Sodium with low cost and high abundance is considered as a substitute element of lithium for batteries and supercapacitors,which need the appropriate host materials to accommodate the relatively large Na^(+) ions.Comp...Sodium with low cost and high abundance is considered as a substitute element of lithium for batteries and supercapacitors,which need the appropriate host materials to accommodate the relatively large Na^(+) ions.Compared to Li^(+) storage,Na^(+) storage makes higher demands on the structural optimization of perovskite bismuth ferrite(BiFeO_(3)).We propose a novel strategy of defect engineering on BiFeO_(3) through Na and V codoping for high-efficiency Na^(+) storage,to reveal the roles of oxygen vacancies and V ions played in the enhanced electrochemical energy storage performances of Na-ion capacitors.The formation of the oxygen vacancies in the Na and V codoped BiFeO_(3)(denoted as NV-BFO),is promoted by Na doping and suppressed by V doping,which can be demonstrated by XPS and EPR spectra.By the first-principles calculations,the oxygen vacancies and V ions in NV-BFO are confirmed to substantially lower the Na^(+)migration energy barriers through the space and electric field effects,to effectively promote the Na^(+) transport in the crystals.Electrochemical kinetic analysis of the NV-BFO//NV-BFO capacitors indicates the dominant capacitive-controlled capacity,which depends on fast Na^(+) deintercalation-intercalation process in the NV-BFO electrode.The NV-BFO//NV-BFO capacitors open up a new avenue for developing highperformance Na-ion capacitors.展开更多
Potassium-ion batteries(PIBs)offer a cost-effective and resource-abundant solution for large-scale energy storage.However,the progress of PIBs is impeded by the lack of high-capacity,long-life,and fast-kinetics anode ...Potassium-ion batteries(PIBs)offer a cost-effective and resource-abundant solution for large-scale energy storage.However,the progress of PIBs is impeded by the lack of high-capacity,long-life,and fast-kinetics anode electrode materials.Here,we propose a dual synergic optimization strategy to enhance the K^(+)storage stability and reaction kinetics of Bi_(2)S_(3) through two-dimensional compositing and cation doping.Externally,Bi_(2)S_(3) nanoparticles are loaded onto the surface of three-dimensional interconnected Ti_(3)C_(2)T_(x) nanosheets to stabilize the electrode structure.Internally,Cu^(2+)doping acts as active sites to accelerate K^(+)storage kinetics.Various theoretical simulations and ex situ techniques are used to elucidate the external–internal dual synergism.During discharge,Ti_(3)C_(2)T_(x) and Cu^(2+)collaboratively facilitate K+intercalation.Subsequently,Cu^(2+)doping primarily promotes the fracture of Bi2S3 bonds,facilitating a conversion reaction.Throughout cycling,the Ti_(3)C_(2)T_(x) composite structure and Cu^(2+)doping sustain functionality.The resulting Cu^(2+)-doped Bi2S3 anchored on Ti_(3)C_(2)T_(x)(C-BT)shows excellent rate capability(600 mAh g^(-1) at 0.1 A g^(–1);105 mAh g^(-1) at 5.0 A g^(-1))and cycling performance(91 mAh g^(-1) at 5.0 A g^(-1) after 1000 cycles)in half cells and a high energy density(179 Wh kg–1)in full cells.展开更多
The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of...The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.展开更多
基金financial supports from National Natural Science Foundation of China(22005174 and 52271133)。
文摘Sodium with low cost and high abundance is considered as a substitute element of lithium for batteries and supercapacitors,which need the appropriate host materials to accommodate the relatively large Na^(+) ions.Compared to Li^(+) storage,Na^(+) storage makes higher demands on the structural optimization of perovskite bismuth ferrite(BiFeO_(3)).We propose a novel strategy of defect engineering on BiFeO_(3) through Na and V codoping for high-efficiency Na^(+) storage,to reveal the roles of oxygen vacancies and V ions played in the enhanced electrochemical energy storage performances of Na-ion capacitors.The formation of the oxygen vacancies in the Na and V codoped BiFeO_(3)(denoted as NV-BFO),is promoted by Na doping and suppressed by V doping,which can be demonstrated by XPS and EPR spectra.By the first-principles calculations,the oxygen vacancies and V ions in NV-BFO are confirmed to substantially lower the Na^(+)migration energy barriers through the space and electric field effects,to effectively promote the Na^(+) transport in the crystals.Electrochemical kinetic analysis of the NV-BFO//NV-BFO capacitors indicates the dominant capacitive-controlled capacity,which depends on fast Na^(+) deintercalation-intercalation process in the NV-BFO electrode.The NV-BFO//NV-BFO capacitors open up a new avenue for developing highperformance Na-ion capacitors.
基金This work received financial support from the National Natural Science Foundation of China(Grant Nos.U23A20574,52250010,and 52201242)the 261 Project MIIT,the Young Elite Scientists Sponsorship Program by CAST(Grant No.2021QNRC001)+1 种基金the Fundamental Research Funds for the Central Universities(Grant No.2242022R40018)the Jiangsu Funding Program for Excellent Postdoctoral Talent(Grant No.2022ZB75).
文摘Potassium-ion batteries(PIBs)offer a cost-effective and resource-abundant solution for large-scale energy storage.However,the progress of PIBs is impeded by the lack of high-capacity,long-life,and fast-kinetics anode electrode materials.Here,we propose a dual synergic optimization strategy to enhance the K^(+)storage stability and reaction kinetics of Bi_(2)S_(3) through two-dimensional compositing and cation doping.Externally,Bi_(2)S_(3) nanoparticles are loaded onto the surface of three-dimensional interconnected Ti_(3)C_(2)T_(x) nanosheets to stabilize the electrode structure.Internally,Cu^(2+)doping acts as active sites to accelerate K^(+)storage kinetics.Various theoretical simulations and ex situ techniques are used to elucidate the external–internal dual synergism.During discharge,Ti_(3)C_(2)T_(x) and Cu^(2+)collaboratively facilitate K+intercalation.Subsequently,Cu^(2+)doping primarily promotes the fracture of Bi2S3 bonds,facilitating a conversion reaction.Throughout cycling,the Ti_(3)C_(2)T_(x) composite structure and Cu^(2+)doping sustain functionality.The resulting Cu^(2+)-doped Bi2S3 anchored on Ti_(3)C_(2)T_(x)(C-BT)shows excellent rate capability(600 mAh g^(-1) at 0.1 A g^(–1);105 mAh g^(-1) at 5.0 A g^(-1))and cycling performance(91 mAh g^(-1) at 5.0 A g^(-1) after 1000 cycles)in half cells and a high energy density(179 Wh kg–1)in full cells.
基金the National Natural Science Foundation of China (92034301,22078063 and 22022804)Major Program of Qingyuan Innovation Laboratory (00121003)the Natural Science Foundation of Fujian Province (2020H6007)。
文摘The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.
