Mg-air batteries have attracted tremendous attention as a potential next-generation power source for portable electronics and e-transportation due to their remarkable high theoretical volumetric energy density,environ...Mg-air batteries have attracted tremendous attention as a potential next-generation power source for portable electronics and e-transportation due to their remarkable high theoretical volumetric energy density,environmental sustainability,and cost-effectiveness.However,the fast hydrogen evolution reaction(HER)in NaCl-based aqueous electrolytes impairs the performance of Mg-air batteries and leads to poor specific capacity,low energy density,and low utilization.Thus,the conventionally used NaCl solute was proposed to be replaced by NaNO_(3)and acetic acid additive as a corrosion inhibitor,therefore an electrolyte engineering for long-life time Mg-air batteries is reported.The resulting Mg-air batteries based on this optimized electrolyte demonstrate an improved discharge voltage reaching~1.8 V for initial 5 h at a current density of 0.5 mA/cm^(2) and significantly prolonged cells'operational lifetime to over 360 h,in contrast to only~17 h observed in NaCl electrolyte.X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry were employed to analyse the composition of surface film and scanning electron microscopy combined with transmission electron microscopy to clarify the morphology changes of the surface layer as a function of acetic acid addition.The thorough studies of chemical composition and morphology of corrosion products have allowed us to elucidate the working mechanism of Mg anode in this optimized electrolyte for Mg-air batteries.展开更多
Copper phthalocyanine(CuPc)is adopted as an electrolyte additive to stabilize lithium anode for lithiumsulfur(Li-S)batteries.CuPc with a planar molecular structure and lithiophilic N-containing group,is likely to be a...Copper phthalocyanine(CuPc)is adopted as an electrolyte additive to stabilize lithium anode for lithiumsulfur(Li-S)batteries.CuPc with a planar molecular structure and lithiophilic N-containing group,is likely to be adsorbed on the surface of Li anode to form a coating layer,which can restrict the direct contact between Li anode and solvents,and guide the uniform deposition of Li^(+)ions.The Li||Li symmetric cells demonstrate a stable cycle performance,and Li||Cu cells show high Coulombic efficiencies.In Li-S batteries,the formed stable solid-electrolyte interface(SEI)film containing copper sulfides can protect Li anode from the polysulfide corrosion and side reactions with the electrolyte,leading to the compact and smooth surface morphology of Li anode.Therefore,the Li-S batteries with CuPc additive deliver much higher capacity,better cycle performance and rate capability as compared to the one without CuPc additive.展开更多
The undesired side reactions at electrode/electrolyte interface as well as the irreversible phase evolution during electrochemical cycling significantly affect the cyclic performances of nickel-rich NMCs electrode mat...The undesired side reactions at electrode/electrolyte interface as well as the irreversible phase evolution during electrochemical cycling significantly affect the cyclic performances of nickel-rich NMCs electrode materials.Electrolyte optimization is an effective approach to suppress such an adverse side reaction,thereby enhancing the electrochemical properties.Herein,a novel boron-based film forming additive,tris(2,2,2-trifluoroethyl)borate(TTFEB),has been introduced to regulate the interphasial chemistry of LiNi0.8Mn0.1Co0.1O2(NMC811)cathode to improve its long-term cyclability and rate properties.The results of multi-model diagnostic study reveal that formation lithium fluoride(LiF)-rich and boron(B)containing cathode electrolyte interphase(CEI)not only stabilizes cathode surface,but also prevents electrolyte decomposition.Moreover,homogenously distributed B containing species serves as a skeleton to form more uniform and denser CEI,reducing the interphasial resistance.Remarkably,the Li/NMC811 cell with the TTFEB additive delivers an exceptional cycling stability with a high-capacity retention of 72.8%after 350 electrochemical cycles at a 1 C current rate,which is significantly higher than that of the cell cycled in the conventional electrolyte(59.7%).These findings provide a feasible pathway for improving the electrochemical performance of Ni-rich NMCs cathode by regulating the interphasial chemistry.展开更多
High conductivity two-dimensional(2D)materials have been proved to be potential electrode materials for flexible supercapacitors because of its outstanding chemical and physical properties.However,electrodes based on ...High conductivity two-dimensional(2D)materials have been proved to be potential electrode materials for flexible supercapacitors because of its outstanding chemical and physical properties.However,electrodes based on 2D materials always suffer from limited electrolyte-accessible surface due to the restacking of the 2D sheets,hindering the full utilization of their surface area.In this regard,an electrolyte-mediated method is used to integrate dense structure reduced graphene oxide/MXene(RGM)-electrolyte composite films.In such composite films,reduced graphene oxide(RGO)and MXene sheets are controllable assembly in compact layered structure with electrolyte filled between the layers.The electrolyte layer between RGO and MXene sheets forms continuous ion transport channels in the composite films.Therefore,the RGM-electrolyte composite films can be used directly as self-supporting electrodes for supercapacitors without additional conductive agents and binders.As a result,the composite films demonstrate enhanced volumetric specific capacity,improved volumetric energy density and higher power density compared with both pure RGO electrode and porous composite electrode prepared by traditional methods.Specifically,when the mass ratio of MXene is 30%,the electrode delivers a volumetric specific capacity of 454.9 F·cm^(−3) with a high energy density of 39.4 Wh·L^(−1).More importantly,supercapacitors based on the composite films exhibit good flexibility electrochemical performance.The investigation provides a new approach to synthesize dense structure films based on 2D materials for application in high volumetric capacitance flexible supercapacitors.展开更多
NiO,an anodic electrochromic material,has applications in energy-saving windows,intelligent displays,and military camouflage.However,its electrochromic mechanism and reasons for its performance degradation in alkaline...NiO,an anodic electrochromic material,has applications in energy-saving windows,intelligent displays,and military camouflage.However,its electrochromic mechanism and reasons for its performance degradation in alkaline aqueous electrolytes are complex and poorly understood,making it challenging to improve NiO thin films.We studied the phases and electrochemical characteristics of NiO films in different states(initial,colored,bleached and after 8000 cycles)and identified three main reasons for performance degradation.First,Ni(OH)_(2)is generated during electrochromic cycling and deposited on the NiO film surface,gradually yielding a NiO@Ni(OH)_(2)core-shell structure,isolating the internal NiO film from the electrolyte,and preventing ion transfer.Second,the core-shell structure causes the mode of electrical conduction to change from first-to second-order conduction,reducing the efficiency of ion transfer to the surface Ni(OH)_(2)layer.Third,Ni(OH)_(2)and NiOOH,which have similar crystal structures but different b-axis lattice parameters,are formed during electrochromic cycling,and large volume changes in the unit cell reduce the structural stability of the thin film.Finally,we clarified the mechanism of electrochromic performance degradation of NiO films in alkaline aqueous electrolytes and provide a route to activation of NiO films,which will promote the development of electrochromic technology.展开更多
For the performance optimization strategies of hard carbon,heteroatom doping is an effective way to enhance the intrinsic transfer properties of sodium ions and electrons for accelerating the reaction kinetics.However...For the performance optimization strategies of hard carbon,heteroatom doping is an effective way to enhance the intrinsic transfer properties of sodium ions and electrons for accelerating the reaction kinetics.However,the previous work focuses mainly on the intrinsic physicochemical property changes of the material,but little attention has been paid to the resulting interfacial regulation of the electrode surface,namely the formation of solid electrolyte interphase(SEI)film.In this work,element F,which has the highest electronegativity,was chosen as the doping source to,more effectively,tune the electronic structure of the hard carbon.The effect of F-doping on the physicochemical properties of hard carbon was not only systematically analyzed but also investigated with spectroscopy,optics,and in situ characterization techniques to further verify that appropriate F-doping plays a positive role in constructing a homogenous and inorganic-rich SEI film.The experimentally demonstrated link between the electronic structure of the electrode and the SEI film properties can reframe the doping optimization strategy as well as provide a new idea for the design of electrode materials with low reduction kinetics to the electrolyte.As a result,the optimized sample with the appropriate F-doping content exhibits the best electrochemical performance with high capacity(434.53 mA h g^(-1)at 20mA g^(-1))and excellent rate capability(141 mAh g^(-1)at 400 mA g^(-1)).展开更多
基金the China Scholarship Council(CSC)for funding(no.201806310116)。
文摘Mg-air batteries have attracted tremendous attention as a potential next-generation power source for portable electronics and e-transportation due to their remarkable high theoretical volumetric energy density,environmental sustainability,and cost-effectiveness.However,the fast hydrogen evolution reaction(HER)in NaCl-based aqueous electrolytes impairs the performance of Mg-air batteries and leads to poor specific capacity,low energy density,and low utilization.Thus,the conventionally used NaCl solute was proposed to be replaced by NaNO_(3)and acetic acid additive as a corrosion inhibitor,therefore an electrolyte engineering for long-life time Mg-air batteries is reported.The resulting Mg-air batteries based on this optimized electrolyte demonstrate an improved discharge voltage reaching~1.8 V for initial 5 h at a current density of 0.5 mA/cm^(2) and significantly prolonged cells'operational lifetime to over 360 h,in contrast to only~17 h observed in NaCl electrolyte.X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry were employed to analyse the composition of surface film and scanning electron microscopy combined with transmission electron microscopy to clarify the morphology changes of the surface layer as a function of acetic acid addition.The thorough studies of chemical composition and morphology of corrosion products have allowed us to elucidate the working mechanism of Mg anode in this optimized electrolyte for Mg-air batteries.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.22269013,22263009)the Natural Science Foundation of Jiangxi Province(Nos.20224ACB213001,20202ACB202004,20213BCJ22024,20212BBE53051)the Key Laboratory of Jiangxi Province for Environment and Energy Catalysis(No.20181BCD40004).
文摘Copper phthalocyanine(CuPc)is adopted as an electrolyte additive to stabilize lithium anode for lithiumsulfur(Li-S)batteries.CuPc with a planar molecular structure and lithiophilic N-containing group,is likely to be adsorbed on the surface of Li anode to form a coating layer,which can restrict the direct contact between Li anode and solvents,and guide the uniform deposition of Li^(+)ions.The Li||Li symmetric cells demonstrate a stable cycle performance,and Li||Cu cells show high Coulombic efficiencies.In Li-S batteries,the formed stable solid-electrolyte interface(SEI)film containing copper sulfides can protect Li anode from the polysulfide corrosion and side reactions with the electrolyte,leading to the compact and smooth surface morphology of Li anode.Therefore,the Li-S batteries with CuPc additive deliver much higher capacity,better cycle performance and rate capability as compared to the one without CuPc additive.
基金supported by the National Natural Science Foundation of China(Grant No.22209106).
文摘The undesired side reactions at electrode/electrolyte interface as well as the irreversible phase evolution during electrochemical cycling significantly affect the cyclic performances of nickel-rich NMCs electrode materials.Electrolyte optimization is an effective approach to suppress such an adverse side reaction,thereby enhancing the electrochemical properties.Herein,a novel boron-based film forming additive,tris(2,2,2-trifluoroethyl)borate(TTFEB),has been introduced to regulate the interphasial chemistry of LiNi0.8Mn0.1Co0.1O2(NMC811)cathode to improve its long-term cyclability and rate properties.The results of multi-model diagnostic study reveal that formation lithium fluoride(LiF)-rich and boron(B)containing cathode electrolyte interphase(CEI)not only stabilizes cathode surface,but also prevents electrolyte decomposition.Moreover,homogenously distributed B containing species serves as a skeleton to form more uniform and denser CEI,reducing the interphasial resistance.Remarkably,the Li/NMC811 cell with the TTFEB additive delivers an exceptional cycling stability with a high-capacity retention of 72.8%after 350 electrochemical cycles at a 1 C current rate,which is significantly higher than that of the cell cycled in the conventional electrolyte(59.7%).These findings provide a feasible pathway for improving the electrochemical performance of Ni-rich NMCs cathode by regulating the interphasial chemistry.
基金This work was supported by the Natural Science Foundation of Shandong Province(Nos.ZR2018BB038 and ZR2019BEM041)the National Natural Science Foundation of China(Nos.21805171,51802178 and 51804189).
文摘High conductivity two-dimensional(2D)materials have been proved to be potential electrode materials for flexible supercapacitors because of its outstanding chemical and physical properties.However,electrodes based on 2D materials always suffer from limited electrolyte-accessible surface due to the restacking of the 2D sheets,hindering the full utilization of their surface area.In this regard,an electrolyte-mediated method is used to integrate dense structure reduced graphene oxide/MXene(RGM)-electrolyte composite films.In such composite films,reduced graphene oxide(RGO)and MXene sheets are controllable assembly in compact layered structure with electrolyte filled between the layers.The electrolyte layer between RGO and MXene sheets forms continuous ion transport channels in the composite films.Therefore,the RGM-electrolyte composite films can be used directly as self-supporting electrodes for supercapacitors without additional conductive agents and binders.As a result,the composite films demonstrate enhanced volumetric specific capacity,improved volumetric energy density and higher power density compared with both pure RGO electrode and porous composite electrode prepared by traditional methods.Specifically,when the mass ratio of MXene is 30%,the electrode delivers a volumetric specific capacity of 454.9 F·cm^(−3) with a high energy density of 39.4 Wh·L^(−1).More importantly,supercapacitors based on the composite films exhibit good flexibility electrochemical performance.The investigation provides a new approach to synthesize dense structure films based on 2D materials for application in high volumetric capacitance flexible supercapacitors.
基金supported by the Special Support Program for High-level Talents of Shaanxi Province(No.2020-44)Innnovative Talent Project of China and The Youth Innovation Team of Shaanxi Universities
文摘NiO,an anodic electrochromic material,has applications in energy-saving windows,intelligent displays,and military camouflage.However,its electrochromic mechanism and reasons for its performance degradation in alkaline aqueous electrolytes are complex and poorly understood,making it challenging to improve NiO thin films.We studied the phases and electrochemical characteristics of NiO films in different states(initial,colored,bleached and after 8000 cycles)and identified three main reasons for performance degradation.First,Ni(OH)_(2)is generated during electrochromic cycling and deposited on the NiO film surface,gradually yielding a NiO@Ni(OH)_(2)core-shell structure,isolating the internal NiO film from the electrolyte,and preventing ion transfer.Second,the core-shell structure causes the mode of electrical conduction to change from first-to second-order conduction,reducing the efficiency of ion transfer to the surface Ni(OH)_(2)layer.Third,Ni(OH)_(2)and NiOOH,which have similar crystal structures but different b-axis lattice parameters,are formed during electrochromic cycling,and large volume changes in the unit cell reduce the structural stability of the thin film.Finally,we clarified the mechanism of electrochromic performance degradation of NiO films in alkaline aqueous electrolytes and provide a route to activation of NiO films,which will promote the development of electrochromic technology.
基金National Key R&D Program of China,Grant/Award Number:2022YFB4000120Fundamental Research Funds for the Central Universities,Grant/Award Number:2022ZYGXZR101。
文摘For the performance optimization strategies of hard carbon,heteroatom doping is an effective way to enhance the intrinsic transfer properties of sodium ions and electrons for accelerating the reaction kinetics.However,the previous work focuses mainly on the intrinsic physicochemical property changes of the material,but little attention has been paid to the resulting interfacial regulation of the electrode surface,namely the formation of solid electrolyte interphase(SEI)film.In this work,element F,which has the highest electronegativity,was chosen as the doping source to,more effectively,tune the electronic structure of the hard carbon.The effect of F-doping on the physicochemical properties of hard carbon was not only systematically analyzed but also investigated with spectroscopy,optics,and in situ characterization techniques to further verify that appropriate F-doping plays a positive role in constructing a homogenous and inorganic-rich SEI film.The experimentally demonstrated link between the electronic structure of the electrode and the SEI film properties can reframe the doping optimization strategy as well as provide a new idea for the design of electrode materials with low reduction kinetics to the electrolyte.As a result,the optimized sample with the appropriate F-doping content exhibits the best electrochemical performance with high capacity(434.53 mA h g^(-1)at 20mA g^(-1))and excellent rate capability(141 mAh g^(-1)at 400 mA g^(-1)).
