By conjugating features of combustion gas jetting flows of the solid-rocket and using mathematical methods, a numerical scheme is systematically derived based on Harten′s standard TVD scheme, which fits for the flow ...By conjugating features of combustion gas jetting flows of the solid-rocket and using mathematical methods, a numerical scheme is systematically derived based on Harten′s standard TVD scheme, which fits for the flow with high temperature, pressure and velocity. The rational calculation formula of pressure partial derivation is also given out. By using the chemical kinetics knowledge, problems of multi-component and finite rate chemical reaction contained in combustion gas of the rocket flow field are discussed. The method for solving the mass source term of chemical reaction is clarified. Taking 9 reaction equations with 12 components as an example and utilizing the established calculation program, the free jetting flow field of the rocket is simulated. Numerical results show the correctness of the numerical scheme.展开更多
Large-scale electrical energy storage with high energy density and round-trip efficiency is important to the resilience of power grids and the effective use of intermittent renewable energy such as solar and wind.Lith...Large-scale electrical energy storage with high energy density and round-trip efficiency is important to the resilience of power grids and the effective use of intermittent renewable energy such as solar and wind.Lithiumoxygen battery,due to its high energy density,is believed to be one of the most promising energy storage systems for the future.However,large overpotentials,poor cycling stability,and degradation of electrolytes and cathodes have been hindering the development of lithium-oxygen batteries.Numerous heterogeneous oxygen electrocatalysts have been investigated to lower the overpotentials and enhance the cycling stability of lithium-oxygen batteries.Unfortunately,the prevailing issues of electrode passivation and clogging remain.Over the past few years,redox mediators were explored as homogenous catalysts to address the issues,while only limited success has been achieved for these soluble catalysts.In conjunction with a flowing electrolyte system,a new redox flow lithium-oxygen battery(RFLOB)has been devised to tackle the aforementioned issues.The working mechanism and schematic processes will be elaborated in this review.In addition,the performance gap of RFLOB with respect to practical requirements will be analysed.With the above,we anticipate RFLOB would be a credible solution for the implementation of lithium-oxygen battery chemistry for the next generation energy storage.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
The electrolyte is one of the most important components of vanadium redox flow battery （VRFB）. and its stability and solubility determines the energy density of a VRFB. The performance of current positive elec- trol...The electrolyte is one of the most important components of vanadium redox flow battery （VRFB）. and its stability and solubility determines the energy density of a VRFB. The performance of current positive elec- trolyte is limited by the low stability of VO2＋ at a higher temperature. Phosphate is proved to be a very effective additive to improve the stability of VO2＋. Even though, the stabilizing mechanism is still not clear, which hinders the further development of VRFBs. In this paper, to clarify the effect of phosphate additive on the positive electrolyte stability, the hydration structures of VO2＋ cations and the reaction mechanisms of precipitation with or without phosphate in the supporting electrolyte of H_2SO_4 solutions were investigated in detail based on calculations of electronic structure. The stable configurations of com- plexes were optimized at the B3LYP/6-311 ＋ G（d,p） level of theory. The zero-point energies and Gibbs free energies for these complexes were further evaluated at the B3LYP/aug-cc-pVTZ level of theory. It shows that a structure of [VO_2（H_2O）_2]＋ surrounded by water molecules in H2S04 solution can be formed at the room temperature. With the temperature rises, [VO_2（H_2O）_2]＋ will lose a proton and form the interme- diate of VO（OH）_3, and the further dehydration among VO（OH）_3 molecules will create the precipitate of V_2O_5. When H_3PO_4 was added into electrolytes, the V-O-P bond-containing neutral compound could be formed through interaction between VO（OH）_3 and H_3PO_4, and the activation energy of forming the V-O-P bond-containing neutral compound is about 7 kcal tool-1 lower than that of the VO（OH）_3 dehydration, which could avoid the precipitation of V_2O_5 and improve the electrolyte stability.展开更多
文摘By conjugating features of combustion gas jetting flows of the solid-rocket and using mathematical methods, a numerical scheme is systematically derived based on Harten′s standard TVD scheme, which fits for the flow with high temperature, pressure and velocity. The rational calculation formula of pressure partial derivation is also given out. By using the chemical kinetics knowledge, problems of multi-component and finite rate chemical reaction contained in combustion gas of the rocket flow field are discussed. The method for solving the mass source term of chemical reaction is clarified. Taking 9 reaction equations with 12 components as an example and utilizing the established calculation program, the free jetting flow field of the rocket is simulated. Numerical results show the correctness of the numerical scheme.
基金supported by the National Research Foundation, Prime Minister’s Office, Singapore, under its Competitive Research Program (CRP Awards No.NRF-CRP10-2012-06)
文摘Large-scale electrical energy storage with high energy density and round-trip efficiency is important to the resilience of power grids and the effective use of intermittent renewable energy such as solar and wind.Lithiumoxygen battery,due to its high energy density,is believed to be one of the most promising energy storage systems for the future.However,large overpotentials,poor cycling stability,and degradation of electrolytes and cathodes have been hindering the development of lithium-oxygen batteries.Numerous heterogeneous oxygen electrocatalysts have been investigated to lower the overpotentials and enhance the cycling stability of lithium-oxygen batteries.Unfortunately,the prevailing issues of electrode passivation and clogging remain.Over the past few years,redox mediators were explored as homogenous catalysts to address the issues,while only limited success has been achieved for these soluble catalysts.In conjunction with a flowing electrolyte system,a new redox flow lithium-oxygen battery(RFLOB)has been devised to tackle the aforementioned issues.The working mechanism and schematic processes will be elaborated in this review.In addition,the performance gap of RFLOB with respect to practical requirements will be analysed.With the above,we anticipate RFLOB would be a credible solution for the implementation of lithium-oxygen battery chemistry for the next generation energy storage.
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supported by the National Natural Science Foundation of China(no.21773102)
文摘The electrolyte is one of the most important components of vanadium redox flow battery （VRFB）. and its stability and solubility determines the energy density of a VRFB. The performance of current positive elec- trolyte is limited by the low stability of VO2＋ at a higher temperature. Phosphate is proved to be a very effective additive to improve the stability of VO2＋. Even though, the stabilizing mechanism is still not clear, which hinders the further development of VRFBs. In this paper, to clarify the effect of phosphate additive on the positive electrolyte stability, the hydration structures of VO2＋ cations and the reaction mechanisms of precipitation with or without phosphate in the supporting electrolyte of H_2SO_4 solutions were investigated in detail based on calculations of electronic structure. The stable configurations of com- plexes were optimized at the B3LYP/6-311 ＋ G（d,p） level of theory. The zero-point energies and Gibbs free energies for these complexes were further evaluated at the B3LYP/aug-cc-pVTZ level of theory. It shows that a structure of [VO_2（H_2O）_2]＋ surrounded by water molecules in H2S04 solution can be formed at the room temperature. With the temperature rises, [VO_2（H_2O）_2]＋ will lose a proton and form the interme- diate of VO（OH）_3, and the further dehydration among VO（OH）_3 molecules will create the precipitate of V_2O_5. When H_3PO_4 was added into electrolytes, the V-O-P bond-containing neutral compound could be formed through interaction between VO（OH）_3 and H_3PO_4, and the activation energy of forming the V-O-P bond-containing neutral compound is about 7 kcal tool-1 lower than that of the VO（OH）_3 dehydration, which could avoid the precipitation of V_2O_5 and improve the electrolyte stability.
