with Bi/TGF as negative electrode demonstrates outstanding rate performance under the current density up to 400 mAcm-2, as well as a long-term stability over 600 charging/discharging cycles at a high cur- rent density of 150mA cm-2. Moreover, it also shows excellent temperature adaptability from -10 ℃ to 50 ℃ and high durability for life test at the temperature of 50 ℃.
基金Project(Xiang Zu [2016] 91) supported by the “100 Talented Teams” of Hunan Province,ChinaProject(2018RS3077) supported by the Huxiang High-level Talents Program,China+2 种基金Project(22002009) supported by the National Natural Science Foundation of ChinaProject(2021JJ40565) supported by the Natural Science Foundation of Hunan Province,ChinaProject(19C0054) supported by the Scientific Research Foundation of Hunan Provincial Education Department,China。
文摘Vanadium redox flow batteries(VRFBs)are one of the most promising energy storage systems owing to their safety,efficiency,flexibility and scalability.However,the commercial viability of VRFBs is still hindered by the low electrochemical performance of the available carbon-based electrodes.Defect engineering is a powerful strategy to enhance the redox catalytic activity of carbon-based electrodes for VRFBs.In this paper,uniform carbon defects are introduced on the surfaces of carbon felt(CF)electrode by Ar plasma etching.Together with a higher specific surface area,the Ar plasma treated CF offers additional catalytic sites,allowing faster and more reversible oxidation/reduction reactions of vanadium ions.As a result,the VRFB using plasma treated electrode shows a power density of 1018.3 mW/cm^(2),an energy efficiency(EE)of 84.5%,and the EE remains stable over 1000 cycles.
基金Natural Science Foundation of Liaoning Province,Grant/Award Number:2020-MZLH-40High-Level Talent Innovation Support Program of Dalian City,Grant/Award Number:2019RQ076National Natural Science Foundation of China,Grant/Award Numbers:21801034,51732007,51872033。
文摘The cerium-based redox flow battery(RFB)is regarded as a compelling gridscale energy storage technology to revolutionize the utilization of renewable energy by storing the energy in liquid electrolytes.However,its widespread implementation is impeded by the cerium redox reactions that exhibit slow kinetics on commercial graphite felt(GF)electrodes.Surface functionalization may be an available activation strategy to achieve a significant boost in the electrochemical performance of GFs.However,conventional chemical and/or electrochemical routes for the surface functionalization of GFs suffer from the issues of complication,and the deterioration of the resulting modified electrode surface over long-term cycle processes leads to catalytic activity decline.Here,we develop a facile and general strategy for introducing the functional groups to the electrode through the addition of L-cysteine into electrolytes.The-COOH,-NH_(2),and-SH groups in L-cysteine can induce oxygen/nitrogen/sulfur trifunctional doping on GF surfaces with lower deterioration rates,which enables the activated GFs to demonstrate a promising electrocatalytic activity toward cerium redox reactions and excellent durability when used as a cerium-based RFB electrode.This study proposes a rational strategy to overcome the intrinsic limitations of existing modification techniques for GFs and provides a potential pathway toward high-performance RFBs.
基金supported by the National Natural Science Foundation of China(No.21576154)the Shenzhen Basic Research Project(Nos.JCYJ20170818115018000,JCYJ20170307154206288,JCYJ20170412170756603)
文摘A phosphorous-doped graphite felt(PGF) is fabricated and examined as electrode for vanadium flow battery(VFB). P doping improves the electrolyte wettability of GF and induces more defect sites on its surface, resulting in significantly enhanced activity and reversibility towards VO2^+/VO2^+ and V^2+/V3^+couples. VFB with PGF electrode demonstrates outstanding performance such as high-rate capability under 50–400 mA cm^-2, wide-temperature tolerance at-20 °C–60 °C, and excellent durability over 1000 charge–discharge cycles. These merits enable PGF a promising electrode for the next-generation VFB,which can operate at high-power and all-climate conditions.
基金support from the EPSRC under grants EP/L014289/1 EP/N032888/1 and EP/M014045/1the STFC Global Challenges Network in Batteries and Electrochemical Energy Devices under the grant ST/N002385/1 for facilitation of travelfunding from the Royal Academy of Engineering
文摘Redox flow batteries offer a potential solution to an increase in renewable energy generation on the grid by offering long-term, large-scale storage and regulation of power. However, they are currently un- derutilised due to cost and performance issues, many of which are linked to the microstructure of the porous carbon electrodes used. Here, for the first time, we offer a detailed study of the in situ effects of compression on a commercially available carbon felt electrode. Visualisation of electrode structure us- ing X-ray computed tomography shows the non-linear way that these materials compress and various metrics are used to elucidate the changes in porosity, pore size distribution and tortuosity factor under compressions from 0%-90%.
基金Supported by the National Natural Science Foundation of China (21276173)the National Science Foundation of Shanxi Province (2012011020-5, 2012011006-1)the International Joint Research Project of Shanxi Province (2011081028)
文摘Nickel hexacyanoferrate (NiHCF) film was synthesized on porous three-dimensional carbon felt (PTCF) substrate by repetitious batch chemical depositions, and the NiHCF/PTCF electrode was used as electrochemically switched ion exchange (ESIX) electrode in a packed bed for continuous separation for cesium ions. The morphologies of the prepared electrodes were characterized by scanning electron microscopy and the effects of solution concentration on the ion-exchange capacity of the electrodes were investigated by cyclic voltammetry technique. Cycling stability and long-term storage stability of NiHCF/PTCF electrodes were also studied. The NiHCF/PTCF electrodes with excellent ion-exchange ability were used to assemble a diaphragm-isolated ESIX reactor for cesium separation. Continuous separation of cesium and regeneration of NiHCF/PTCF electrode based on the diaphragm-isolated reactor were performed in a laboratory-scale two-electrode system.
基金a fellowship from the Alexander von Humboldt Foundation (AvH)
文摘This paper addresses the damaging role of the parasitic hydrogen evolution reaction (HER) in the negative half-cell of a vanadium redox flow battery (VRFB) on state-of-the-art carbon felt electrodes at different temperatures. It was found that increasing the temperature resulted in a better catalytic performance for both the positive and negative half-cell reactions. In addition, increasing the temperature significantly enhanced the undesired HER at the negative side. Operating the VRFB cell at higher temperature led to a decrease in the coulombic efficiency attributed to the higher hydrogen production. More pronounced hydrogen production caused an oxidation on the surface of the carb on fibers and a degradation of the electrode as indicated from scanning electron microscopy and X-ray photoelectron spectroscopy measurements. This observed degradation results in fading of the overall performance of the vanadium redox flow battery over time.
基金Project (2008ZX07313-005) supported by the National Water Pollution Control and Management of Major Special Science and Technology Foundation
文摘Prussian blue (PB) modified carbon felt electrodes were prepared. The electrochemical behavior was investigated by cyclic voltammetry, electrochemical impedance spectroscopy and charge-discharge experiments. In order to distinguish the mechanism of the PB modified carbon felt electrode, the electrochemical quartz crystal microbalance (EQCM) was employed. The results of cyclic voltammetry show that the modification can improve the reversibility and the suitable PB deposition is the amount of 10 circles deposition. PB modified carbon felt electrode can effectively decrease the charge transfer resistance. The voltage efficiency of VRB employing PB modified carbon felt electrode can be increased by 12%. The mass change of the PB modified Pt crystal electrode in the process of the potential scan is obvious. The reaction of substitution of VO2+ for high-spin Fe ion in PB is probable to happen and the possible reaction equation is given. The preliminary exploration shows that PB modified carbon felt is electrochemically promising for redox flow battery.
基金Project (03GKY3015) supported by the Foundation of Hunan Provincial Department of Science and Technology
文摘PAN-based graphite felt （PGF） treated in 98% sulphuric acid for 5 h and then kept at 450 ℃ for 2 h was evaluated for their electrochemical performance as electrodes of vanadium redox battery （VRB）. Structure and characteristic of treated PAN-based graphite felt （TPGF） were determined by means of Fourier Transform Infi-ared Spectroscopy, Scanning Electron Microscopy, Brunauer-Emmett-Teller surface area analysis and VRB test system. The results show that the acid and heat synergistic effect increase the number of --COOH functional groups on the PGF surface, and the PGF is eroded by sulphuric acid oxidation, resulting in the surface area increases from 0.31 m^2/g to 0.45 m^2/g. The V（ Ⅱ ）/V（Ⅲ） redox reaction is electrochemically reversible on the TPGF electrode, while the V（Ⅳ）/V（Ⅴ） couple is a quasi reversible process. The diffusion coefficients of the oxidation for V（Ⅳ）/V（Ⅴ） obtained from the scope of peak current Ip vs scan rate v^1/2 is 4.4×10^-5 cm^2/s. The improvement of electrochemical activity for the electrode is mainly ascribed to the increase of the number of ---COOH groups on the TPGF, which behaves as active sites catalyzing the vanadium species reactions and accelerating electron transfer reaction and oxygen transfer.
文摘The electrode is one of the main components in redox flow batteries(RFBs), as it provides the reactions sites for redox couples and can influence the cell performance through its effect on cell voltage losses associated with activation overpotential, concentration overpotential and ohmic losses. Extensive research has thus been carried out on material selection, structural design and modification of electrodes as well as electrocatalysis for redox reactions. This review provides an historical overview of the screening and modification of electrode materials together with recent progress in novel electrode architectures, electrode modification and electrocatalysis methods. RFB systems such as iron/chromium, polysulfide/bromine and all vanadium batteries are discussed in detail.
