Aqueous Zn-ion batteries(ZIBs)hold great potential in large-scale energy storage systems due to the merits of low-cost and high safety.However,the unstable structure of cathode materials and sluggish(de)intercalation ...Aqueous Zn-ion batteries(ZIBs)hold great potential in large-scale energy storage systems due to the merits of low-cost and high safety.However,the unstable structure of cathode materials and sluggish(de)intercalation kinetics of Zn2+pose challenges for further development.Herein,highly reversible aqueous ZIBs are constructed with layered hydrated vanadium oxide as a cathode material.The electrochemical performances are further tested with the optimized electrolyte of 3M Zn(CF3SO3)2 and a cut-off voltage of 0.4 to 1.3 V,exhibiting a remarkable capacity of 290mAh g−1 at 0.5Ag−1,and long-term cycling stability at high current density.Furthermore,the Zn2+storage mechanism of V3O7⋅H2O is recognized as a highly reversible(de)intercalation process with good structural stability,implying the potential application in the field of large-scale energy storage.展开更多
A new layered mixed valence vanadium oxide, [CH 3NH 3] 2[(V ⅣO) 2(V ⅤO 4) 2], which contains interlamellar organic cations was prepared under hydrothermal conditions and its single crystal structure was determined. ...A new layered mixed valence vanadium oxide, [CH 3NH 3] 2[(V ⅣO) 2(V ⅤO 4) 2], which contains interlamellar organic cations was prepared under hydrothermal conditions and its single crystal structure was determined. It crystallizes in a triclinic system with space group P 1, a =0 625 59(8) nm, b =0 639 84(9) nm, c =0 747 19(10) nm, α =78 718(2)°, β =80 099(2)°, γ =77 100(2). The compound contains mixed valence V 4+ /V 5+ vanadium oxide layers constructed from VO 4 tetrahedra, pairs of edge sharing VO 5 square pyramid and methylamine with protonated organic amines occupying the interlayer space.展开更多
Vanadium oxide films were grown by atomic layer deposition using the tetrakis[ethylmethylamino] vanadium as the vanadium precursor and H2O as the oxide source. The effect of the source temperature on the quality of va...Vanadium oxide films were grown by atomic layer deposition using the tetrakis[ethylmethylamino] vanadium as the vanadium precursor and H2O as the oxide source. The effect of the source temperature on the quality of vanadium oxide films and valence state was investigated. The crystallinity, surface morphology, film thickness, and photoelectric properties of the films were characterized by x-ray diffraction, atomic force microscope, scanning electron microscope, I–V characteristics curves, and UV–visible spectrophotometer. By varying the source temperature, the content of V6O11, VO2, and V6O13 in the vanadium oxide film increased, that is, as the temperature increased, the average oxidation state generally decreased to a lower value, which is attributed to the rising of the vapor pressure and the change of the ionization degree for organometallics. Meanwhile, the root-mean-square roughness decreased and the metal–insulator transition temperature reduced. Our study is great significance for the fabrication of vanadium oxide films by atomic layer deposition.展开更多
We present an enhancement of the uorescence of shallow (<10 nm) nitrogen-vacancy (NV-) centers by using atomic layer deposition to deposit titanium oxide layers on the diamond surface. In this way, the shallow NV-c...We present an enhancement of the uorescence of shallow (<10 nm) nitrogen-vacancy (NV-) centers by using atomic layer deposition to deposit titanium oxide layers on the diamond surface. In this way, the shallow NV-center charge states were stabilized, leading to the increasing uorescence intensity of about 2 times. This surface coating technique could produce a protective layer of controllable thickness without any damages to the solid-state quantum system surface, which might be an approach to the further passivation or packaging techniques for the solid-state quantum devices.展开更多
The specific capacities and power performances of conventional cathode materials are still needed to improve in order to meet the demand for electrical vehicles.Li-rich layered oxide delivers a high specific capacity,...The specific capacities and power performances of conventional cathode materials are still needed to improve in order to meet the demand for electrical vehicles.Li-rich layered oxide delivers a high specific capacity,but poor rate performances.Chemical doping is an effective way to address this challenge due to the expanded crystal lattice.Unlike a single ion substitution in the literature,here Li-rich layered oxides were doped by Sn and K to achieve the favorite rate performance,where Sn and K were assumed to replace transition metal ion and Li ion,respectively.Results indicate the co-doped samples result in an increasing capacity retention by more than 40%from 107.9(contrast sample)to 151.5 mAh g^(-1)(co-doped sample)at 10 C-rate.Electrochemical impedance spectroscopy(EIS)and calculated diffusion coefficient of Li^(+) also confirmed the favorite rate performances for co-doped sample.Combining results of Rietveld structure refinement,we proposed that the reason for rate performances comes from the enlarged crystal lattices,which provides a smooth diffusion tunnel for Lithium ions during the charge/discharge processes.The as-adopted method provides a possibility to achieve the improved rate performances by co-doping big-size ions at the different crystal sites.展开更多
Calcium-ion batteries(CIBs)have generated intense interest due to the growing demand for safer,cheaper,and large-scale energy storage systems.However,their development is still in its infancy,owing to the lack of suit...Calcium-ion batteries(CIBs)have generated intense interest due to the growing demand for safer,cheaper,and large-scale energy storage systems.However,their development is still in its infancy,owing to the lack of suitable cathodes for sustaining reversiblc Ca^(2+)intercalation/deintercalation.Herein,layered H_(2)V_(3)O_(8)(HVO)with Zn^(2+)pre-insertion(ZHVO)is reported as a high-rate and highly durable cathode material for CIBs.The existence of Zn^(2+)and H_(2)O pillars could expand the interlayer spacing up to 1.8 nm,which is favorable for the diffusion of bulky Ca^(2+).The formation of Zn-O bonds facilitates electron transfer and enhances electrical conduction.Consequently,the ZHVO cathode achieves superior capacity performance(213.9 mAh·g^(-1)at 0.2 A·g^(-1))and long lifespan(78.3%for 1,000 cycles at 5 A·g^(-1))compared to pristine HVO.Density functional theory(DFT)calculations revealed that Zn^(2+)moved during Ca^(2+)intercalation,thereby reducing the diffusion energy barrier and facilitating Ca^(2+)diffusion.Finally,a safe aqueous calcium ion cell was successfully assembled.展开更多
针对背沟道刻蚀(Back Channel Etch,BCE)技术的非晶铟镓锌氧化物(a-IGZO)薄膜晶体管(Thin Film Transistor,TFTs),建立了一种高浓度掺杂态密度模型(High Concentration Doping Density Of States model,HCD-DOS model),并通过数值模拟...针对背沟道刻蚀(Back Channel Etch,BCE)技术的非晶铟镓锌氧化物(a-IGZO)薄膜晶体管(Thin Film Transistor,TFTs),建立了一种高浓度掺杂态密度模型(High Concentration Doping Density Of States model,HCD-DOS model),并通过数值模拟研究态密度关键参数对器件性能的影响,以此揭示a-IGZO TFTs中制备工艺对导电沟道修复的物理机理.首先,采用结合强度较高的钼/铜双层结构作为栅/源/漏电极,引入BCE方法制备了底栅顶接触(BottomGate Top-Contact,BG-TC)TFTs.其次,建立了适用于BCE技术的a-IGZO TFTs的HCD-DOS模型.随后,基于TCAD(Technology Computer Aided Design)仿真器对态密度关键参数进行数值研究,结果表明,不同态密度参数对a-IGZO TFTs器件转移特性曲线、电学特性以及沟道内部电子浓度分布的影响有所差异.最后,基于HCD-DOS模型探索SiO_(x)钝化层沉积和N_(2)O等离子体处理对器件内部机理的影响.研究发现,N2O等离子体处理对态密度分布和沟道载流子浓度有显著影响,进而导致阈值电压正向漂移.展开更多
The high price of state-of-the-art Pt electrocatalysts has plagued the acidic water electrolysis technique for decades. As a cheaper alternative to Pt, ruthenium is considered an inferior hydrogen evolution reaction (...The high price of state-of-the-art Pt electrocatalysts has plagued the acidic water electrolysis technique for decades. As a cheaper alternative to Pt, ruthenium is considered an inferior hydrogen evolution reaction (HER) catalyst than Pt due to its high susceptibility to oxidation and loss of activity. Herein, we reveal that the HER activity on Ru based catalysts could surpass Pt via tuning Ru oxidation state. Specifically, RuP clusters encapsulated in few layers of N, P-doped carbon (RuP@NPC) display a minimum over potential of 15.6 mV to deliver 10 mA·cm^(−2). Moreover, we for the first time show that a Ru based catalyst could afford current density up to 4 A·cm^(−2) in a practical water electrolysis cell, with voltage even lower than the Pt/C-based cell, as well as high robustness during 200 h operation. Using a combination of experiment probing and calculation, we postulate that the suitably charged Ru (∼ +2.4) catalytic center is the origin for its superior catalytic behavior. While the moderately charged Ru is empowered with optimized H adsorption behavior, the carbon encapsulation layers protect RuP clusters from over oxidation, thereby conferring the catalyst with high robustness.展开更多
Here we reported the fabrication of efficient polymer solar cells from regioregular poly（3-hexylthiophene） （P3HT）：fullerene derivative [6,6]-phenyl-C61 butyric acid methyl ester （PC6jBM） mixtures, in which solu...Here we reported the fabrication of efficient polymer solar cells from regioregular poly（3-hexylthiophene） （P3HT）：fullerene derivative [6,6]-phenyl-C61 butyric acid methyl ester （PC6jBM） mixtures, in which solution- processed vanadium oxide （VOx） was used as a hole-extracting layer （HEL）. The obtained devices exhibited a high power conversion efficiency of 3.96%, and can be enhanced to 4.06% and 4.16%, respectively, when two types of PEDOT：PSS with different conductivities were used in conjunction with the VOx layer. All the VOx-based devices showed a high fill factor （FF） over 70%, which was ascribed to efficient hole extracting efficiency associated with the solution-processed VOx hole-extracting layer. The origins of the improvement were also studied by transmission spectra, atomic force microscope （AFM）, and capacitance-voltage characteristics.展开更多
基金This study was supported by the National Natural Science Foundation of China(Grant no.51932011,51972346,51802356,and 51872334)Innovation-Driven Project of Central South University(No.2020CX024).
文摘Aqueous Zn-ion batteries(ZIBs)hold great potential in large-scale energy storage systems due to the merits of low-cost and high safety.However,the unstable structure of cathode materials and sluggish(de)intercalation kinetics of Zn2+pose challenges for further development.Herein,highly reversible aqueous ZIBs are constructed with layered hydrated vanadium oxide as a cathode material.The electrochemical performances are further tested with the optimized electrolyte of 3M Zn(CF3SO3)2 and a cut-off voltage of 0.4 to 1.3 V,exhibiting a remarkable capacity of 290mAh g−1 at 0.5Ag−1,and long-term cycling stability at high current density.Furthermore,the Zn2+storage mechanism of V3O7⋅H2O is recognized as a highly reversible(de)intercalation process with good structural stability,implying the potential application in the field of large-scale energy storage.
基金Supported by the National Natural Science Foundation of China(No.2 0 1710 10 )
文摘A new layered mixed valence vanadium oxide, [CH 3NH 3] 2[(V ⅣO) 2(V ⅤO 4) 2], which contains interlamellar organic cations was prepared under hydrothermal conditions and its single crystal structure was determined. It crystallizes in a triclinic system with space group P 1, a =0 625 59(8) nm, b =0 639 84(9) nm, c =0 747 19(10) nm, α =78 718(2)°, β =80 099(2)°, γ =77 100(2). The compound contains mixed valence V 4+ /V 5+ vanadium oxide layers constructed from VO 4 tetrahedra, pairs of edge sharing VO 5 square pyramid and methylamine with protonated organic amines occupying the interlayer space.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11674038,61674021,61704011,and 61904017)the Developing Project of Science and Technology of Jilin Province,China(Grant Nos.20170520118JH and 20160520027JH)the Youth Foundation of Changchun University of Science and Technology(Grant No.XQNJJ-2018-18).
文摘Vanadium oxide films were grown by atomic layer deposition using the tetrakis[ethylmethylamino] vanadium as the vanadium precursor and H2O as the oxide source. The effect of the source temperature on the quality of vanadium oxide films and valence state was investigated. The crystallinity, surface morphology, film thickness, and photoelectric properties of the films were characterized by x-ray diffraction, atomic force microscope, scanning electron microscope, I–V characteristics curves, and UV–visible spectrophotometer. By varying the source temperature, the content of V6O11, VO2, and V6O13 in the vanadium oxide film increased, that is, as the temperature increased, the average oxidation state generally decreased to a lower value, which is attributed to the rising of the vapor pressure and the change of the ionization degree for organometallics. Meanwhile, the root-mean-square roughness decreased and the metal–insulator transition temperature reduced. Our study is great significance for the fabrication of vanadium oxide films by atomic layer deposition.
基金National Natu- ral Science Foundation of China (No.11374280 and No.50772110). The authors wish to thank Guo-ping Guo, Jie You and Yang Li from the Key Lab of Quan- tum Information for the support of electron beam lithography. We also thank Ming-ling Li at University of Science and Technology of China for the technical support of ALD.
文摘We present an enhancement of the uorescence of shallow (<10 nm) nitrogen-vacancy (NV-) centers by using atomic layer deposition to deposit titanium oxide layers on the diamond surface. In this way, the shallow NV-center charge states were stabilized, leading to the increasing uorescence intensity of about 2 times. This surface coating technique could produce a protective layer of controllable thickness without any damages to the solid-state quantum system surface, which might be an approach to the further passivation or packaging techniques for the solid-state quantum devices.
基金This work was financially supported by the National Natural Science Foundation of China under Grant No.51772296,51672071,51802085the Foundation for State Key Laboratory of Biochemical Engineering,and“111”Project(D17007).
文摘The specific capacities and power performances of conventional cathode materials are still needed to improve in order to meet the demand for electrical vehicles.Li-rich layered oxide delivers a high specific capacity,but poor rate performances.Chemical doping is an effective way to address this challenge due to the expanded crystal lattice.Unlike a single ion substitution in the literature,here Li-rich layered oxides were doped by Sn and K to achieve the favorite rate performance,where Sn and K were assumed to replace transition metal ion and Li ion,respectively.Results indicate the co-doped samples result in an increasing capacity retention by more than 40%from 107.9(contrast sample)to 151.5 mAh g^(-1)(co-doped sample)at 10 C-rate.Electrochemical impedance spectroscopy(EIS)and calculated diffusion coefficient of Li^(+) also confirmed the favorite rate performances for co-doped sample.Combining results of Rietveld structure refinement,we proposed that the reason for rate performances comes from the enlarged crystal lattices,which provides a smooth diffusion tunnel for Lithium ions during the charge/discharge processes.The as-adopted method provides a possibility to achieve the improved rate performances by co-doping big-size ions at the different crystal sites.
基金financially supported by the Open Research Found of Songshan Lake Materials Laboratory(No.2021SLABFN04)National Natural Science Foundation of China(Nos.22109134 and 52171025)+1 种基金Guangdong Basic and Applied Basic Research Foundation(No.2022A1515010920)the Outstanding Youth Basic Research Project of Shenzhen(No.RCYX20221008092934093)。
文摘Calcium-ion batteries(CIBs)have generated intense interest due to the growing demand for safer,cheaper,and large-scale energy storage systems.However,their development is still in its infancy,owing to the lack of suitable cathodes for sustaining reversiblc Ca^(2+)intercalation/deintercalation.Herein,layered H_(2)V_(3)O_(8)(HVO)with Zn^(2+)pre-insertion(ZHVO)is reported as a high-rate and highly durable cathode material for CIBs.The existence of Zn^(2+)and H_(2)O pillars could expand the interlayer spacing up to 1.8 nm,which is favorable for the diffusion of bulky Ca^(2+).The formation of Zn-O bonds facilitates electron transfer and enhances electrical conduction.Consequently,the ZHVO cathode achieves superior capacity performance(213.9 mAh·g^(-1)at 0.2 A·g^(-1))and long lifespan(78.3%for 1,000 cycles at 5 A·g^(-1))compared to pristine HVO.Density functional theory(DFT)calculations revealed that Zn^(2+)moved during Ca^(2+)intercalation,thereby reducing the diffusion energy barrier and facilitating Ca^(2+)diffusion.Finally,a safe aqueous calcium ion cell was successfully assembled.
文摘针对背沟道刻蚀(Back Channel Etch,BCE)技术的非晶铟镓锌氧化物(a-IGZO)薄膜晶体管(Thin Film Transistor,TFTs),建立了一种高浓度掺杂态密度模型(High Concentration Doping Density Of States model,HCD-DOS model),并通过数值模拟研究态密度关键参数对器件性能的影响,以此揭示a-IGZO TFTs中制备工艺对导电沟道修复的物理机理.首先,采用结合强度较高的钼/铜双层结构作为栅/源/漏电极,引入BCE方法制备了底栅顶接触(BottomGate Top-Contact,BG-TC)TFTs.其次,建立了适用于BCE技术的a-IGZO TFTs的HCD-DOS模型.随后,基于TCAD(Technology Computer Aided Design)仿真器对态密度关键参数进行数值研究,结果表明,不同态密度参数对a-IGZO TFTs器件转移特性曲线、电学特性以及沟道内部电子浓度分布的影响有所差异.最后,基于HCD-DOS模型探索SiO_(x)钝化层沉积和N_(2)O等离子体处理对器件内部机理的影响.研究发现,N2O等离子体处理对态密度分布和沟道载流子浓度有显著影响,进而导致阈值电压正向漂移.
基金The authors acknowledge funding from the National Key R&D Program of China (No. 2018YFB1502400)the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDA21090400)the Jilin Province Science and Technology Development Program (Nos. 20190201300JC and 20180101030JC).
文摘The high price of state-of-the-art Pt electrocatalysts has plagued the acidic water electrolysis technique for decades. As a cheaper alternative to Pt, ruthenium is considered an inferior hydrogen evolution reaction (HER) catalyst than Pt due to its high susceptibility to oxidation and loss of activity. Herein, we reveal that the HER activity on Ru based catalysts could surpass Pt via tuning Ru oxidation state. Specifically, RuP clusters encapsulated in few layers of N, P-doped carbon (RuP@NPC) display a minimum over potential of 15.6 mV to deliver 10 mA·cm^(−2). Moreover, we for the first time show that a Ru based catalyst could afford current density up to 4 A·cm^(−2) in a practical water electrolysis cell, with voltage even lower than the Pt/C-based cell, as well as high robustness during 200 h operation. Using a combination of experiment probing and calculation, we postulate that the suitably charged Ru (∼ +2.4) catalytic center is the origin for its superior catalytic behavior. While the moderately charged Ru is empowered with optimized H adsorption behavior, the carbon encapsulation layers protect RuP clusters from over oxidation, thereby conferring the catalyst with high robustness.
基金H.-B.W.sincerely thank National Basic Research Program of China，National Natural Science Foundation of China，Program for New Century Excellent Talents in University (NCET-10-0400) for the financial support
文摘Here we reported the fabrication of efficient polymer solar cells from regioregular poly（3-hexylthiophene） （P3HT）：fullerene derivative [6,6]-phenyl-C61 butyric acid methyl ester （PC6jBM） mixtures, in which solution- processed vanadium oxide （VOx） was used as a hole-extracting layer （HEL）. The obtained devices exhibited a high power conversion efficiency of 3.96%, and can be enhanced to 4.06% and 4.16%, respectively, when two types of PEDOT：PSS with different conductivities were used in conjunction with the VOx layer. All the VOx-based devices showed a high fill factor （FF） over 70%, which was ascribed to efficient hole extracting efficiency associated with the solution-processed VOx hole-extracting layer. The origins of the improvement were also studied by transmission spectra, atomic force microscope （AFM）, and capacitance-voltage characteristics.
