Although lithium-sulfur batteries(LSBs)exhibit high theoretical energy density,their practical application is hindered by poor conductivity of the sulfur cathode,the shuttle effect,and the irreversible deposition of L...Although lithium-sulfur batteries(LSBs)exhibit high theoretical energy density,their practical application is hindered by poor conductivity of the sulfur cathode,the shuttle effect,and the irreversible deposition of Li_(2)S.To address these issues,a novel composite,using electrospinning technology,consisting of Fe_(3)Se_(4)and porous nitrogen-doped carbon nanofibers was designed for the interlayer of LSBs.The porous carbon nanofiber structure facilitates the transport of ions and electrons,while the Fe_(3)Se_(4)material adsorbs lithium polysulfides(LiPSs)and accelerates its catalytic conversion process.Furthermore,the Fe_(3)Se_(4)material interacts with soluble LiPSs to generate a new polysulfide intermediate,Li_(x)FeS_(y)complex,which changes the electrochemical reaction pathway and facilitates the three-dimensional deposition of Li_(2)S,enhancing the reversibility of LSBs.The designed LSB demonstrates a high specific capacity of1529.6 mA h g^(-1)in the first cycle at 0.2 C.The rate performance is also excellent,maintaining an ultra-high specific capacity of 779.7 mA h g^(-1)at a high rate of 8 C.This investigation explores the mechanism of the interaction between the interlayer and LiPSs,and provides a new strategy to regulate the reaction kinetics and Li_(2)S deposition in LSBs.展开更多
Sluggish storage kinetics is considered as the main bottleneck of cathode materials for fast-charging aqueous zinc-ion batteries(AZIBs).In this report,we propose a novel in-situ self-etching strategy to unlock the Pal...Sluggish storage kinetics is considered as the main bottleneck of cathode materials for fast-charging aqueous zinc-ion batteries(AZIBs).In this report,we propose a novel in-situ self-etching strategy to unlock the Palm tree-like vanadium oxide/carbon nanofiber membrane(P-VO/C)as a robust freestanding electrode.Comprehensive investigations including the finite element simulation,in-situ X-ray diffraction,and in-situ electrochemical impedance spectroscopy disclosed it an electrochemically induced phase transformation mechanism from VO to layered Zn_(x)V_(2)O_5·nH_(2)O,as well as superior storage kinetics with ultrahigh pseudocapacitive contribution.As demonstrated,such electrode can remain a specific capacity of 285 mA h g^(-1)after 100 cycles at 1 A g^(-1),144.4 mA h g^(-1)after 1500 cycles at 30 A g^(-1),and even 97 mA h g^(-1)after 3000 cycles at 60 A g^(-1),respectively.Unexpectedly,an impressive power density of 78.9 kW kg^(-1)at the super-high current density of 100 A g^(-1)also can be achieved.Such design concept of in-situ self-etching free-standing electrode can provide a brand-new insight into extending the pseudocapacitive storage limit,so as to promote the development of high-power energy storage devices including but not limited to AZIBs.展开更多
Large volumetric expansion of cathode hosts and sluggish transport kinetics in the cathode–electrolyte interface,as well as dendrite growth and hydrogen evolution at Zn anode side are considered as the system problem...Large volumetric expansion of cathode hosts and sluggish transport kinetics in the cathode–electrolyte interface,as well as dendrite growth and hydrogen evolution at Zn anode side are considered as the system problems that cause the electrochemical failure of aqueous Zn-vanadium oxide battery.In this work,a multifunctional anti-proton electrolyte was proposed to synchronously solve all those issues.Theoretical and experimental studies confirm that PEG 400 additive can regulate the Zn^(2+) solvation structure and inhibit the ionization of free water molecules of the electrolyte.Then,smaller lattice expansion of vanadium oxide hosts and less associated by-product formation can be realized by using such electrolyte.Besides,such electrolyte is also beneficial to guide the uniform Zn deposition and suppress the side reaction of hydrogen evolution.Owing to the integrated synergetic modifica-tion,a high-rate and ultrastable aqueous Zn-V_(2)O_(3)/C battery can be constructed,which can remain a specific capacity of 222.8 m Ah g^(-1)after 6000 cycles at 5 A g^(-1),and 121.8 m Ah g^(-1) even after 18,000 cycles at 20 A g^(-1),respectively.Such“all-in-one”solution based on the electrolyte design provides a new strategy for developing high-performance aqueous Zn-ion battery.展开更多
Self-aggregation and sluggish transport kinetics of cathode materials would usually lead to the poor electrochemical performance for aqueous zinc-ion batteries(AZIBs).In this work,we report the construction of C@VO_(2...Self-aggregation and sluggish transport kinetics of cathode materials would usually lead to the poor electrochemical performance for aqueous zinc-ion batteries(AZIBs).In this work,we report the construction of C@VO_(2) composite via anti-aggregation growth and hierarchical porous carbon encapsulation.Both of the morphology of composite and pore structure of carbon layer can be regulated by tuning the adding amount of glucose.When acting as cathode applied for AZIBs,the C@VO_(2)-3:3 composite can deliver a high capacity of 281 m Ah g^(-1) at 0.2 A g^(-1).Moreover,such cathode also exhibits a remarkably rate capability and cyclic stability,which can release a specific capacity of 195 m Ah g^(-1) at 5 A g^(-1) with the capacity retention of 95.4%after 1000 cycles.Besides that,the evolution including the crystal structure,valence state and transport kinetics upon cycling were also deeply investigated.In conclusion,benefited from the synergistic effect of anti-aggregation morphology and hierarchical porous carbon encapsulation,the building of such C@VO_(2) composite can be highly expected to enhance the ion accessible site,boost the transport kinetics and thus performing a superior storage performance.Such design concept can be applied for other kinds of electrode materials and accelerating the development of highperformance AZIBs.展开更多
Hybrid CuO-Co_(3)O_(4)nanosphere building blocks have been embedded between the layered nanosheets of reduced graphene oxides with a three dimensional(3D)hybrid architecture(CuO-Co_(3)O_(4)-RGO),which are successfully...Hybrid CuO-Co_(3)O_(4)nanosphere building blocks have been embedded between the layered nanosheets of reduced graphene oxides with a three dimensional(3D)hybrid architecture(CuO-Co_(3)O_(4)-RGO),which are successfully applied as enhanced anodes for lithium-ion batteries(LIBs).The CuO-Co_(3)O_(4)-RGO sandwiched nanostructures exhibit a reversible capacity of~847 mA·h·g^(-1)after 200 cycles’cycling at 100 mA·g^(-1)with a capacity retention of 79%.The CuO-Co_(3)O_(4)-RGO compounds show superior electrochemical properties than the comparative CuO-Co_(3)O_(4),Co_(3)O_(4)and CuO anodes,which may be ascribed to the following reasons:the hybridizing multicomponent can probably give the complementary advantages;the mutual benefit of uniformly distributing nanospheres across the layered RGO nanosheets can avoid the agglomeration of both the RGO nanosheets and the CuO-Co_(3)O_(4) nanospheres;the 3D storage structure as well as the graphene wrapped composite could enhance the electrical conductivity and reduce volume expansion effect associated with the discharge-charge process.展开更多
The ripple effect induced by uncontrollable Zn deposition is considered as the Achilles heel for developing high-performance aqueous Zn-ion batteries.For this problem,this work reports a design concept of 3D artificia...The ripple effect induced by uncontrollable Zn deposition is considered as the Achilles heel for developing high-performance aqueous Zn-ion batteries.For this problem,this work reports a design concept of 3D artificial array interface engineering to achieve volume stress elimination,preferred orientation growth and dendrite-free stable Zn metal anode.The mechanism of MXene array interface on modulating the growth kinetics and deposition behavior of Zn atoms were firstly disclosed on the multi-scale level,including the in-situ optical microscopy and transient simulation at the mesoscopic scale,in-situ Raman spectroscopy and in-situ X-ray diffraction at the microscopic scale,as well as density functional theory calculation at the atomic scale.As indicated by the electrochemical performance tests,such engineered electrode exhibits the comprehensive enhancements not only in the resistance of corrosion and hydrogen evolution,but also the rate capability and cyclic stability.High-rate performance(20 mA cm^(-2))and durable cycle lifespan(1350 h at 0.5 mA cm^(-2),1500 h at 1 mA cm^(-2)and 800 h at 5 mA cm^(-2))can be realized.Moreover,the improvement of rate capability(214.1 mAh g^(-1)obtained at 10 A g^(-1))and cyclic stability also can be demonstrated in the case of 3D MXene array@Zn/VO2battery.Beyond the previous 2D closed interface engineering,this research offers a unique 3D open array interface engineering to stabilize Zn metal anode,the controllable Zn deposition mechanism revealed is also expected to deepen the fundamental of rechargeable batteries including but not limited to aqueous Zn metal batteries.展开更多
White matter hyperintensities(WMHs)on fluid-attenuated inversion recovery(FLAIR)images are imaging features in various neurological diseases and essential markers for clinical impairment and disease progression.WMHs a...White matter hyperintensities(WMHs)on fluid-attenuated inversion recovery(FLAIR)images are imaging features in various neurological diseases and essential markers for clinical impairment and disease progression.WMHs are associated with brain aging and pathological changes in the human brain,such as in Alzheimer’s disease(AD)[1],Parkinson’s disease(PD)[2],cerebral small vessel disease(SVD)[3],multiple sclerosis(MS)[4].展开更多
The deterioration of aqueous zinc-ion batteries(AZIBs)is confronted with challenges such as unregulated Zn^(2+)diffusion,dendrite growth and severe decay in battery performance under harsh environments.Here,a design c...The deterioration of aqueous zinc-ion batteries(AZIBs)is confronted with challenges such as unregulated Zn^(2+)diffusion,dendrite growth and severe decay in battery performance under harsh environments.Here,a design concept of eutectic electrolyte is presented by mixing long chain polymer molecules,polyethylene glycol dimethyl ether(PEGDME),with H_(2)O based on zinc trifluoromethyl sulfonate(Zn(OTf)2),to reconstruct the Zn^(2+)solvated structure and in situ modified the adsorption layer on Zn electrode surface.Molecular dynamics simulations(MD),density functional theory(DFT)calculations were combined with experiment to prove that the long-chain polymer-PEGDME could effectively reduce side reactions,change the solvation structure of the electrolyte and priority absorbed on Zn(002),achieving a stable dendrite-free Zn anode.Due to the comprehensive regulation of solvation structure and zinc deposition by PEGDME,it can stably cycle for over 3200 h at room temperature at 0.5 mA/cm^(2)and 0.5 mAh/cm^(2).Even at high-temperature environments of 60℃,it can steadily work for more than 800 cycles(1600 h).Improved cyclic stability and rate performance of aqueous Zn‖VO_(2)batteries in modified electrolyte were also achieved at both room and high temperatures.Beyond that,the demonstration of stable and high-capacity Zn‖VO_(2)pouch cells also implies its practical application.展开更多
Potassium ion batteries(PIBs)with high-volumetric energy densities are promising for next-generation low-cost energy storage devices.Metallic bismuth(Bi)with a structure similar to graphite,is a promising anode materi...Potassium ion batteries(PIBs)with high-volumetric energy densities are promising for next-generation low-cost energy storage devices.Metallic bismuth(Bi)with a structure similar to graphite,is a promising anode material for PIBs due to its high theoretical volumetric capacity(3763 mA h cm^−3)and relatively low working potential(−2.93 V vs.standard hydrogen electrode).However,it experiences severe capacity decay caused by a huge volume expansion of Bi when alloying with potassium.This study reports a flexible and free-standing Bi nanosheet(BiNS)/reduced graphene oxide composite membrane with designed porosity close to the expansion ratio of BiNS after charging.The controlled pore structure improves the electron and ion transport during cycling,and strengthens the structural stability of the electrode during potassiation and depotassiation,leading to excellent electrochemical performance for potassium-ion storage.In particular,it delivers a high reversible volumetric capacity of 451 mA h cm^−3 at the current density of 0.5 A g^−1,which is much higher than the previously reported commercial graphite material.展开更多
Electrochemical nitrate reduction reaction(NO_(3)−RR)is an ideal route to produce ammonia(NH_(3))under ambient conditions.Although a markedly improved NH3 production rate has been achieved on the NO_(3)−RR compared wi...Electrochemical nitrate reduction reaction(NO_(3)−RR)is an ideal route to produce ammonia(NH_(3))under ambient conditions.Although a markedly improved NH3 production rate has been achieved on the NO_(3)−RR compared with the nitrogen reduction reaction(NRR),the NH_(3) production rate of NO_(3)−RR is still well below the industrial Haber-Bosch route due to the lack of robust electrocatalysts for yielding high current densitieswith concurrently good suppression of hydrogen evolution reaction(HER).Herein,we describe an in situ electrochemical strategy for the synthesis of hollow carbon-coated Cu nanoparticles(NPs)(HSCu@C)with abundant grain boundaries(HSCu-AGB@C)for highly efficient NO_(3)−RR in both alkaline and neutral media.Impressively,in alkaline media,the HSCu-AGB@C can achieve a maximum NH3 Faradaic efficiency of 94.2% with an ultrahigh NH_(3) rate of 487.8 mmol g^(−1) cat h^(−1) at−0.2 V versus a reversible hydrogen electrode,more than 2.4-fold of the rate obtained in the Haber-Bosch.Both theoretic computations and experimental results uncover that the grain boundaries play the key to improve the NO_(3)−RR performance.Herein,the industrial-scale NH_(3) production ratemay open exciting opportunities for the practical electrosynthesis NH_(3) under ambient conditions.展开更多
The strong intrinsic Coulomb interactions of Frenkel excitons in crystalline carbon nitride(CCN) greatly limits their dissociation into electrons and holes, resulting in unsatisfactory charges separation and photocata...The strong intrinsic Coulomb interactions of Frenkel excitons in crystalline carbon nitride(CCN) greatly limits their dissociation into electrons and holes, resulting in unsatisfactory charges separation and photocatalytic efficiency. Herein, we propose a strategy to facilitate excitons dissociation by molecular regulation induced built-in electric field(BIEF). The electron-rich pyrimidine-ring into CCN changes the charge density distribution over heptazine-rings to induce BIEF between melon chains. Such BIEF is sufficient to overcome the considerable exciton binding energy(EBE) and reduce it from 38.4 meV to 16.4 meV,increasing the excitons dissociation efficiency(EDE) from 21.5% to 51.9%. Our results establish a strategy to facilitate excitons dissociation through molecular regulation induced BIEF, targeting the intrinsic high EBE and low EDE of polymer photocatalysts.展开更多
基金financially supported by the National Natural Science Foundation of China(No.22372103)Guangdong Basic and Applied Basic Research Foundation,China(2021A1515010241,2024A1515010032)the Shenzhen Science and Technology Foundation,China(JCYJ20220531103216037)。
文摘Although lithium-sulfur batteries(LSBs)exhibit high theoretical energy density,their practical application is hindered by poor conductivity of the sulfur cathode,the shuttle effect,and the irreversible deposition of Li_(2)S.To address these issues,a novel composite,using electrospinning technology,consisting of Fe_(3)Se_(4)and porous nitrogen-doped carbon nanofibers was designed for the interlayer of LSBs.The porous carbon nanofiber structure facilitates the transport of ions and electrons,while the Fe_(3)Se_(4)material adsorbs lithium polysulfides(LiPSs)and accelerates its catalytic conversion process.Furthermore,the Fe_(3)Se_(4)material interacts with soluble LiPSs to generate a new polysulfide intermediate,Li_(x)FeS_(y)complex,which changes the electrochemical reaction pathway and facilitates the three-dimensional deposition of Li_(2)S,enhancing the reversibility of LSBs.The designed LSB demonstrates a high specific capacity of1529.6 mA h g^(-1)in the first cycle at 0.2 C.The rate performance is also excellent,maintaining an ultra-high specific capacity of 779.7 mA h g^(-1)at a high rate of 8 C.This investigation explores the mechanism of the interaction between the interlayer and LiPSs,and provides a new strategy to regulate the reaction kinetics and Li_(2)S deposition in LSBs.
基金financially supported by the Shenzhen Science and Technology Program (JCYJ20200109105805902,JCYJ20220818095805012)the National Natural Science Foundation of China (22208221,22178221,42377487)+2 种基金the Scientific and Technological Plan of Guangdong Province (2019B090905005,2019B090911004)the Natural Science Foundation of Guangdong Province (2021A1515110751)the Guangdong Basic and Applied Basic Research Foundation (2022A1515110477,2021B1515120004)。
文摘Sluggish storage kinetics is considered as the main bottleneck of cathode materials for fast-charging aqueous zinc-ion batteries(AZIBs).In this report,we propose a novel in-situ self-etching strategy to unlock the Palm tree-like vanadium oxide/carbon nanofiber membrane(P-VO/C)as a robust freestanding electrode.Comprehensive investigations including the finite element simulation,in-situ X-ray diffraction,and in-situ electrochemical impedance spectroscopy disclosed it an electrochemically induced phase transformation mechanism from VO to layered Zn_(x)V_(2)O_5·nH_(2)O,as well as superior storage kinetics with ultrahigh pseudocapacitive contribution.As demonstrated,such electrode can remain a specific capacity of 285 mA h g^(-1)after 100 cycles at 1 A g^(-1),144.4 mA h g^(-1)after 1500 cycles at 30 A g^(-1),and even 97 mA h g^(-1)after 3000 cycles at 60 A g^(-1),respectively.Unexpectedly,an impressive power density of 78.9 kW kg^(-1)at the super-high current density of 100 A g^(-1)also can be achieved.Such design concept of in-situ self-etching free-standing electrode can provide a brand-new insight into extending the pseudocapacitive storage limit,so as to promote the development of high-power energy storage devices including but not limited to AZIBs.
基金financially supported by the National Natural Science Foundation of China(Nos.22178221,51774203)Shenzhen Science and Technology Program(Nos.JCYJ20200109105805902,JCYJ20200109105801725)+1 种基金Natural Science Foundation of Guangdong Province(Nos.2021A1515110751)China Postdoctoral Science Foundation(Nos.2021M702255)。
文摘Large volumetric expansion of cathode hosts and sluggish transport kinetics in the cathode–electrolyte interface,as well as dendrite growth and hydrogen evolution at Zn anode side are considered as the system problems that cause the electrochemical failure of aqueous Zn-vanadium oxide battery.In this work,a multifunctional anti-proton electrolyte was proposed to synchronously solve all those issues.Theoretical and experimental studies confirm that PEG 400 additive can regulate the Zn^(2+) solvation structure and inhibit the ionization of free water molecules of the electrolyte.Then,smaller lattice expansion of vanadium oxide hosts and less associated by-product formation can be realized by using such electrolyte.Besides,such electrolyte is also beneficial to guide the uniform Zn deposition and suppress the side reaction of hydrogen evolution.Owing to the integrated synergetic modifica-tion,a high-rate and ultrastable aqueous Zn-V_(2)O_(3)/C battery can be constructed,which can remain a specific capacity of 222.8 m Ah g^(-1)after 6000 cycles at 5 A g^(-1),and 121.8 m Ah g^(-1) even after 18,000 cycles at 20 A g^(-1),respectively.Such“all-in-one”solution based on the electrolyte design provides a new strategy for developing high-performance aqueous Zn-ion battery.
基金financially supported by the National Natural Science Foundation of China(Nos.51774203)the Shenzhen Science and Technology Program(Nos.JCYJ20200109105801725)。
文摘Self-aggregation and sluggish transport kinetics of cathode materials would usually lead to the poor electrochemical performance for aqueous zinc-ion batteries(AZIBs).In this work,we report the construction of C@VO_(2) composite via anti-aggregation growth and hierarchical porous carbon encapsulation.Both of the morphology of composite and pore structure of carbon layer can be regulated by tuning the adding amount of glucose.When acting as cathode applied for AZIBs,the C@VO_(2)-3:3 composite can deliver a high capacity of 281 m Ah g^(-1) at 0.2 A g^(-1).Moreover,such cathode also exhibits a remarkably rate capability and cyclic stability,which can release a specific capacity of 195 m Ah g^(-1) at 5 A g^(-1) with the capacity retention of 95.4%after 1000 cycles.Besides that,the evolution including the crystal structure,valence state and transport kinetics upon cycling were also deeply investigated.In conclusion,benefited from the synergistic effect of anti-aggregation morphology and hierarchical porous carbon encapsulation,the building of such C@VO_(2) composite can be highly expected to enhance the ion accessible site,boost the transport kinetics and thus performing a superior storage performance.Such design concept can be applied for other kinds of electrode materials and accelerating the development of highperformance AZIBs.
基金financially supported by the National Natural Science Foundation of China (21471100, 22005199)the Shenzhen Natural Science Fundation (20200813081943001)the Natural Science Foundation of Guangdong Province,China(2021A1515010241, 2021A1515010142)
文摘Hybrid CuO-Co_(3)O_(4)nanosphere building blocks have been embedded between the layered nanosheets of reduced graphene oxides with a three dimensional(3D)hybrid architecture(CuO-Co_(3)O_(4)-RGO),which are successfully applied as enhanced anodes for lithium-ion batteries(LIBs).The CuO-Co_(3)O_(4)-RGO sandwiched nanostructures exhibit a reversible capacity of~847 mA·h·g^(-1)after 200 cycles’cycling at 100 mA·g^(-1)with a capacity retention of 79%.The CuO-Co_(3)O_(4)-RGO compounds show superior electrochemical properties than the comparative CuO-Co_(3)O_(4),Co_(3)O_(4)and CuO anodes,which may be ascribed to the following reasons:the hybridizing multicomponent can probably give the complementary advantages;the mutual benefit of uniformly distributing nanospheres across the layered RGO nanosheets can avoid the agglomeration of both the RGO nanosheets and the CuO-Co_(3)O_(4) nanospheres;the 3D storage structure as well as the graphene wrapped composite could enhance the electrical conductivity and reduce volume expansion effect associated with the discharge-charge process.
基金financially the National Natural Science Foundation of China(Nos.22178221,22208221)Shenzhen Science and Technology Program(Nos.JCYJ20200109105805902)+1 种基金Natural Science Foundation of Guangdong Province(Nos.2021A1515110751)China Postdoctoral Science Foundation(Nos.2021M702255)。
文摘The ripple effect induced by uncontrollable Zn deposition is considered as the Achilles heel for developing high-performance aqueous Zn-ion batteries.For this problem,this work reports a design concept of 3D artificial array interface engineering to achieve volume stress elimination,preferred orientation growth and dendrite-free stable Zn metal anode.The mechanism of MXene array interface on modulating the growth kinetics and deposition behavior of Zn atoms were firstly disclosed on the multi-scale level,including the in-situ optical microscopy and transient simulation at the mesoscopic scale,in-situ Raman spectroscopy and in-situ X-ray diffraction at the microscopic scale,as well as density functional theory calculation at the atomic scale.As indicated by the electrochemical performance tests,such engineered electrode exhibits the comprehensive enhancements not only in the resistance of corrosion and hydrogen evolution,but also the rate capability and cyclic stability.High-rate performance(20 mA cm^(-2))and durable cycle lifespan(1350 h at 0.5 mA cm^(-2),1500 h at 1 mA cm^(-2)and 800 h at 5 mA cm^(-2))can be realized.Moreover,the improvement of rate capability(214.1 mAh g^(-1)obtained at 10 A g^(-1))and cyclic stability also can be demonstrated in the case of 3D MXene array@Zn/VO2battery.Beyond the previous 2D closed interface engineering,this research offers a unique 3D open array interface engineering to stabilize Zn metal anode,the controllable Zn deposition mechanism revealed is also expected to deepen the fundamental of rechargeable batteries including but not limited to aqueous Zn metal batteries.
基金supported by the Fundamental Research Funds for the Central Universities(2022CX1100)the Beijing Municipal Natural Science Foundation(JQ20035)+1 种基金the National Natural Science Foundation of China(81870958 and 81571631)the Special Fund of the Pediatric Medical Coordinated Development Center of Beijing Hospitals Authority(XTYB201831)。
文摘White matter hyperintensities(WMHs)on fluid-attenuated inversion recovery(FLAIR)images are imaging features in various neurological diseases and essential markers for clinical impairment and disease progression.WMHs are associated with brain aging and pathological changes in the human brain,such as in Alzheimer’s disease(AD)[1],Parkinson’s disease(PD)[2],cerebral small vessel disease(SVD)[3],multiple sclerosis(MS)[4].
基金supported by the National Natural Science Foundation of China(Nos.22208221,22178221)the Natural Science Foundation of Guangdong Province(Nos.2024A1515011078,2024A1515011507)+1 种基金the Shenzhen Science and Technology Program(Nos.JCYJ20220818095805012,JCYJ20230808105109019)the Start-up Research Funding of Shenzhen University(No.868-000001032522).
文摘The deterioration of aqueous zinc-ion batteries(AZIBs)is confronted with challenges such as unregulated Zn^(2+)diffusion,dendrite growth and severe decay in battery performance under harsh environments.Here,a design concept of eutectic electrolyte is presented by mixing long chain polymer molecules,polyethylene glycol dimethyl ether(PEGDME),with H_(2)O based on zinc trifluoromethyl sulfonate(Zn(OTf)2),to reconstruct the Zn^(2+)solvated structure and in situ modified the adsorption layer on Zn electrode surface.Molecular dynamics simulations(MD),density functional theory(DFT)calculations were combined with experiment to prove that the long-chain polymer-PEGDME could effectively reduce side reactions,change the solvation structure of the electrolyte and priority absorbed on Zn(002),achieving a stable dendrite-free Zn anode.Due to the comprehensive regulation of solvation structure and zinc deposition by PEGDME,it can stably cycle for over 3200 h at room temperature at 0.5 mA/cm^(2)and 0.5 mAh/cm^(2).Even at high-temperature environments of 60℃,it can steadily work for more than 800 cycles(1600 h).Improved cyclic stability and rate performance of aqueous Zn‖VO_(2)batteries in modified electrolyte were also achieved at both room and high temperatures.Beyond that,the demonstration of stable and high-capacity Zn‖VO_(2)pouch cells also implies its practical application.
基金This work was supported by the National Natural Science Foundation of China(51902176)China Postdoctoral Science Foundation(2018M631462)+1 种基金Guangdong Innovative and Entrepreneurial Research Team Program(2017ZT07C341)Shenzhen Municipal Development and Reform Commission and the Development and Reform Commission of Shenzhen Municipality for the development of the“Low-Dimensional Materials and Devices”Discipline.
文摘Potassium ion batteries(PIBs)with high-volumetric energy densities are promising for next-generation low-cost energy storage devices.Metallic bismuth(Bi)with a structure similar to graphite,is a promising anode material for PIBs due to its high theoretical volumetric capacity(3763 mA h cm^−3)and relatively low working potential(−2.93 V vs.standard hydrogen electrode).However,it experiences severe capacity decay caused by a huge volume expansion of Bi when alloying with potassium.This study reports a flexible and free-standing Bi nanosheet(BiNS)/reduced graphene oxide composite membrane with designed porosity close to the expansion ratio of BiNS after charging.The controlled pore structure improves the electron and ion transport during cycling,and strengthens the structural stability of the electrode during potassiation and depotassiation,leading to excellent electrochemical performance for potassium-ion storage.In particular,it delivers a high reversible volumetric capacity of 451 mA h cm^−3 at the current density of 0.5 A g^−1,which is much higher than the previously reported commercial graphite material.
基金the National Natural Science Foundation(NNSF)of China(nos.21975162 and 51902208)Shenzhen Government’s Plan of Science and Technology(nos.JCYJ20200109105803806 and JCYJ20190808142219049).
文摘Electrochemical nitrate reduction reaction(NO_(3)−RR)is an ideal route to produce ammonia(NH_(3))under ambient conditions.Although a markedly improved NH3 production rate has been achieved on the NO_(3)−RR compared with the nitrogen reduction reaction(NRR),the NH_(3) production rate of NO_(3)−RR is still well below the industrial Haber-Bosch route due to the lack of robust electrocatalysts for yielding high current densitieswith concurrently good suppression of hydrogen evolution reaction(HER).Herein,we describe an in situ electrochemical strategy for the synthesis of hollow carbon-coated Cu nanoparticles(NPs)(HSCu@C)with abundant grain boundaries(HSCu-AGB@C)for highly efficient NO_(3)−RR in both alkaline and neutral media.Impressively,in alkaline media,the HSCu-AGB@C can achieve a maximum NH3 Faradaic efficiency of 94.2% with an ultrahigh NH_(3) rate of 487.8 mmol g^(−1) cat h^(−1) at−0.2 V versus a reversible hydrogen electrode,more than 2.4-fold of the rate obtained in the Haber-Bosch.Both theoretic computations and experimental results uncover that the grain boundaries play the key to improve the NO_(3)−RR performance.Herein,the industrial-scale NH_(3) production ratemay open exciting opportunities for the practical electrosynthesis NH_(3) under ambient conditions.
基金jointly supported by the Natural Science Foundation of China(Nos.51874199,22078200,22102103)the grant from SZIIT(No.SZIIT2022KJ026)+1 种基金Guangdong Basic and Applied Basic Research Foundation(Nos.2019A1515111021,2021A1515010162)Shenzhen Innovation Program(No.JCYJ20170818142642395)。
文摘The strong intrinsic Coulomb interactions of Frenkel excitons in crystalline carbon nitride(CCN) greatly limits their dissociation into electrons and holes, resulting in unsatisfactory charges separation and photocatalytic efficiency. Herein, we propose a strategy to facilitate excitons dissociation by molecular regulation induced built-in electric field(BIEF). The electron-rich pyrimidine-ring into CCN changes the charge density distribution over heptazine-rings to induce BIEF between melon chains. Such BIEF is sufficient to overcome the considerable exciton binding energy(EBE) and reduce it from 38.4 meV to 16.4 meV,increasing the excitons dissociation efficiency(EDE) from 21.5% to 51.9%. Our results establish a strategy to facilitate excitons dissociation through molecular regulation induced BIEF, targeting the intrinsic high EBE and low EDE of polymer photocatalysts.
