The exploitation of high performance redox-active substances is critically important for the development of non-aqueous redoxflow batteries.Herein,three tetrathiofulvalene(TTF)derivatives with different substitution gr...The exploitation of high performance redox-active substances is critically important for the development of non-aqueous redoxflow batteries.Herein,three tetrathiofulvalene(TTF)derivatives with different substitution groups,namely TTF diethyl ester(TTFDE),TTF tetramethyl ester(TTFTM),and TTF tetraethyl ester(TTFTE),are prepared and their energy storage properties are evaluated.It has been found that the redox potential and solubility of these TTF derivatives in conventional carbonate electrolytes increases with the number of ester groups.The battery with a catholyte of 0.2 mol L^(-1) of TTFTE delivers a specific capacity of more than 10 Ah L^(-1) at the current density of 0.5 C with two discharge voltage platforms locating at as high as 3.85 and 3.60 V vs.Li/Liþ.Its capacity retention can be improved from 2.34 Ah L^(-1) to 3.60 Ah L^(-1) after 100 cycles by the use of an anion exchange membrane to block the crossover of TTF species.The excellent cycling stability of the TIF esters is supported by their well-delocalized electrons,as revealed by the density function theory calculations.Therefore,the introduction of more and larger electron-withdrawing groups is a promising strategy to simultaneously increase the redox-potential and solubility of redox-active ma-terials for non-aqueous redoxflow batteries.展开更多
Flow batteries with high energy density and long cycle life have been pursued to advance the progress of energy storage and grid application. Non-aqueous batteries with wide voltage windows represent a promising techn...Flow batteries with high energy density and long cycle life have been pursued to advance the progress of energy storage and grid application. Non-aqueous batteries with wide voltage windows represent a promising technology without the limitation of water electrolysis, but they suffer from low electrolyte concentration and unsatisfactory battery performance. Here, a non-aqueous lithium bromine rechargeable battery is proposed, which is based on Br;/Br;and Li;/Li as active redox pairs, with fast redox kinetics and good stability. The Li/Br battery combines the advantages of high output voltage（;.1 V）,electrolyte concentration（3.0 mol/L）, maximum power density（29.1 m W/cm;） and practical energy density（232.6 Wh/kg）. Additionally, the battery displays a columbic efficiency（CE） of 90.0%, a voltage efficiency（VE） of 88.0% and an energy efficiency（EE） of 80.0% at 1.0 m A/cm;after continuously running for more than 1000 cycles, which is by far the longest cycle life reported for non-aqueous flow batteries.展开更多
A pore-network model physically based on pore level multiphase flow was used to study the water-non-aqueous phase liquid （NAPL） displacement process, especially the effects of wettability, water-NAPL interracial ten...A pore-network model physically based on pore level multiphase flow was used to study the water-non-aqueous phase liquid （NAPL） displacement process, especially the effects of wettability, water-NAPL interracial tension, the fraction of NAPL-wet pores, and initial water saturation on the displacement. The computed data show that with the wettability of the mineral surfaces changing from strongly water-wet to NAPL-wet, capillary pressure and the NAPL relative permeability gradually decrease, while water-NAPL interfacial tension has little effect on water relative permeability, but initial water saturation has a strong effect on water and NAPL relative permeabilities. The analytical results may help to understand the micro-structure displacement process of non-aqueous phase liquid and to provide the theoretical basis for controlling NAPL migration.展开更多
Polyoxometalates have been explored as multi-electron active species in both aqueous and non-aqueous redox flow batteries. Although non-aqueous systems in principle offer a wider voltage window for redox flow battery ...Polyoxometalates have been explored as multi-electron active species in both aqueous and non-aqueous redox flow batteries. Although non-aqueous systems in principle offer a wider voltage window for redox flow battery operation, realization of this potential requires a judicious choice of solvent as well as polyoxometalate properties. We demonstrate here the superior performance of N,N-dimethylformamide(DMF)compared to acetonitrile as a solvent for redox flow batteries based on Li3PMo12O40. This compound displays two 1-electron transfers in acetonitrile but can access an extra quasi-reversible 2-electron redox process in DMF. A cell containing 10 mM solution of Li3PMo12O40 in DMF produced a cell voltage of 0.7 V with 2-electron transfers(State of Charge = 60%) and showed a good cyclability. As a means to boost energy density, operation of the redox flow battery at a higher concentration of 0.1 M Li3PMo12O40 produced cells with cell voltage of 0.6 V in acetonitrile and a cell voltage of 1.0 V in DMF;both showed excellent coulombic efficiencies of more than 90% over the course of 30 cycles. Energy density was also increased by employing an asymmetric cell with different polyoxometalates on each side to extend cell voltage.Li6P2W18O62 exhibited 3 quasi-reversible 2-electron transfers in the potential range between-2.05 V and-0.5 V vs. Ag/Ag+. 10 mM Li6P2W18O62/Li3PMo12O40 in DMF produced a cell with cell voltage of 1.3 V involving 4-electron transfers(State of Charge = 50%) with coulombic efficiency of nearly 100% and energy efficiency of nearly 70% throughout the test with more than 20 cycles. These promising results demonstrate proof-of-concept approaches to improving the performance of polyoxometalates in non-aqueous redox flow batteries.展开更多
yb3＋/Dy3＋ co-doped A1203 nanopowders have been prepared by the non-aqueous sol-gel method and their up- conversion photoluminescence spectra are measured under excitation by a 980-nm semiconductor laser. The results...yb3＋/Dy3＋ co-doped A1203 nanopowders have been prepared by the non-aqueous sol-gel method and their up- conversion photoluminescence spectra are measured under excitation by a 980-nm semiconductor laser. The results show that there are comparatively abundant spectra of up-conversion emissions centered at 378, 408, 527 and 543, and 663 nm, corresponding to 4C9/2→ 6H13/2, 4C9/2→ 6Hll/2, 4115/2 → 6H13/2, and 4F9/2 →6Hll/2 transitions of Dy3＋, respectively. Two-photon and three-photon processes are involved in ultraviolet, violet, green, and red up-conversion emissions. The energy transition between Yb3＋ and Dy3＋ is discussed.展开更多
Non-aqueous extraction(NAE)of bitumen from oil sands has been gaining great attention from both the industry and academia as an alternative to the water-based extraction.A fine solids removal step is important for a N...Non-aqueous extraction(NAE)of bitumen from oil sands has been gaining great attention from both the industry and academia as an alternative to the water-based extraction.A fine solids removal step is important for a NAE process in order to obtain high-quality bitumen product,which,however,remains a great challenge to reduce the fine solids content to the desired level.Here,we introduce a strategy of destabilizing the bitumen-coated silica particles in toluene with the addition of water and biomolecules extracted from Cyamopsiste tragonolobuosr L.Taup.,i.e.,high molecular weight guar gum(HGG)and low molecular weight guar gum(LGG),respectively.By virtue of sedimentation tests and focused beam reflectance measurement analysis,we demonstrate that the introduced water droplets modified with these biomolecules can facilitate the settling of the solid particles in toluene although the underlying mechanisms differ between these two biomolecule cases.Specifically,in the case of LGG,the added water droplets with the interfacial amphiphilic LGG can strengthen the attachment of solid particles from bulk toluene to the LGG surface.This research work provides useful insight into the development of effective approaches for destabilization and removal of bitumen-coated fine solids from NAE bitumen.展开更多
Western Canada’s oil sands hold the third-largest hydrocarbon deposits in the world.Bitumen,a very heavy petroleum,is currently recovered by surface mining with warm water or in situ.Recovery processes that use organ...Western Canada’s oil sands hold the third-largest hydrocarbon deposits in the world.Bitumen,a very heavy petroleum,is currently recovered by surface mining with warm water or in situ.Recovery processes that use organic solvents are being developed to reduce water usage and tailings production.While solvent-based methods can effectively extract bitumen,removal of residual fine solids from diluted bitumen product(DBP)to meet the pipeline transport requirement of<0.5 wt%solids and water in DBP remains a major challenge.We propose a novel area of application of polymer flocculants for fine solids removal from DBP.In principle,polymer flocculants can be applied to help remove these residual solids in conjunction with physical separation processes to increase process effectiveness and energy efficiency.Several polymers are selected and screened for flocculation behavior using kaolinite suspended in DBP and toluene,as a model system.Focused beam reflectance measurements and force tensiometer techniques are used to determine flocculation and sedimentation in DBP.The observed flocculation and sedimentation rate enhancements indicate that the polymers tested have only minor effects,providing opportunities for advanced polymer development.These findings exemplify the challenges in identifying polymers that may be effective as flocculants in heavy petroleum media.展开更多
基金supported by the National Natural Science Foundation of China(Nos:51503038 and 51873037).
文摘The exploitation of high performance redox-active substances is critically important for the development of non-aqueous redoxflow batteries.Herein,three tetrathiofulvalene(TTF)derivatives with different substitution groups,namely TTF diethyl ester(TTFDE),TTF tetramethyl ester(TTFTM),and TTF tetraethyl ester(TTFTE),are prepared and their energy storage properties are evaluated.It has been found that the redox potential and solubility of these TTF derivatives in conventional carbonate electrolytes increases with the number of ester groups.The battery with a catholyte of 0.2 mol L^(-1) of TTFTE delivers a specific capacity of more than 10 Ah L^(-1) at the current density of 0.5 C with two discharge voltage platforms locating at as high as 3.85 and 3.60 V vs.Li/Liþ.Its capacity retention can be improved from 2.34 Ah L^(-1) to 3.60 Ah L^(-1) after 100 cycles by the use of an anion exchange membrane to block the crossover of TTF species.The excellent cycling stability of the TIF esters is supported by their well-delocalized electrons,as revealed by the density function theory calculations.Therefore,the introduction of more and larger electron-withdrawing groups is a promising strategy to simultaneously increase the redox-potential and solubility of redox-active ma-terials for non-aqueous redoxflow batteries.
基金financial supported by the Natural Science Foundation of China(Grant No.21476224,21406219 and 51361135701)
文摘Flow batteries with high energy density and long cycle life have been pursued to advance the progress of energy storage and grid application. Non-aqueous batteries with wide voltage windows represent a promising technology without the limitation of water electrolysis, but they suffer from low electrolyte concentration and unsatisfactory battery performance. Here, a non-aqueous lithium bromine rechargeable battery is proposed, which is based on Br;/Br;and Li;/Li as active redox pairs, with fast redox kinetics and good stability. The Li/Br battery combines the advantages of high output voltage（;.1 V）,electrolyte concentration（3.0 mol/L）, maximum power density（29.1 m W/cm;） and practical energy density（232.6 Wh/kg）. Additionally, the battery displays a columbic efficiency（CE） of 90.0%, a voltage efficiency（VE） of 88.0% and an energy efficiency（EE） of 80.0% at 1.0 m A/cm;after continuously running for more than 1000 cycles, which is by far the longest cycle life reported for non-aqueous flow batteries.
文摘A pore-network model physically based on pore level multiphase flow was used to study the water-non-aqueous phase liquid （NAPL） displacement process, especially the effects of wettability, water-NAPL interracial tension, the fraction of NAPL-wet pores, and initial water saturation on the displacement. The computed data show that with the wettability of the mineral surfaces changing from strongly water-wet to NAPL-wet, capillary pressure and the NAPL relative permeability gradually decrease, while water-NAPL interfacial tension has little effect on water relative permeability, but initial water saturation has a strong effect on water and NAPL relative permeabilities. The analytical results may help to understand the micro-structure displacement process of non-aqueous phase liquid and to provide the theoretical basis for controlling NAPL migration.
文摘Polyoxometalates have been explored as multi-electron active species in both aqueous and non-aqueous redox flow batteries. Although non-aqueous systems in principle offer a wider voltage window for redox flow battery operation, realization of this potential requires a judicious choice of solvent as well as polyoxometalate properties. We demonstrate here the superior performance of N,N-dimethylformamide(DMF)compared to acetonitrile as a solvent for redox flow batteries based on Li3PMo12O40. This compound displays two 1-electron transfers in acetonitrile but can access an extra quasi-reversible 2-electron redox process in DMF. A cell containing 10 mM solution of Li3PMo12O40 in DMF produced a cell voltage of 0.7 V with 2-electron transfers(State of Charge = 60%) and showed a good cyclability. As a means to boost energy density, operation of the redox flow battery at a higher concentration of 0.1 M Li3PMo12O40 produced cells with cell voltage of 0.6 V in acetonitrile and a cell voltage of 1.0 V in DMF;both showed excellent coulombic efficiencies of more than 90% over the course of 30 cycles. Energy density was also increased by employing an asymmetric cell with different polyoxometalates on each side to extend cell voltage.Li6P2W18O62 exhibited 3 quasi-reversible 2-electron transfers in the potential range between-2.05 V and-0.5 V vs. Ag/Ag+. 10 mM Li6P2W18O62/Li3PMo12O40 in DMF produced a cell with cell voltage of 1.3 V involving 4-electron transfers(State of Charge = 50%) with coulombic efficiency of nearly 100% and energy efficiency of nearly 70% throughout the test with more than 20 cycles. These promising results demonstrate proof-of-concept approaches to improving the performance of polyoxometalates in non-aqueous redox flow batteries.
基金Project supported by the National Natural Science Foundation of China （Grant No. 11004092） and the Scientific Research Fund of Education Department of Liaoning Province, China （Grant No. 2009A417）.
文摘yb3＋/Dy3＋ co-doped A1203 nanopowders have been prepared by the non-aqueous sol-gel method and their up- conversion photoluminescence spectra are measured under excitation by a 980-nm semiconductor laser. The results show that there are comparatively abundant spectra of up-conversion emissions centered at 378, 408, 527 and 543, and 663 nm, corresponding to 4C9/2→ 6H13/2, 4C9/2→ 6Hll/2, 4115/2 → 6H13/2, and 4F9/2 →6Hll/2 transitions of Dy3＋, respectively. Two-photon and three-photon processes are involved in ultraviolet, violet, green, and red up-conversion emissions. The energy transition between Yb3＋ and Dy3＋ is discussed.
基金the financial support from Institute for Oil Sands Innovation(IOSI),Imperial Oil,the Natural Sciences and Engineering Research Council of Canada(NSERC)and Alberta Innovates to the research workthe financial support from the Canada Foundation for Innovation(CFI),the Future Energy Systems underthe Canada First Research Excellence Fund and the Canada Research Chairs Program。
文摘Non-aqueous extraction(NAE)of bitumen from oil sands has been gaining great attention from both the industry and academia as an alternative to the water-based extraction.A fine solids removal step is important for a NAE process in order to obtain high-quality bitumen product,which,however,remains a great challenge to reduce the fine solids content to the desired level.Here,we introduce a strategy of destabilizing the bitumen-coated silica particles in toluene with the addition of water and biomolecules extracted from Cyamopsiste tragonolobuosr L.Taup.,i.e.,high molecular weight guar gum(HGG)and low molecular weight guar gum(LGG),respectively.By virtue of sedimentation tests and focused beam reflectance measurement analysis,we demonstrate that the introduced water droplets modified with these biomolecules can facilitate the settling of the solid particles in toluene although the underlying mechanisms differ between these two biomolecule cases.Specifically,in the case of LGG,the added water droplets with the interfacial amphiphilic LGG can strengthen the attachment of solid particles from bulk toluene to the LGG surface.This research work provides useful insight into the development of effective approaches for destabilization and removal of bitumen-coated fine solids from NAE bitumen.
文摘Western Canada’s oil sands hold the third-largest hydrocarbon deposits in the world.Bitumen,a very heavy petroleum,is currently recovered by surface mining with warm water or in situ.Recovery processes that use organic solvents are being developed to reduce water usage and tailings production.While solvent-based methods can effectively extract bitumen,removal of residual fine solids from diluted bitumen product(DBP)to meet the pipeline transport requirement of<0.5 wt%solids and water in DBP remains a major challenge.We propose a novel area of application of polymer flocculants for fine solids removal from DBP.In principle,polymer flocculants can be applied to help remove these residual solids in conjunction with physical separation processes to increase process effectiveness and energy efficiency.Several polymers are selected and screened for flocculation behavior using kaolinite suspended in DBP and toluene,as a model system.Focused beam reflectance measurements and force tensiometer techniques are used to determine flocculation and sedimentation in DBP.The observed flocculation and sedimentation rate enhancements indicate that the polymers tested have only minor effects,providing opportunities for advanced polymer development.These findings exemplify the challenges in identifying polymers that may be effective as flocculants in heavy petroleum media.
