BiVO_(4)(BVO)is a promising material as the photoanode for use in photoelectrochemical applications.However,the high charge recombination and slow charge transfer of the BVO have been obstacles to achieving satisfacto...BiVO_(4)(BVO)is a promising material as the photoanode for use in photoelectrochemical applications.However,the high charge recombination and slow charge transfer of the BVO have been obstacles to achieving satisfactory photoelectrochemical performance.To address this,various modifications have been attempted,including the use of ferroelectric materials.Ferroelectric materials can form a permanent polarization within the layer,enhancing the separation and transport of photo-excited electron-hole pairs.In this study,we propose a novel approach by depositing an epitaxial BiFeO_(3)(BFO)thin film underneath the BVO thin film(BVO/BFO)to harness the ferroelectric property of BFO.The self-polarization of the inserted BFO thin film simultaneously functions as a buffer layer to enhance charge transport and a hole-blocking layer to reduce charge recombination.As a result,the BVO/BFO photoanodes showed more than 3.5 times higher photocurrent density(0.65 mA cm^(-2))at 1.23 V_(RHE)under the illumination compared to the bare BVO photoanodes(0.18 m A cm^(-2)),which is consistent with the increase of the applied bias photon-to-current conversion efficiencies(ABPE)and the result of electrochemical impedance spectroscopy(EIS)analysis.These results can be attributed to the self-polarization exhibited by the inserted BFO thin film,which promoted the charge separation and transfer efficiency of the BVO photoanodes.展开更多
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
基金supported by the program of Future Hydrogen Original Technology Development(2021M3I3A1084747),through the National Research Foundation of Korea(NRF)funded by the Korean government(Ministry of Science and ICT(MSIT))by the NRF grant funded by the Korea government(MSIT)(No.2020R1A2C1005590)。
文摘BiVO_(4)(BVO)is a promising material as the photoanode for use in photoelectrochemical applications.However,the high charge recombination and slow charge transfer of the BVO have been obstacles to achieving satisfactory photoelectrochemical performance.To address this,various modifications have been attempted,including the use of ferroelectric materials.Ferroelectric materials can form a permanent polarization within the layer,enhancing the separation and transport of photo-excited electron-hole pairs.In this study,we propose a novel approach by depositing an epitaxial BiFeO_(3)(BFO)thin film underneath the BVO thin film(BVO/BFO)to harness the ferroelectric property of BFO.The self-polarization of the inserted BFO thin film simultaneously functions as a buffer layer to enhance charge transport and a hole-blocking layer to reduce charge recombination.As a result,the BVO/BFO photoanodes showed more than 3.5 times higher photocurrent density(0.65 mA cm^(-2))at 1.23 V_(RHE)under the illumination compared to the bare BVO photoanodes(0.18 m A cm^(-2)),which is consistent with the increase of the applied bias photon-to-current conversion efficiencies(ABPE)and the result of electrochemical impedance spectroscopy(EIS)analysis.These results can be attributed to the self-polarization exhibited by the inserted BFO thin film,which promoted the charge separation and transfer efficiency of the BVO photoanodes.
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.
