Viologens known as a kind of promising negolyte materials for aqueous organic redox flow batteries,face a critical stability challenge due to the S_N2 nucleophilic attack by hydroxide ions(OH-)during the battery cycli...Viologens known as a kind of promising negolyte materials for aqueous organic redox flow batteries,face a critical stability challenge due to the S_N2 nucleophilic attack by hydroxide ions(OH-)during the battery cycling.In this work,a N-cyclic quaternary ammonium-grafted viologen molecule,viz.1,1'-bis(4,4'-dime thylpiperidiniumyl)-4,4'-bipyridinium tetrachloride((DBPPy)Cl_(4)),is developed by the molecular engineering strategy.The obtained(DBPPy)Cl_(4) molecule shows a decent solubility of 1.84 M and a redox potential of-0.52 V vs.Ag/AgCl,Experimental and theoretical results reveal that the grafted N-cyclic quaternary ammonium groups act as the steric hindrance to prevent nucleophilic attack by OH~-,increasing the alkali resistance of the electroactive molecule.The symmetrical battery with 0.50 M(DBPPy)Cl4shows negligible decay during the 13-day cycling test.As demonstration,the flow battery utilizing 1.0 M(DBPPy)Cl_(4) as the negolyte and 1-(1-oxyl-2,2',6,6'-tetramethylpiperidin-4-yl)-1'-(3-(trimethylammonio)propyl)-4,4'-bipyridinium trichloride as the posolyte exhibits a high capacity retention rate of 99.99%per cycle at 60 mA cm^(-2).展开更多
Abstract A new microfluidic system with four different microchambers （a circle and three equilateral concave polygons） was designed and fabricated using poly（dimethylsiloxane） （PDMS） and the soft lithography met...Abstract A new microfluidic system with four different microchambers （a circle and three equilateral concave polygons） was designed and fabricated using poly（dimethylsiloxane） （PDMS） and the soft lithography method. Using this microfluidic device at six flow rates （5, 10, 20, 30, 40, and 50 μL/h）, the effects of microenvironmental geometry and aqueous flow on bacterial adhesion behaviors were investigated. Escherichia coli HB101 pGLO, which could produce a green fluorescent protein induced by L-arabinose, was utilized as the model bacteria. The results demonstrated that bacterial adhesion was significantly related to culture time, microenvironment geometry, and aqueous flow rates. Adhered bacterial density increased with the culture time. Initially, the adhesion occurred at the microchamber sides, and then the entire chamber was gradually covered with increased culture time. Adhesion densities in the side zones were larger than those in the center zones because of the lower shearing force in the side zone. Also, the adhesion densities in the complex chambers were larger than those in the simple chambers. At low flow rates, the orientation of adhered bacteria was random and disorderly. At high flow rates, bacterial orientation became close to the streamline and oriented toward the flow direction; All these results implied that bacterial adhesion tended to occur in complicated aqueous flow areas.The present study provided an on-chip flow system for physiological behavior of biological cells, as well as provided a strategic cue for the prevention of bacterial infection and biofilm formation.展开更多
Aqueous flow batteries(AFBs) are among the most promising electrochemical energy storage solutions for the massive-scale adoption of renewable electricity because of decoupled energy and power, design flexibility, imp...Aqueous flow batteries(AFBs) are among the most promising electrochemical energy storage solutions for the massive-scale adoption of renewable electricity because of decoupled energy and power, design flexibility, improved safety and low cost. The development of high-voltage AFB is, however, limited by the lack of stable anolytes that have low redox potential. Here we report Eu-based anolytes for high-voltage p H-neutral AFB applications. Eu^(3+) has a reduction potential of -0.39 V vs. SHE, which can be dramatically lowered when forming stable complex with inexpensive organic chelates. A typical complex, Eu DTPA,features a low redox potential of -1.09 V vs. SHE, fast redox kinetics, and a high water solubility of 1.5 M. When paired with ferrocyanide, the battery had an open-circuit voltage of 1.56 V and demonstrated stable cell cycling performance, including a capacity retention rate of 99.997% per cycle over500 cycles at 40 m A cm^(-2), a current efficiency of >99.9%, and an energy efficiency of >83.3%. A high concentration anolyte at 1.5 M exhibited a volumetric capacity of 40.2 Ah L^(-1), which is one of the highest known for p H-neutral AFBs, promising a potent solution for the grid-scale storage of renewable electricity.展开更多
The wide deployment of renewable sources such as wind and solar power is the key to achieve a low-carbon world[1].However,renewable energies are intermittent,unstable,and uncontrollable,and large-scale integration wil...The wide deployment of renewable sources such as wind and solar power is the key to achieve a low-carbon world[1].However,renewable energies are intermittent,unstable,and uncontrollable,and large-scale integration will seriously affect the safe,efficient,and reliable operation of the power grid.Energy storage is the key to smooth output and further realize the application of renewable energies[2].Among different types of energy storage techniques,aqueous flow batteries(FBs)are one of the preferred technologies for large-scale and efficient energy storage due to their advantages of high safety,long cycle life(15 to 20 years),and high efficiency[3-5].展开更多
Aqueous organic redox flow batteries(AORFBs),which exploit the reversible electrochemical reactions of water-soluble organic electrolytes to store electricity,have emerged as an efficient electrochemical energy storag...Aqueous organic redox flow batteries(AORFBs),which exploit the reversible electrochemical reactions of water-soluble organic electrolytes to store electricity,have emerged as an efficient electrochemical energy storage technology for the grid-scale integration of renewable electricity.pH-neutral AORFBs that feature high safety,low corrosivity,and environmental benignity are particularly promising,and their battery performance is significantly impacted by redox-active molecules and ion-exchange membranes(IEMs).Here,representative anolytes and catholytes engineered for use in pH-neutral AORFBs are outlined and summarized,as well as their side reactions that cause irreversible battery capacity fading.In addition,the recent achievements of IEMs for pH-neutral AORFBs are discussed,with a focus on the construction and tuning of ion transport channels.Finally,the critical challenges and potential research opportunities for developing practically relevant pH-neutral AORFBs are presented.展开更多
Due to the diversity and feasibility of structural modification for organic molecules,organic-based redox flow batteries(ORFBs)have been widely investigated,especially in aqueous solution under neutral circumstance.In...Due to the diversity and feasibility of structural modification for organic molecules,organic-based redox flow batteries(ORFBs)have been widely investigated,especially in aqueous solution under neutral circumstance.In this work,a symmetric aqueous redox flow battery(SARFB)was rationally designed by employing a bipolar redox active molecule(N,N’-dimethyl-4,4-bipyridinium diiodide,MVI2)as both cathode and anode materials and combining with an anion exchange membrane.For one MVI2 flow battery,MV2+/MV·+and I-/I3-serve as the redox couples of anode and cathode,respectively.The MVI2 battery with a working voltage of 1.02 V exhibited a high voltage efficiency of 90.30%and energy efficiency of 89.44%after 450 cycles,and crossover problem was prohibited.The comparable conductivity of MVI2 water solution enabled to construct a battery even without using supporting electrolyte.Besides,the bipolar character of MVI2 battery with/without supporting electrolyte was investigated in the voltage range between-1.2 V and 1.2 V,showing excellent stable cycling stability during the polarity-reversal test.展开更多
Aqueous redox flow batteries,by using redox-active molecules dissolved in nonflammable water solutions as electrolytes,are a promising technology for grid-scale energy storage.Organic redox-active materials offer a ne...Aqueous redox flow batteries,by using redox-active molecules dissolved in nonflammable water solutions as electrolytes,are a promising technology for grid-scale energy storage.Organic redox-active materials offer a new opportunity for the construction of advanced flow batteries due to their advantages of potentially low cost,extensive structural diversity,tunable electrochemical properties,and high natural abundance.In this review,we present the emergence and development of organic redox-active materials for aqueous organic redox flow batteries(AORFBs),in particular,molecular engineering concepts and strategies of organic redox-active molecules.The typical design strategies based on organic redox species for high-capacity,high-stability,and high-voltage AORFBs are outlined and discussed.Molecular engineering of organic redox-active molecules for high aqueous solubility,high chemical/electrochemical stability,and multiple electron numbers as well as satisfactory redox potential gap between the redox pair is essential to realizing high-performance AORFBs.Beyond molecular engineering,the redoxtargeting strategy is an effective way to obtain high-capacity AORFBs.We further discuss and analyze the redox reaction mechanisms of organic redox species based on a series of electrochemical and spectroscopic approaches,and succinctly summarize the capacity degradation mechanisms of AORFBs.Furthermore,the current challenges,opportunities,and future directions of organic redox-active materials for AORFBs are presented in detail.展开更多
Five-membered pyrroline nitroxides with high-potential is fascinating as catholyte for aqueous organic redox flow batteries(AORFBs),however,it suffers from a primary deficiency of insufficient stability due to ring-op...Five-membered pyrroline nitroxides with high-potential is fascinating as catholyte for aqueous organic redox flow batteries(AORFBs),however,it suffers from a primary deficiency of insufficient stability due to ring-opening side reaction.Herein we report a spatial structure regulation strategy by host-vip chemistry,encapsulating 3-carbamoyl-2,2,5,5-tetramethylpyrroline-1-oxyl(CPL)into hydrosoluble cyclodextrins(CDs)with an inclusion structure of N–O⋅head towards cavity bottom,to boost the solubility and cyclability of pyrroline nitroxides significantly.The armor-clad CPL(CPL⊂HP-β-CD)catholyte in 0.05–0.5 M presents a battery capacity fade rate as low as 0.002%/cycle(0.233%/day)compared to the sole CPL in 0.05 M(0.039%/cycle or 5.23%/day)over 500 cycles in assembled AORFBs.The optimized reclining spatial structure with N–O⋅head towards CD cavity bottom effectively inhibits the attack of Lewis base species on the hydrogen abstraction site in pyrroline ring,and thus avoids the ring-opening side reaction of pyrroline nitroxides.展开更多
In the Review Article“Recent advances and future perspectives of membranes in iron-based aqueous redox flow batteries”,three production errors need to be corrected[1].In Eq.1 within the section on“Iron-chromium RFB...In the Review Article“Recent advances and future perspectives of membranes in iron-based aqueous redox flow batteries”,three production errors need to be corrected[1].In Eq.1 within the section on“Iron-chromium RFBs”,the reaction product is“Cr^(2+)”(not Cr^(3+)),and the potential is−0.41 V(not−0.44 V).展开更多
Iron-based aqueous redox flow batteries(IBA-RFBs)represent a promising solution for long-duration energy storage,supporting the integration of intermittent renewable energy into the grid,thanks to their commendable sa...Iron-based aqueous redox flow batteries(IBA-RFBs)represent a promising solution for long-duration energy storage,supporting the integration of intermittent renewable energy into the grid,thanks to their commendable safety profile and cost-effectiveness.Membranes,serving as pivotal components in redox flow batteries(RFBs),play a crucial role in facilitating ion conduction for internal circuit formation while preventing the crossover of redox-active species.Given their direct impact on RFB performance and cost,membranes merit considerable attention.This review provides an overview of recent advancements in membranes tailored for IBA-RFBs.Initially,it delineates the operational mechanisms of various IBA-RFB configurations.Subsequently,it delves into key performance metrics for evaluating membrane efficacy,dissecting the intricate interplay between membrane performance and overall IBA-RFB efficiency.Building upon this foundation,the review spotlights recent breakthroughs in ion exchange membranes and porous membranes designed specifically for IBA-RFBs,showcasing their remarkable ability to bolster battery efficiency,cycling stability,and cost-effectiveness.Lastly,this review outlines future directions for membrane development,offering some insights to propel the widespread adoption of IBA-RFBs on a large scale.展开更多
基金jointly supported by the Guangdong Major Project of Basic and Applied Basic Research (2023B0303000002)National Natural Science Foundation of China (22178126,22325802,U22A20417,22208110)+3 种基金Guangdong Basic and Applied Basic Research Foundation (2023B1515120005)Science and Technology Program of Guangzhou (2023B03J1281,2023A04J1357)China Postdoctoral Science Foundation (2023T160223)the State Key Laboratory of Pulp and Paper Engineering (2023ZD03)。
文摘Viologens known as a kind of promising negolyte materials for aqueous organic redox flow batteries,face a critical stability challenge due to the S_N2 nucleophilic attack by hydroxide ions(OH-)during the battery cycling.In this work,a N-cyclic quaternary ammonium-grafted viologen molecule,viz.1,1'-bis(4,4'-dime thylpiperidiniumyl)-4,4'-bipyridinium tetrachloride((DBPPy)Cl_(4)),is developed by the molecular engineering strategy.The obtained(DBPPy)Cl_(4) molecule shows a decent solubility of 1.84 M and a redox potential of-0.52 V vs.Ag/AgCl,Experimental and theoretical results reveal that the grafted N-cyclic quaternary ammonium groups act as the steric hindrance to prevent nucleophilic attack by OH~-,increasing the alkali resistance of the electroactive molecule.The symmetrical battery with 0.50 M(DBPPy)Cl4shows negligible decay during the 13-day cycling test.As demonstration,the flow battery utilizing 1.0 M(DBPPy)Cl_(4) as the negolyte and 1-(1-oxyl-2,2',6,6'-tetramethylpiperidin-4-yl)-1'-(3-(trimethylammonio)propyl)-4,4'-bipyridinium trichloride as the posolyte exhibits a high capacity retention rate of 99.99%per cycle at 60 mA cm^(-2).
基金supported by the National Natural Science Foundation of China (Nos.20975082 and 20775059)the Ministry of Education of the People’s Republic of China (NCET-08-0464),the Scientific Research Foundation for Returned Overseas Chinese Scholars,by the State Education Ministry,by the Northwest A&F University
文摘Abstract A new microfluidic system with four different microchambers （a circle and three equilateral concave polygons） was designed and fabricated using poly（dimethylsiloxane） （PDMS） and the soft lithography method. Using this microfluidic device at six flow rates （5, 10, 20, 30, 40, and 50 μL/h）, the effects of microenvironmental geometry and aqueous flow on bacterial adhesion behaviors were investigated. Escherichia coli HB101 pGLO, which could produce a green fluorescent protein induced by L-arabinose, was utilized as the model bacteria. The results demonstrated that bacterial adhesion was significantly related to culture time, microenvironment geometry, and aqueous flow rates. Adhered bacterial density increased with the culture time. Initially, the adhesion occurred at the microchamber sides, and then the entire chamber was gradually covered with increased culture time. Adhesion densities in the side zones were larger than those in the center zones because of the lower shearing force in the side zone. Also, the adhesion densities in the complex chambers were larger than those in the simple chambers. At low flow rates, the orientation of adhered bacteria was random and disorderly. At high flow rates, bacterial orientation became close to the streamline and oriented toward the flow direction; All these results implied that bacterial adhesion tended to occur in complicated aqueous flow areas.The present study provided an on-chip flow system for physiological behavior of biological cells, as well as provided a strategic cue for the prevention of bacterial infection and biofilm formation.
基金project has been supported by the National Natural Science Foundation of China (Nos. 21878281, 21922510 and 21720102003)the DNL Cooperation Fund, CAS (DNL201910)。
文摘Aqueous flow batteries(AFBs) are among the most promising electrochemical energy storage solutions for the massive-scale adoption of renewable electricity because of decoupled energy and power, design flexibility, improved safety and low cost. The development of high-voltage AFB is, however, limited by the lack of stable anolytes that have low redox potential. Here we report Eu-based anolytes for high-voltage p H-neutral AFB applications. Eu^(3+) has a reduction potential of -0.39 V vs. SHE, which can be dramatically lowered when forming stable complex with inexpensive organic chelates. A typical complex, Eu DTPA,features a low redox potential of -1.09 V vs. SHE, fast redox kinetics, and a high water solubility of 1.5 M. When paired with ferrocyanide, the battery had an open-circuit voltage of 1.56 V and demonstrated stable cell cycling performance, including a capacity retention rate of 99.997% per cycle over500 cycles at 40 m A cm^(-2), a current efficiency of >99.9%, and an energy efficiency of >83.3%. A high concentration anolyte at 1.5 M exhibited a volumetric capacity of 40.2 Ah L^(-1), which is one of the highest known for p H-neutral AFBs, promising a potent solution for the grid-scale storage of renewable electricity.
文摘The wide deployment of renewable sources such as wind and solar power is the key to achieve a low-carbon world[1].However,renewable energies are intermittent,unstable,and uncontrollable,and large-scale integration will seriously affect the safe,efficient,and reliable operation of the power grid.Energy storage is the key to smooth output and further realize the application of renewable energies[2].Among different types of energy storage techniques,aqueous flow batteries(FBs)are one of the preferred technologies for large-scale and efficient energy storage due to their advantages of high safety,long cycle life(15 to 20 years),and high efficiency[3-5].
基金funded by the National Key Research and Development Program of China(Nos.2022YFB3805303,2022YFB3805304)the National Natural Science Foundation of China(Grant/Award Numbers:22308345,U20A20127)+1 种基金the Anhui Provincial Natural Science Foundation(No.2308085QB68)the Fundamental Research Funds for the Central Universities(No.WK2060000059).
文摘Aqueous organic redox flow batteries(AORFBs),which exploit the reversible electrochemical reactions of water-soluble organic electrolytes to store electricity,have emerged as an efficient electrochemical energy storage technology for the grid-scale integration of renewable electricity.pH-neutral AORFBs that feature high safety,low corrosivity,and environmental benignity are particularly promising,and their battery performance is significantly impacted by redox-active molecules and ion-exchange membranes(IEMs).Here,representative anolytes and catholytes engineered for use in pH-neutral AORFBs are outlined and summarized,as well as their side reactions that cause irreversible battery capacity fading.In addition,the recent achievements of IEMs for pH-neutral AORFBs are discussed,with a focus on the construction and tuning of ion transport channels.Finally,the critical challenges and potential research opportunities for developing practically relevant pH-neutral AORFBs are presented.
基金supported by the National Key R&D Program of China(Nos.2016YFA0202500 and 2016YFB0901502)the National Natural Science Foundation of China(NSFC,Nos.21673243,51771094 and 21805141)the Ministry of Education(MOE)of China(No.B12015)and Tianjin High-Tech(No.18JCZDJC31500)。
文摘Due to the diversity and feasibility of structural modification for organic molecules,organic-based redox flow batteries(ORFBs)have been widely investigated,especially in aqueous solution under neutral circumstance.In this work,a symmetric aqueous redox flow battery(SARFB)was rationally designed by employing a bipolar redox active molecule(N,N’-dimethyl-4,4-bipyridinium diiodide,MVI2)as both cathode and anode materials and combining with an anion exchange membrane.For one MVI2 flow battery,MV2+/MV·+and I-/I3-serve as the redox couples of anode and cathode,respectively.The MVI2 battery with a working voltage of 1.02 V exhibited a high voltage efficiency of 90.30%and energy efficiency of 89.44%after 450 cycles,and crossover problem was prohibited.The comparable conductivity of MVI2 water solution enabled to construct a battery even without using supporting electrolyte.Besides,the bipolar character of MVI2 battery with/without supporting electrolyte was investigated in the voltage range between-1.2 V and 1.2 V,showing excellent stable cycling stability during the polarity-reversal test.
基金Scientific and Technological Innovation Special Fund for Carbon Peak and Carbon Neutrality of Jiangsu Province,Grant/Award Number:BK20220008Suzhou Gusu Leading Talent Program of Science and Technology Innovation and Entrepreneurship in Wujiang District,Grant/Award Number:ZXL2021273+5 种基金Central University Basic Research Fund of China,Grant/Award Numbers:020514380266,020514380272,020514380274Natural Science Foundation of Jiangsu Province,Grant/Award Number:BK20200306Research Grants Council of the Hong Kong Special Administrative Region,China,Grant/Award Number:T23‐601/17‐RNational Natural Science Foundation of China,Grant/Award Numbers:21872069,22022505Nanjing International Collaboration Research Program,Grant/Award Numbers:202201007,2022SX00000955National Key R&D Program of China,Grant/Award Number:2017YFA0208200。
文摘Aqueous redox flow batteries,by using redox-active molecules dissolved in nonflammable water solutions as electrolytes,are a promising technology for grid-scale energy storage.Organic redox-active materials offer a new opportunity for the construction of advanced flow batteries due to their advantages of potentially low cost,extensive structural diversity,tunable electrochemical properties,and high natural abundance.In this review,we present the emergence and development of organic redox-active materials for aqueous organic redox flow batteries(AORFBs),in particular,molecular engineering concepts and strategies of organic redox-active molecules.The typical design strategies based on organic redox species for high-capacity,high-stability,and high-voltage AORFBs are outlined and discussed.Molecular engineering of organic redox-active molecules for high aqueous solubility,high chemical/electrochemical stability,and multiple electron numbers as well as satisfactory redox potential gap between the redox pair is essential to realizing high-performance AORFBs.Beyond molecular engineering,the redoxtargeting strategy is an effective way to obtain high-capacity AORFBs.We further discuss and analyze the redox reaction mechanisms of organic redox species based on a series of electrochemical and spectroscopic approaches,and succinctly summarize the capacity degradation mechanisms of AORFBs.Furthermore,the current challenges,opportunities,and future directions of organic redox-active materials for AORFBs are presented in detail.
基金supported by grants from the National Natural Science Foundation of China(No.21875181,22209130,and 22279100)the Natural Science Basic Research Program of Shaanxi(No.2019JLP-13)the China Postdoctoral Science Foundation(No.2022M722524)。
文摘Five-membered pyrroline nitroxides with high-potential is fascinating as catholyte for aqueous organic redox flow batteries(AORFBs),however,it suffers from a primary deficiency of insufficient stability due to ring-opening side reaction.Herein we report a spatial structure regulation strategy by host-vip chemistry,encapsulating 3-carbamoyl-2,2,5,5-tetramethylpyrroline-1-oxyl(CPL)into hydrosoluble cyclodextrins(CDs)with an inclusion structure of N–O⋅head towards cavity bottom,to boost the solubility and cyclability of pyrroline nitroxides significantly.The armor-clad CPL(CPL⊂HP-β-CD)catholyte in 0.05–0.5 M presents a battery capacity fade rate as low as 0.002%/cycle(0.233%/day)compared to the sole CPL in 0.05 M(0.039%/cycle or 5.23%/day)over 500 cycles in assembled AORFBs.The optimized reclining spatial structure with N–O⋅head towards CD cavity bottom effectively inhibits the attack of Lewis base species on the hydrogen abstraction site in pyrroline ring,and thus avoids the ring-opening side reaction of pyrroline nitroxides.
文摘In the Review Article“Recent advances and future perspectives of membranes in iron-based aqueous redox flow batteries”,three production errors need to be corrected[1].In Eq.1 within the section on“Iron-chromium RFBs”,the reaction product is“Cr^(2+)”(not Cr^(3+)),and the potential is−0.41 V(not−0.44 V).
基金supported by the National Natural Science Foundation of China(22022813)the Zhejiang Provincial Natural Science Foundation of China(LQ24B030002)+1 种基金the China Postdoctoral Science Foundation(2022M722729 and 2023T160571)the technology project of Institute of Wenzhou(XMGL-CX-202204 and XMGL-KJZX-202208).
文摘Iron-based aqueous redox flow batteries(IBA-RFBs)represent a promising solution for long-duration energy storage,supporting the integration of intermittent renewable energy into the grid,thanks to their commendable safety profile and cost-effectiveness.Membranes,serving as pivotal components in redox flow batteries(RFBs),play a crucial role in facilitating ion conduction for internal circuit formation while preventing the crossover of redox-active species.Given their direct impact on RFB performance and cost,membranes merit considerable attention.This review provides an overview of recent advancements in membranes tailored for IBA-RFBs.Initially,it delineates the operational mechanisms of various IBA-RFB configurations.Subsequently,it delves into key performance metrics for evaluating membrane efficacy,dissecting the intricate interplay between membrane performance and overall IBA-RFB efficiency.Building upon this foundation,the review spotlights recent breakthroughs in ion exchange membranes and porous membranes designed specifically for IBA-RFBs,showcasing their remarkable ability to bolster battery efficiency,cycling stability,and cost-effectiveness.Lastly,this review outlines future directions for membrane development,offering some insights to propel the widespread adoption of IBA-RFBs on a large scale.
