Hematite(α-Fe_(2)O_(3)) based photoanodes have been extensively studied due to various intriguing features that make them viable candidates for a photoelectrochemical(PEC) water splitting photoanode.Herein,we propose...Hematite(α-Fe_(2)O_(3)) based photoanodes have been extensively studied due to various intriguing features that make them viable candidates for a photoelectrochemical(PEC) water splitting photoanode.Herein,we propose a Zr-doped Fe_(2)O_(3) photoanode decorated with facilely spin-coated Au nanoparticles(NPs) and microwave-assisted attached Si co-doping in conjunction with a SiO_(x) overlayer that displayed a remarkable photocurrent density of 2.01 mA/cm^(2) at 1.23 V vs.RHE.The kinetic dynamics at the photoelectrode/-electrolyte interface was examined by employing systematic electrochemical investigations.The Au NPs played a dual role in increasing PEC water splitting.First,the Schottky interface that was formed between Au NPs and Zr-Fe_(2)O_(3) lectrode ensured the prevention of electron flow from the photoanode to the metal,increasing the number of available charges as well as suppressing surface charge recombination.Second,Au extracted photoholes from the bulk of the Zr-Fe_(2)O_(3) and transported them to the outer SiO_(x) overlayer,while the SiO_(x) overlayer efficiently collected the photoholes and promoted the hole injection into the electrolyte.Further,Si co-doping enhanced bulk conductivity by reducing bulk charge transfer resistance and improving charge carrier density.This study outlines a technique to design a metallic charge transfer path with an overlayer for solar energy conversion.展开更多
Indium oxide(In_(2)O_(3)),as a promising candidate for CO_(2)hydrogenation to C_(1) products,often suffers from sintering and activity decline,closely related to the undesirable structural evolution under reaction con...Indium oxide(In_(2)O_(3)),as a promising candidate for CO_(2)hydrogenation to C_(1) products,often suffers from sintering and activity decline,closely related to the undesirable structural evolution under reaction conditions.Based on the comprehension of the dynamic evolution,this study presents an efficient strategy to alleviate the agglomeration of In_(2)O_(3)nanoparticles by the surface decoration with highly dispersed silica species(SiO_(x)).Various structural characterizations combined with density functional theory calculations demonstrated that the sintering resulted from the over-reduction,while the enhanced stability originated from the anchoring effect of highly stable In-OSi bonds,which hinders the substantial formation of metallic In(In^(0))and the subsequent agglomeration.0.6Si/In_(2)O_(3)exhibited CO_(2)conversion rate of10.0 mmol g^(-1)h^(-1)at steady state vs.3.5 mmol g^(-1)h^(-1)on In_(2)O_(3)in CO_(2)hydrogenation.Enhanced steady-state activity was also achieved on Pd-modified catalysts.Compared to the traditional Pd/In_(2)O_(3)catalyst,the methanol production rate of Pd catalyst supported on 0.6Si/In_(2)O_(3)was enhanced by 23%,showing the potential of In_(2)O_(3)modified by SiO_(x)in serving as a platform material.This work provides a promising method to design new In_(2)O_(3)-based catalysts with improved activity and stability in CO_(2)hydrogenation.展开更多
Macro-and micro-interface instability of SiO_(x)anode caused by its dramatic volume variation during cycling will result in low Coulombic efficiency and rapid capacity degradation.In this work,an organic-inorganic com...Macro-and micro-interface instability of SiO_(x)anode caused by its dramatic volume variation during cycling will result in low Coulombic efficiency and rapid capacity degradation.In this work,an organic-inorganic composite interfacial layer rich in benzene ring groups,polyisocyanates,and LiF was obtained on SiO_(x)anode by the introduction of 4-fluorophenyl isocyanate(FPI)and fluoroethylene carbonate(FEC)co-additives in electrolyte.The SiO_(x)anode material shows a capacity retention of 69.2%after 100 cycles at a current density of 1 A g^(-1)and rate capacity of 523 m A h g^(-1)at the current density of 3A g^(-1),while the SiO_(x)anode cycling in reference electrolyte has almost no capacity.展开更多
The commercialized binder carboxymethyl cellulose sodium(CMC-Na)is considered unsuitable for micro-sized SiO_(x) anode as it cannot endure the large volume change to retain the conductive network during repeated charg...The commercialized binder carboxymethyl cellulose sodium(CMC-Na)is considered unsuitable for micro-sized SiO_(x) anode as it cannot endure the large volume change to retain the conductive network during repeated charge/discharge cycles.Herein,a small amount of silicon nanoparticles(SiNPs)is added during slurry preparation process as“nano-combs”to unfold the convoluted CMC-Na polymer chains so that they undergo a coilto-stretch transition by interaction between polar groups(e.g.,-OH,-COONa)of polymer and SiNPs’large surface.Through maximizing the utilization of binders,a uniform conductive network is constructed with increased interfacial contact with micro-sized SiO_(x).As a result,the SiO_(x) electrode with optimized(10 wt%)SiNPs addition shows significantly improved initial capacity and cycling performance.Through revisiting CMCNa,a currently deemed unqualified binder in SiO_(x) anode,this work gives a brand-new perspective on the failing mechanism of Si-based anode materials and an improving strategy for electrode preparation.展开更多
Relieving the stress or strain associated with volume change is highly desirable for high-performance SiOx anodes in terms of stable solid electrolyte interphase(SEI)-film growth.Herein,a Si-valence gradient is optimi...Relieving the stress or strain associated with volume change is highly desirable for high-performance SiOx anodes in terms of stable solid electrolyte interphase(SEI)-film growth.Herein,a Si-valence gradient is optimized in SiOx composites to circumvent the large volume strain accompanied by lithium insertion/extraction.SiO_(x)@C annealed at 850℃ has a gentle Si-valence gradient along the radial direction and excellent electrochemical performances,delivering a high capacity of 506.9 mAh g^(−1) at 1.0 A g^(−1) with a high Coulombic efficiency of~99.8%over 400 cycles.Combined with the theoretical prediction,the obtained results indicate that the gentle Si-valence gradient in SiO_(x)@C is useful for suppressing plastic deformation and maintaining the inner connection integrity within the SiO_(x)@C particle.Moreover,a gentle Si-valence gradient is expected to form a stress gradient and affect the distribution of dangling bonds,resulting in local stress relief during the lithiation/delithiation process and enhanced Li-ion kinetic diffusion.Furthermore,the lowest interfacial stress variation ensures a stable SEI film at the interface and consequently increases cycling stability.Therefore,rational design of a Si-valence gradient in SiOx can provide further insights into achieving high-performance SiOx anodes with large-scale production.展开更多
Polycrystalline Si(poly-Si)-based passivating contacts are promising candidates for high-efficiency crystalline Si solar cells.We show that nanosecond-scale pulsed laser melting(PLM)is an industrially viable technique...Polycrystalline Si(poly-Si)-based passivating contacts are promising candidates for high-efficiency crystalline Si solar cells.We show that nanosecond-scale pulsed laser melting(PLM)is an industrially viable technique to fabricate such contacts with precisely controlled dopant concentration profiles that exceed the solid solubility limit.We demonstrate that conventionally doped,hole-selective poly-Si/SiO_(x)contacts that provide poor surface passivation of c-Si can be replaced with Ga-or B-doped contacts based on non-equilibrium doping.We overcome the solid solubility limit for both dopants in poly-Si by rapid cooling and recrystallization over a timescale of∼25 ns.We show an active Ga dopant concentration of∼3×10^(20)cm^(−3)in poly-Si which is six times higher than its solubility limit in c-Si,and a B dopant concentration as high as∼10^(21) cm^(−3).We measure an implied open-circuit voltage of 735 mV for Ga-doped poly-Si/SiO_(x)contacts on Czochralski Si with a low contact resistivity of 35.5±2.4 mΩcm^(2).Scanning spreading resistance microscopy and Kelvin probe force microscopy show large diffusion and drift current in the p-n junction that contributes to the low contact resistivity.Our results suggest that PLM can be extended for hyperdoping of other semiconductors with low solubility atoms to enable high-efficiency devices.展开更多
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(NRF-2021R1A2C1095669,NRF-2021R1F1A1049366 and NRF2023R1A2C1003088)supported by the GRDC(Global Research Development Center)Cooperative Hub Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(MSIT)(RS-202300258911)。
文摘Hematite(α-Fe_(2)O_(3)) based photoanodes have been extensively studied due to various intriguing features that make them viable candidates for a photoelectrochemical(PEC) water splitting photoanode.Herein,we propose a Zr-doped Fe_(2)O_(3) photoanode decorated with facilely spin-coated Au nanoparticles(NPs) and microwave-assisted attached Si co-doping in conjunction with a SiO_(x) overlayer that displayed a remarkable photocurrent density of 2.01 mA/cm^(2) at 1.23 V vs.RHE.The kinetic dynamics at the photoelectrode/-electrolyte interface was examined by employing systematic electrochemical investigations.The Au NPs played a dual role in increasing PEC water splitting.First,the Schottky interface that was formed between Au NPs and Zr-Fe_(2)O_(3) lectrode ensured the prevention of electron flow from the photoanode to the metal,increasing the number of available charges as well as suppressing surface charge recombination.Second,Au extracted photoholes from the bulk of the Zr-Fe_(2)O_(3) and transported them to the outer SiO_(x) overlayer,while the SiO_(x) overlayer efficiently collected the photoholes and promoted the hole injection into the electrolyte.Further,Si co-doping enhanced bulk conductivity by reducing bulk charge transfer resistance and improving charge carrier density.This study outlines a technique to design a metallic charge transfer path with an overlayer for solar energy conversion.
基金financially supported by the National Natural Science Foundation of China(22172013)the Special Project for Key Research and Development Program of Xinjiang Autonomous Region(2022B01033-3)+3 种基金the Liaoning Revitalization Talent Program(XLYC2008032 and XLYC2203126)the Fundamental Research Funds for the Central Universities(DUT22LK24,DUT22QN207 and DUT22LAB602)the CUHK Research Startup Fund(No.#4930981)financial support from Catalyst:Seeding funding(CSG-VUW2201)provided by the New Zealand Ministry of Business,Innovation and Employment and administered by the Royal Society Aparangi。
文摘Indium oxide(In_(2)O_(3)),as a promising candidate for CO_(2)hydrogenation to C_(1) products,often suffers from sintering and activity decline,closely related to the undesirable structural evolution under reaction conditions.Based on the comprehension of the dynamic evolution,this study presents an efficient strategy to alleviate the agglomeration of In_(2)O_(3)nanoparticles by the surface decoration with highly dispersed silica species(SiO_(x)).Various structural characterizations combined with density functional theory calculations demonstrated that the sintering resulted from the over-reduction,while the enhanced stability originated from the anchoring effect of highly stable In-OSi bonds,which hinders the substantial formation of metallic In(In^(0))and the subsequent agglomeration.0.6Si/In_(2)O_(3)exhibited CO_(2)conversion rate of10.0 mmol g^(-1)h^(-1)at steady state vs.3.5 mmol g^(-1)h^(-1)on In_(2)O_(3)in CO_(2)hydrogenation.Enhanced steady-state activity was also achieved on Pd-modified catalysts.Compared to the traditional Pd/In_(2)O_(3)catalyst,the methanol production rate of Pd catalyst supported on 0.6Si/In_(2)O_(3)was enhanced by 23%,showing the potential of In_(2)O_(3)modified by SiO_(x)in serving as a platform material.This work provides a promising method to design new In_(2)O_(3)-based catalysts with improved activity and stability in CO_(2)hydrogenation.
基金financially supporting from the Key-Area Research and Development Program of Guangdong Province(2020B090919005)the Fundamental Research Funds for the Central Universities(HIT.OCEF.2021008)+2 种基金the Key Research and Development Program of Heilongjiang Province(GA21A102)the Natural Science Foundation of Chongqing(cstc2021jcyj-msxmX0958)the National Natural Science Foundation of China(51772068)。
文摘Macro-and micro-interface instability of SiO_(x)anode caused by its dramatic volume variation during cycling will result in low Coulombic efficiency and rapid capacity degradation.In this work,an organic-inorganic composite interfacial layer rich in benzene ring groups,polyisocyanates,and LiF was obtained on SiO_(x)anode by the introduction of 4-fluorophenyl isocyanate(FPI)and fluoroethylene carbonate(FEC)co-additives in electrolyte.The SiO_(x)anode material shows a capacity retention of 69.2%after 100 cycles at a current density of 1 A g^(-1)and rate capacity of 523 m A h g^(-1)at the current density of 3A g^(-1),while the SiO_(x)anode cycling in reference electrolyte has almost no capacity.
基金support from the National Key R&D Program of China(2016YFB0700600,2020YFB0704500)China Postdoctoral Science Foundation(2019M660317)+1 种基金Engineering and Physical Sciences Research Council,UK(EP/S000933/1)Shenzhen Science and Technology Program(Grant No.RCBS20200714114820077).
文摘The commercialized binder carboxymethyl cellulose sodium(CMC-Na)is considered unsuitable for micro-sized SiO_(x) anode as it cannot endure the large volume change to retain the conductive network during repeated charge/discharge cycles.Herein,a small amount of silicon nanoparticles(SiNPs)is added during slurry preparation process as“nano-combs”to unfold the convoluted CMC-Na polymer chains so that they undergo a coilto-stretch transition by interaction between polar groups(e.g.,-OH,-COONa)of polymer and SiNPs’large surface.Through maximizing the utilization of binders,a uniform conductive network is constructed with increased interfacial contact with micro-sized SiO_(x).As a result,the SiO_(x) electrode with optimized(10 wt%)SiNPs addition shows significantly improved initial capacity and cycling performance.Through revisiting CMCNa,a currently deemed unqualified binder in SiO_(x) anode,this work gives a brand-new perspective on the failing mechanism of Si-based anode materials and an improving strategy for electrode preparation.
基金This study was supported by a grant from the National Natural Science Foundation of China(No.61804030)the Solar Energy Conversion&Energy Storage Engineering Technology Innovation Platform(No.2018L3006)the Fujian Natural Science Foundation for Distinguished Young Scholars(Grant No.2020J06042).
文摘Relieving the stress or strain associated with volume change is highly desirable for high-performance SiOx anodes in terms of stable solid electrolyte interphase(SEI)-film growth.Herein,a Si-valence gradient is optimized in SiOx composites to circumvent the large volume strain accompanied by lithium insertion/extraction.SiO_(x)@C annealed at 850℃ has a gentle Si-valence gradient along the radial direction and excellent electrochemical performances,delivering a high capacity of 506.9 mAh g^(−1) at 1.0 A g^(−1) with a high Coulombic efficiency of~99.8%over 400 cycles.Combined with the theoretical prediction,the obtained results indicate that the gentle Si-valence gradient in SiO_(x)@C is useful for suppressing plastic deformation and maintaining the inner connection integrity within the SiO_(x)@C particle.Moreover,a gentle Si-valence gradient is expected to form a stress gradient and affect the distribution of dangling bonds,resulting in local stress relief during the lithiation/delithiation process and enhanced Li-ion kinetic diffusion.Furthermore,the lowest interfacial stress variation ensures a stable SEI film at the interface and consequently increases cycling stability.Therefore,rational design of a Si-valence gradient in SiOx can provide further insights into achieving high-performance SiOx anodes with large-scale production.
基金the National Renewable Energy Laboratory,operated by Alliance for Sustainable Energy,LLC,for the U.S.Department of Energy(DOE)under Contract No.DE-AC36-08GO28308.
文摘Polycrystalline Si(poly-Si)-based passivating contacts are promising candidates for high-efficiency crystalline Si solar cells.We show that nanosecond-scale pulsed laser melting(PLM)is an industrially viable technique to fabricate such contacts with precisely controlled dopant concentration profiles that exceed the solid solubility limit.We demonstrate that conventionally doped,hole-selective poly-Si/SiO_(x)contacts that provide poor surface passivation of c-Si can be replaced with Ga-or B-doped contacts based on non-equilibrium doping.We overcome the solid solubility limit for both dopants in poly-Si by rapid cooling and recrystallization over a timescale of∼25 ns.We show an active Ga dopant concentration of∼3×10^(20)cm^(−3)in poly-Si which is six times higher than its solubility limit in c-Si,and a B dopant concentration as high as∼10^(21) cm^(−3).We measure an implied open-circuit voltage of 735 mV for Ga-doped poly-Si/SiO_(x)contacts on Czochralski Si with a low contact resistivity of 35.5±2.4 mΩcm^(2).Scanning spreading resistance microscopy and Kelvin probe force microscopy show large diffusion and drift current in the p-n junction that contributes to the low contact resistivity.Our results suggest that PLM can be extended for hyperdoping of other semiconductors with low solubility atoms to enable high-efficiency devices.
