Redox p-type organic compounds are promising cathode materials for dual-ion batteries.However,the triphenylamine-based polymers usually with agglomerate and intertwined molecular chain nature limit the maximum reactio...Redox p-type organic compounds are promising cathode materials for dual-ion batteries.However,the triphenylamine-based polymers usually with agglomerate and intertwined molecular chain nature limit the maximum reaction of their active sites with large-sized anions.Herein,we demonstrate the application of a small molecule with rigid spirofluorene structu re,namely 2,2’,7,7’-tetrakis(diphenylamine)-9,9’-spirobifluorene(Spiro-TAD),as a cathode material for lithium dual-ion batteries.The inherent sterical structure endows the Spiro-TAD with good chemical stability and large internal space for fast diffusion kinetics of anions in the organic electrolyte.As a result,the Spiro-TAD electrode shows significant insolubility and less steric hindrance,and gives a high actual capacity of 109 mA h g^(-1)(active groups utilization ratio approximately 100%) at 50 mA g^(-1)with a high discharge voltage of 3.6 V(vs.Li+/Li),excellent rate capability(60 mA h g^(-1)at 2000 mA g^(-1)) and extremely stable cycling life(98.4% capacity retention after 1400 cycles at 500 mA g^(-1)) in half cells.Such good electrochemical performance is attributed to the robust and rapid adsorption/desorption of ClO4-anions,which can be proved by the in-situ FTIR and XPS.Moreover,an all-organic lithium dual-ion battery(a-OLDIBs) is constructed using the Spiro-TAD as cathode and 3,4,9,10-Perylenetetracarboxylic diimide(PTCDI) as anode and displays long-term cycling performance of 87.5 mA h g^(-1)after 800 cycles.This study will stimulate further developments in designing all organic battery systems.展开更多
Rechargeable aqueous zinc-ion batteries are recently gaining incremental attention because of low cost and material abundance, but their development is plagued by limited choice of cathode materials with satisfactory ...Rechargeable aqueous zinc-ion batteries are recently gaining incremental attention because of low cost and material abundance, but their development is plagued by limited choice of cathode materials with satisfactory cycling performance. Here, we report a porous V2O5 nanofibers cathode with high Znstorage performance in an aqueous Zn(CF3SO3)2 electrolyte. We propose a reaction mechanism based on phase transition from orthorhombic V2O5 to zinc pyrovanadate on first discharging and reversible Zn^2+ (de)intercalation in the open-structured hosts during subsequent cycling. This open and stable architecture enables a high reversible capacity of 319 mAh g^-1 at 20 mAg^-1 and a capacity retention of 81% over 500 cycles. The remarkable electrochemical performance makes V2O5 a promising cathode for aqueous zinc-ion batteries.展开更多
Organic materials with redox-active centers are regarded as promising candidates for rechargeable batteries in recent years for their light weight, low cost, environmental friendliness and structural diversity [1–4]....Organic materials with redox-active centers are regarded as promising candidates for rechargeable batteries in recent years for their light weight, low cost, environmental friendliness and structural diversity [1–4]. Organic materials, such as conducting polymers (polyacetylene, polypyrrole, polyaniline, etc.)[5], conjugated carbonyl compounds (quinone compounds, imides, etc.)[6–9] and nitroxide radical (N-O.)[10,11] compounds have been attempted as cathode materials in lithium-ion batteries (LIBs).展开更多
This work investigates the security issue of the energy-constrained untrusted relay network with imperfect channel reciprocity,where the relay without the built-in power supply can only scavenge energy from radio-freq...This work investigates the security issue of the energy-constrained untrusted relay network with imperfect channel reciprocity,where the relay without the built-in power supply can only scavenge energy from radio-frequency signals radiated by the source and destination.A hybrid power-splitting(PS)-and time-switching(TS)-based relaying(HPTR)protocol is presented to improve the degraded secrecy performance due to the incomplete self-interference cancellation at the destination.To evaluate the secrecy throughput(ST)of the studied system,the analytical expression of the secrecy outage probability under the delay-limited transmission mode and the closed-form lower bound of the ergodic secrecy capacity under delay-tolerant transmission mode are derived.Both linear and nonlinear models for the energy harvester at the relay are compared.The optimal PS and TS ratios are evaluated numerically.The theoretical derivations are validated by numerical results,revealing that the residual jamming has a negative effect on the secrecy performance of untrusted relay networks,which can be alleviated by the HPTR protocol.Besides,we compare the ST performance of the HPTR protocol with that of the PS and TS relaying schemes,and the results show that the HPTR protocol outperforms both PS and TS relaying protocols in terms of the ST.展开更多
Na-O_(2) and K-O_(2) batteries have attracted extensive attention in recent years.However,the parasitic reactions involving the discharge product of NaO_(2) or K anode with electrolytes and the severe Na or K dendrite...Na-O_(2) and K-O_(2) batteries have attracted extensive attention in recent years.However,the parasitic reactions involving the discharge product of NaO_(2) or K anode with electrolytes and the severe Na or K dendrites plague their rechargeability and cycle stability.Herein,we report a hybrid Na//K^(+)-containing electrolyte//O_(2) battery consisting of a Na anode,1.0 M of potassium trifate in diglyme,and a porous carbon cathode.Upon discharging,KO_(2) is preferentially produced via oxygen reduction in the cathode with Na+stripped from the Na anode,and reversely,the KO_(2) is electrochemically decomposed with Na+plated back onto the anode.Te new reaction pathway can circumvent the parasitic reactions involving instable NaO_(2) and active K anode,and alternatively,the good stability and conductivity of KO_(2) and stable Na stripping/plating in the presence of K^(+) enable the hybrid battery to exhibit an average discharge/charge voltage gap of 0.15 V,high Coulombic efciency of>96%,and superior cycling stability of 120 cycles.Tis will pave a new pathway to promote metal-air batteries.展开更多
基金supported by the National Natural Science Foundation of China (21905205 and 22109037)the Natural Science Foundation of Tianjin City (20JCYBJC00380)+1 种基金the Advanced Talents Incubation Program of Hebei University (521000981408)the Haihe Laboratory of Sustainable Chemical Transformations(YYJC202110)。
文摘Redox p-type organic compounds are promising cathode materials for dual-ion batteries.However,the triphenylamine-based polymers usually with agglomerate and intertwined molecular chain nature limit the maximum reaction of their active sites with large-sized anions.Herein,we demonstrate the application of a small molecule with rigid spirofluorene structu re,namely 2,2’,7,7’-tetrakis(diphenylamine)-9,9’-spirobifluorene(Spiro-TAD),as a cathode material for lithium dual-ion batteries.The inherent sterical structure endows the Spiro-TAD with good chemical stability and large internal space for fast diffusion kinetics of anions in the organic electrolyte.As a result,the Spiro-TAD electrode shows significant insolubility and less steric hindrance,and gives a high actual capacity of 109 mA h g^(-1)(active groups utilization ratio approximately 100%) at 50 mA g^(-1)with a high discharge voltage of 3.6 V(vs.Li+/Li),excellent rate capability(60 mA h g^(-1)at 2000 mA g^(-1)) and extremely stable cycling life(98.4% capacity retention after 1400 cycles at 500 mA g^(-1)) in half cells.Such good electrochemical performance is attributed to the robust and rapid adsorption/desorption of ClO4-anions,which can be proved by the in-situ FTIR and XPS.Moreover,an all-organic lithium dual-ion battery(a-OLDIBs) is constructed using the Spiro-TAD as cathode and 3,4,9,10-Perylenetetracarboxylic diimide(PTCDI) as anode and displays long-term cycling performance of 87.5 mA h g^(-1)after 800 cycles.This study will stimulate further developments in designing all organic battery systems.
基金financially supported by Tianjin Natural Science Foundation (No. 18JCZDJC31100)MOST(2017YFA0206700 and 2016YFA0202503)+1 种基金MOE(B12015)the Fundamental Research Funds for the Central Universities
文摘Rechargeable aqueous zinc-ion batteries are recently gaining incremental attention because of low cost and material abundance, but their development is plagued by limited choice of cathode materials with satisfactory cycling performance. Here, we report a porous V2O5 nanofibers cathode with high Znstorage performance in an aqueous Zn(CF3SO3)2 electrolyte. We propose a reaction mechanism based on phase transition from orthorhombic V2O5 to zinc pyrovanadate on first discharging and reversible Zn^2+ (de)intercalation in the open-structured hosts during subsequent cycling. This open and stable architecture enables a high reversible capacity of 319 mAh g^-1 at 20 mAg^-1 and a capacity retention of 81% over 500 cycles. The remarkable electrochemical performance makes V2O5 a promising cathode for aqueous zinc-ion batteries.
基金financially supported by the National Key R&D Program of China(2017YFA0206700)the National Natural Science Foundation of China(grant No.21822506&51671107)+1 种基金the 111 project of B12015the Natural Science Foundation of Tianjin(grant No.19JCJQJC62400)。
文摘Organic materials with redox-active centers are regarded as promising candidates for rechargeable batteries in recent years for their light weight, low cost, environmental friendliness and structural diversity [1–4]. Organic materials, such as conducting polymers (polyacetylene, polypyrrole, polyaniline, etc.)[5], conjugated carbonyl compounds (quinone compounds, imides, etc.)[6–9] and nitroxide radical (N-O.)[10,11] compounds have been attempted as cathode materials in lithium-ion batteries (LIBs).
基金Special Foundation for Chongqing Science and Technology Talent(cstc2019yszx-jcyj X0006 and cstc2020yszx-jscx X0004)Advanced Research Project of Civil Aerospace Technologies in 13th Five-year Plan(D010201)。
文摘This work investigates the security issue of the energy-constrained untrusted relay network with imperfect channel reciprocity,where the relay without the built-in power supply can only scavenge energy from radio-frequency signals radiated by the source and destination.A hybrid power-splitting(PS)-and time-switching(TS)-based relaying(HPTR)protocol is presented to improve the degraded secrecy performance due to the incomplete self-interference cancellation at the destination.To evaluate the secrecy throughput(ST)of the studied system,the analytical expression of the secrecy outage probability under the delay-limited transmission mode and the closed-form lower bound of the ergodic secrecy capacity under delay-tolerant transmission mode are derived.Both linear and nonlinear models for the energy harvester at the relay are compared.The optimal PS and TS ratios are evaluated numerically.The theoretical derivations are validated by numerical results,revealing that the residual jamming has a negative effect on the secrecy performance of untrusted relay networks,which can be alleviated by the HPTR protocol.Besides,we compare the ST performance of the HPTR protocol with that of the PS and TS relaying schemes,and the results show that the HPTR protocol outperforms both PS and TS relaying protocols in terms of the ST.
基金Financial support from National Key R&D Program of China(2017YFA0206700)NSFC(grant No.21603108&51671107)+1 种基金National Natural Science Foundation of ChinaResearch Grants Council of Hong Kong joint project(NSFCRGC project of 51761165025)the 111 project of B12015 is acknowledged.
文摘Na-O_(2) and K-O_(2) batteries have attracted extensive attention in recent years.However,the parasitic reactions involving the discharge product of NaO_(2) or K anode with electrolytes and the severe Na or K dendrites plague their rechargeability and cycle stability.Herein,we report a hybrid Na//K^(+)-containing electrolyte//O_(2) battery consisting of a Na anode,1.0 M of potassium trifate in diglyme,and a porous carbon cathode.Upon discharging,KO_(2) is preferentially produced via oxygen reduction in the cathode with Na+stripped from the Na anode,and reversely,the KO_(2) is electrochemically decomposed with Na+plated back onto the anode.Te new reaction pathway can circumvent the parasitic reactions involving instable NaO_(2) and active K anode,and alternatively,the good stability and conductivity of KO_(2) and stable Na stripping/plating in the presence of K^(+) enable the hybrid battery to exhibit an average discharge/charge voltage gap of 0.15 V,high Coulombic efciency of>96%,and superior cycling stability of 120 cycles.Tis will pave a new pathway to promote metal-air batteries.