The large volumetric variations experienced by metal selenides within conversion reaction result in inferior rate capability and cycling stability,ultimately hindering the achievement of superior electrochemical perfo...The large volumetric variations experienced by metal selenides within conversion reaction result in inferior rate capability and cycling stability,ultimately hindering the achievement of superior electrochemical performance.Herein,metallic Cu_(2)Se encapsulated with N-doped carbon(Cu_(2)Se@NC)was prepared using Cu_(2)O nanocubes as templates through a combination of dopamine polymerization and hightemperature selenization.The unique nanocubic structure and uniform N-doped carbon coating could shorten the ion transport distance,accelerate electron/charge diffusion,and suppress volume variation,ultimately ensuring Cu_(2)Se@NC with excellent electrochemical performance in sodium ion batteries(SIBs)and potassium ion batteries(PIBs).The composite exhibited excellent rate performance(187.7 mA h g^(-1)at 50 A g^(-1)in SIBs and 179.4 mA h g^(-1)at 5 A g^(-1)in PIBs)and cyclic stability(246,8 mA h g^(-1)at 10 A g^(-1)in SIBs over 2500 cycles).The reaction mechanism of intercalation combined with conversion in both SIBs and PIBs was disclosed by in situ X-ray diffraction(XRD)and ex situ transmission electron microscope(TEM).In particular,the final products in PIBs of K_(2)Se and K_(2)Se_(3)species were determined after discharging,which is different from that in SIBs with the final species of Na_(2)Se.The density functional theory calculation showed that carbon induces strong coupling and charge interactions with Cu_(2)Se,leading to the introduction of built-in electric field on heterojunction to improve electron mobility.Significantly,the theoretical calculations discovered that the underlying cause for the relatively superior rate capability in SIBs to that in PIBs is the agile Na~+diffusion with low energy barrier and moderate adsorption energy.These findings offer theoretical support for in-depth understanding of the performance differences of Cu-based materials in different ion storage systems.展开更多
通过还原法制备了Cu_(2)O/还原氧化石墨烯(Cu_(2)O/rGO)复合材料,采用SEM、FTIR、EDS、XRD、XPS、氮气吸附-脱附、循环伏安曲线对其结构和氧还原性能进行了表征和测试。将Cu_(2)O/rGO复合材料负载于碳布制得了Cu_(2)O/rGO阴极,以硝酸盐...通过还原法制备了Cu_(2)O/还原氧化石墨烯(Cu_(2)O/rGO)复合材料,采用SEM、FTIR、EDS、XRD、XPS、氮气吸附-脱附、循环伏安曲线对其结构和氧还原性能进行了表征和测试。将Cu_(2)O/rGO复合材料负载于碳布制得了Cu_(2)O/rGO阴极,以硝酸盐作为模型污染物,将其作为微生物燃料电池(MFC)的阴极,探究其对MFC产电脱氮性能和微生物菌落结构的影响。结果表明,Cu_(2)O/rGO复合材料具有大量的介孔结构和良好的氧还原可逆性。与Pt/C阴极相比,Cu_(2)O/rGO阴极的交换电流密度升高了47.77%,电荷转移阻抗降低了65.53%。Cu_(2)O/rGO-MFC在处理NO_(3)^(–)-N废水时平均最大输出电压为662.54 m V、最大功率密度为26.27 m W/cm^(2)、平均库仑效率为32.02%、NO_(3)^(–)-N去除速率为83.33 mg/(L·h),均高于Pt/C-MFC[485.33 m V、16.98 m W/cm^(2)、7.38%、41.67 mg/(L·h)]。Cu_(2)O/rGO-MFC阴极生物膜中反硝化关键酶活性和胞外聚合物含量增加,同时,功能性微生物Betaproteobacteria和Alphaproteobacteria纲的丰度分别较Pt/C-MFC增加了35.66%和36.96%。展开更多
The environmentally friendly Cu_(2)ZnSn(S,Se)_(4)(CZTSSe) compounds are promising direct bandgap materials for application in thin film solar cells, but the spontaneous surface defects disordering would lead to large ...The environmentally friendly Cu_(2)ZnSn(S,Se)_(4)(CZTSSe) compounds are promising direct bandgap materials for application in thin film solar cells, but the spontaneous surface defects disordering would lead to large open-circuit voltage deficit(V_(oc,deficit)) and significantly limit kesterite photovoltaics performance,primarily arising from the generated more recombination centers and insufficient p to n conversion at p-n junction. Herein, we establish a surface defects ordering structure in CZTSSe system via local substitution of Cu by Ag to suppress disordered Cu_(Zn) defects and generate benign n-type Zn_(Ag) donors. Taking advantage of the decreased annealing temperature of Ag F post deposition treatment(PDT), the high concentration of Ag incorporated into surface absorber facilitates the formation of surface ordered defect environment similar to that of efficient CIGS PV. The manipulation of highly doped surface structure could effectively reduce recombination centers, increase depletion region width and enlarge the band bending near p-n junction. As a result, the Ag F-PDT device finally achieves maximum efficiency of 12.34% with enhanced V_(oc) of 0.496 V. These results offer a new solution route in surface defects and energy-level engineering, and open the way to build up high quality p-n junction for future development of kesterite technology.展开更多
It is very important to understand why a small amount of alkali metal doping in Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells can improve the conversion efficiency.In this work,Na-doped CZTSSe is prepared by a simple soluti...It is very important to understand why a small amount of alkali metal doping in Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells can improve the conversion efficiency.In this work,Na-doped CZTSSe is prepared by a simple solution method,and then the effects on the surface properties of the absorber layer,the buffer layer growth,and the modifications of the solar cell performance induced by the Na doping are studied.The surface of the absorber layer is more Cu-depletion and less roughness due to the Na doping.In addition,the contact angle of the surface increases because of Na doping.As a consequence,the thickness of the CdS buffer layer is significantly reduced and the optical losses in the CdS buffer layer are decreased.The difference of quasi-Fermi levels(EFn-EFp) increases with a small amount of Na doping in the CZTSSe solar cell,so that open circuit voltage(VOC) increased significantly.This work offers new insights into the effects of Na doping on CZTSSe via a solution-based approach and provides a deeper understanding of the origin of the efficiency improvement of Na-doped CZTSSe thin film solar cells.展开更多
The nanoporous Cu_(2-x)Se with Cu(Se-5%)surface catalysts were prepared through in situ dynamic restructuring strategy during the electrochemical process,which achieves highly selective electrochemical CO_(2) reductio...The nanoporous Cu_(2-x)Se with Cu(Se-5%)surface catalysts were prepared through in situ dynamic restructuring strategy during the electrochemical process,which achieves highly selective electrochemical CO_(2) reduction to methanol.In situ and quasi-operando spectroscopic results provide a deep insight into the catalytic active centres of reconstructed heterogeneous catalysts for CO_(2) electroreduction.展开更多
Photo-generated carrier recombination loss at the CZTSSe/Cd S front interface is a key issue to the opencircuit voltage(V_(OC)) deficit of Cu_(2)ZnSnS_(x)Se_(4-x)(CZTSSe) solar cells. Here, by the aid of an easy-handl...Photo-generated carrier recombination loss at the CZTSSe/Cd S front interface is a key issue to the opencircuit voltage(V_(OC)) deficit of Cu_(2)ZnSnS_(x)Se_(4-x)(CZTSSe) solar cells. Here, by the aid of an easy-handling spin-coating method, a thin PCBM([6,6]-phenyl-C61-butyric acid methyl ester) layer as an electron extraction layer has been introduced on the top of CdS buffer layer to modify CZTSSe/CdS/ZnO-ITO(In_(2)O_(3):Sn) interfacial properties. Based on Sn^(4+)/DMSO(dimethyl sulfoxide) solution system, a totalarea efficiency of 12.87% with a VOC of 529 m V has been achieved. A comprehensive investigation on the influence of PCBM layer on carrier extraction, transportation and recombination processes has been carried out. It is found that the PCBM layer can smooth over the Cd S film roughness, thus beneficial for a dense and flat window layer. Furthermore, this CZTSSe/Cd S/PCBM heterostructure can accelerate carrier separation and extraction and block holes from the front interface as well, which is mainly ascribed to the downward band bending of the absorber and a widened space charge region. Our work provides a feasible way to improve the front interfacial property and the cell performance of CZTSSe solar cells by the aid of organic interfacial materials.展开更多
Focusing on the low open circuit voltage(V_(OC))and fill factor(FF)in flexible Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells,indium(In)ions are introduced into the CZTSSe absorbers near Mo foils to modify the back interface...Focusing on the low open circuit voltage(V_(OC))and fill factor(FF)in flexible Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells,indium(In)ions are introduced into the CZTSSe absorbers near Mo foils to modify the back interface and passivate deep level defects in CZTSSe bulk concurrently for improving the performance of flexible device.The results show that In doping effectively inhibits the formation of secondary phase(Cu(S,Se)_(2))and VSndefects.Further studies demonstrate that the barrier height at the back interface is decreased and the deep level defects(Cu_(Sn)defects)in CZTSSe bulk are passivated.Moreover,the carrier concentration is increased and the V_(OC) deficit(V_(OC,def))is decreased significantly due to In doping.Finally,the flexible CZTSSe solar cell with 10.01%power conversion efficiency(PCE)has been obtained.The synergistic strategy of interface modification and bulk defects passivation through In incorporation provides a new thought for the fabrication of efficient flexible kesterite-based solar cells.展开更多
Bulk group IB transition-metal chalcogenides have been widely explored due to their applications in thermoelectrics.However,a layered two-dimensional form of these materials has been rarely reported.Here,we realize se...Bulk group IB transition-metal chalcogenides have been widely explored due to their applications in thermoelectrics.However,a layered two-dimensional form of these materials has been rarely reported.Here,we realize semiconducting Cu_(2)Se by direct selenization of Cu(111).Scanning tunneling microcopy measurements combined with first-principles calculations allow us to determine the structural and electronic properties of the obtained structure.X-ray photoelectron spectroscopy data reveal chemical composition of the sample,which is Cu_(2)Se.The observed moire pattern indicates a lattice mismatch between Cu_(2)Se and the underlying Cu(111)-√3×√3 surface.Differential conductivity obtained by scanning tunneling spectroscopy demonstrates that the synthesized Cu_(2)Se exhibits a band gap of 0.78 eV.Furthermore,the calculated density of states and band structure demonstrate that the isolated Cu_(2)Se is a semiconductor with an indirect band gap of-0.8 eV,which agrees quite well with the experimental results.Our study provides a simple pathway varying toward the synthesis of novel layered 2D transition chalcogenides materials.展开更多
Three-dimentional(3D)transition metal selenides with sufficient channels could produce significant superiority on enhancing reaction kinetics for sodium-ion batteries.However,the thorough exploration of 3D architectur...Three-dimentional(3D)transition metal selenides with sufficient channels could produce significant superiority on enhancing reaction kinetics for sodium-ion batteries.However,the thorough exploration of 3D architecture with a facile strategy is still challenging.Here we report that a polycrystalline Cu_(2-x)Se film was epitaxial grown on(220)facets-exposed Cu by direct selenization of a nanoporous Cu skeleton,which is obtained by dealloying rolled Cu Mn@Cu alloy foil.Density functional theory calculation result shows strong adsorption energy for Se atoms on Cu(220)planes during selenization reaction,rendering a low energy consumption.By virtue of this core-shell 3D nanoporous architecture to offer abundant active sites and endow fast electron/ion transportation,the nanoporous Cu_(2-x)Se@Cu-0.15 composite electrode exhibits remarkable sodium-ion storage properties with high reversible capacity of 950.6μAh/cm^(2)at 50μA/cm^(2),suprior rate capability of 457.6μAh/cm^(2)at 500μA/cm^(2),as well as an ultra-long stability at a high current density.Mechanism investigation reveals that the electrochemical reaction is a typical conversion-type reaction with different intermediates.This novel electrode synthetic strategy provides useful instructions to design the high-performance anode material for sodium-ion batteries.展开更多
基金The Natural Science Foundation of Henan Province(222300420083)the Opening Foundation of State Key Laboratory of Chemistry and Utilization of Carbon-based Energy Resource of Xinjiang University(KFKT2021004)。
文摘The large volumetric variations experienced by metal selenides within conversion reaction result in inferior rate capability and cycling stability,ultimately hindering the achievement of superior electrochemical performance.Herein,metallic Cu_(2)Se encapsulated with N-doped carbon(Cu_(2)Se@NC)was prepared using Cu_(2)O nanocubes as templates through a combination of dopamine polymerization and hightemperature selenization.The unique nanocubic structure and uniform N-doped carbon coating could shorten the ion transport distance,accelerate electron/charge diffusion,and suppress volume variation,ultimately ensuring Cu_(2)Se@NC with excellent electrochemical performance in sodium ion batteries(SIBs)and potassium ion batteries(PIBs).The composite exhibited excellent rate performance(187.7 mA h g^(-1)at 50 A g^(-1)in SIBs and 179.4 mA h g^(-1)at 5 A g^(-1)in PIBs)and cyclic stability(246,8 mA h g^(-1)at 10 A g^(-1)in SIBs over 2500 cycles).The reaction mechanism of intercalation combined with conversion in both SIBs and PIBs was disclosed by in situ X-ray diffraction(XRD)and ex situ transmission electron microscope(TEM).In particular,the final products in PIBs of K_(2)Se and K_(2)Se_(3)species were determined after discharging,which is different from that in SIBs with the final species of Na_(2)Se.The density functional theory calculation showed that carbon induces strong coupling and charge interactions with Cu_(2)Se,leading to the introduction of built-in electric field on heterojunction to improve electron mobility.Significantly,the theoretical calculations discovered that the underlying cause for the relatively superior rate capability in SIBs to that in PIBs is the agile Na~+diffusion with low energy barrier and moderate adsorption energy.These findings offer theoretical support for in-depth understanding of the performance differences of Cu-based materials in different ion storage systems.
文摘通过还原法制备了Cu_(2)O/还原氧化石墨烯(Cu_(2)O/rGO)复合材料,采用SEM、FTIR、EDS、XRD、XPS、氮气吸附-脱附、循环伏安曲线对其结构和氧还原性能进行了表征和测试。将Cu_(2)O/rGO复合材料负载于碳布制得了Cu_(2)O/rGO阴极,以硝酸盐作为模型污染物,将其作为微生物燃料电池(MFC)的阴极,探究其对MFC产电脱氮性能和微生物菌落结构的影响。结果表明,Cu_(2)O/rGO复合材料具有大量的介孔结构和良好的氧还原可逆性。与Pt/C阴极相比,Cu_(2)O/rGO阴极的交换电流密度升高了47.77%,电荷转移阻抗降低了65.53%。Cu_(2)O/rGO-MFC在处理NO_(3)^(–)-N废水时平均最大输出电压为662.54 m V、最大功率密度为26.27 m W/cm^(2)、平均库仑效率为32.02%、NO_(3)^(–)-N去除速率为83.33 mg/(L·h),均高于Pt/C-MFC[485.33 m V、16.98 m W/cm^(2)、7.38%、41.67 mg/(L·h)]。Cu_(2)O/rGO-MFC阴极生物膜中反硝化关键酶活性和胞外聚合物含量增加,同时,功能性微生物Betaproteobacteria和Alphaproteobacteria纲的丰度分别较Pt/C-MFC增加了35.66%和36.96%。
基金supported by the National Natural Science Foundation of China(61874159,62074052,61974173,52072327,51702085 and 51802081)the Joint Talent Cultivation Funds of NSFC-HN(U1704151 and U1904192)+1 种基金the Zhongyuan Thousand Talents(Zhongyuan Scholars)Program of Henan Province(202101510004)the Science and Technology Innovation Talents in Universities of Henan Province(21HASTIT023)。
文摘The environmentally friendly Cu_(2)ZnSn(S,Se)_(4)(CZTSSe) compounds are promising direct bandgap materials for application in thin film solar cells, but the spontaneous surface defects disordering would lead to large open-circuit voltage deficit(V_(oc,deficit)) and significantly limit kesterite photovoltaics performance,primarily arising from the generated more recombination centers and insufficient p to n conversion at p-n junction. Herein, we establish a surface defects ordering structure in CZTSSe system via local substitution of Cu by Ag to suppress disordered Cu_(Zn) defects and generate benign n-type Zn_(Ag) donors. Taking advantage of the decreased annealing temperature of Ag F post deposition treatment(PDT), the high concentration of Ag incorporated into surface absorber facilitates the formation of surface ordered defect environment similar to that of efficient CIGS PV. The manipulation of highly doped surface structure could effectively reduce recombination centers, increase depletion region width and enlarge the band bending near p-n junction. As a result, the Ag F-PDT device finally achieves maximum efficiency of 12.34% with enhanced V_(oc) of 0.496 V. These results offer a new solution route in surface defects and energy-level engineering, and open the way to build up high quality p-n junction for future development of kesterite technology.
基金supported by the National Key R&D Program of China(2019YFB1503500,2018YFB1500200,2018YEE0203400)the Natural Science Foundation of China(U1902218,11774187)the 111 project(B16027)。
文摘It is very important to understand why a small amount of alkali metal doping in Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells can improve the conversion efficiency.In this work,Na-doped CZTSSe is prepared by a simple solution method,and then the effects on the surface properties of the absorber layer,the buffer layer growth,and the modifications of the solar cell performance induced by the Na doping are studied.The surface of the absorber layer is more Cu-depletion and less roughness due to the Na doping.In addition,the contact angle of the surface increases because of Na doping.As a consequence,the thickness of the CdS buffer layer is significantly reduced and the optical losses in the CdS buffer layer are decreased.The difference of quasi-Fermi levels(EFn-EFp) increases with a small amount of Na doping in the CZTSSe solar cell,so that open circuit voltage(VOC) increased significantly.This work offers new insights into the effects of Na doping on CZTSSe via a solution-based approach and provides a deeper understanding of the origin of the efficiency improvement of Na-doped CZTSSe thin film solar cells.
基金supported by the National Natural Science Foundation of China(51771072)the Outstanding Youth Scientist Foundation of Hunan Province(2020JJ2006)+2 种基金the Youth 1000 Talent Program of ChinaFundamental Research Funds for the Central UniversitiesHunan University State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body Independent Research Project(71860007)。
文摘The nanoporous Cu_(2-x)Se with Cu(Se-5%)surface catalysts were prepared through in situ dynamic restructuring strategy during the electrochemical process,which achieves highly selective electrochemical CO_(2) reduction to methanol.In situ and quasi-operando spectroscopic results provide a deep insight into the catalytic active centres of reconstructed heterogeneous catalysts for CO_(2) electroreduction.
基金supported by the National Natural Science Foundation of China(U2002216,52172261,51627803,51972332,22075150,and U1902218)the National Key Research and Development Program of China(2019YFE0118100)。
文摘Photo-generated carrier recombination loss at the CZTSSe/Cd S front interface is a key issue to the opencircuit voltage(V_(OC)) deficit of Cu_(2)ZnSnS_(x)Se_(4-x)(CZTSSe) solar cells. Here, by the aid of an easy-handling spin-coating method, a thin PCBM([6,6]-phenyl-C61-butyric acid methyl ester) layer as an electron extraction layer has been introduced on the top of CdS buffer layer to modify CZTSSe/CdS/ZnO-ITO(In_(2)O_(3):Sn) interfacial properties. Based on Sn^(4+)/DMSO(dimethyl sulfoxide) solution system, a totalarea efficiency of 12.87% with a VOC of 529 m V has been achieved. A comprehensive investigation on the influence of PCBM layer on carrier extraction, transportation and recombination processes has been carried out. It is found that the PCBM layer can smooth over the Cd S film roughness, thus beneficial for a dense and flat window layer. Furthermore, this CZTSSe/Cd S/PCBM heterostructure can accelerate carrier separation and extraction and block holes from the front interface as well, which is mainly ascribed to the downward band bending of the absorber and a widened space charge region. Our work provides a feasible way to improve the front interfacial property and the cell performance of CZTSSe solar cells by the aid of organic interfacial materials.
基金supported by the National Natural Science Foundation of China(62074037)the Science and Technology Department of Fujian Province(2020I0006)the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZZ124)。
文摘Focusing on the low open circuit voltage(V_(OC))and fill factor(FF)in flexible Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)solar cells,indium(In)ions are introduced into the CZTSSe absorbers near Mo foils to modify the back interface and passivate deep level defects in CZTSSe bulk concurrently for improving the performance of flexible device.The results show that In doping effectively inhibits the formation of secondary phase(Cu(S,Se)_(2))and VSndefects.Further studies demonstrate that the barrier height at the back interface is decreased and the deep level defects(Cu_(Sn)defects)in CZTSSe bulk are passivated.Moreover,the carrier concentration is increased and the V_(OC) deficit(V_(OC,def))is decreased significantly due to In doping.Finally,the flexible CZTSSe solar cell with 10.01%power conversion efficiency(PCE)has been obtained.The synergistic strategy of interface modification and bulk defects passivation through In incorporation provides a new thought for the fabrication of efficient flexible kesterite-based solar cells.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51772087,11904094,51972106,and 11804089)the Strategic Priority Research Program of Chinese Academy of Sciences(Grant No.XDB30000000)Natural Science Foundation of Hunan Province,China(Grant Nos.2019JJ50034 and 2019JJ50073).
文摘Bulk group IB transition-metal chalcogenides have been widely explored due to their applications in thermoelectrics.However,a layered two-dimensional form of these materials has been rarely reported.Here,we realize semiconducting Cu_(2)Se by direct selenization of Cu(111).Scanning tunneling microcopy measurements combined with first-principles calculations allow us to determine the structural and electronic properties of the obtained structure.X-ray photoelectron spectroscopy data reveal chemical composition of the sample,which is Cu_(2)Se.The observed moire pattern indicates a lattice mismatch between Cu_(2)Se and the underlying Cu(111)-√3×√3 surface.Differential conductivity obtained by scanning tunneling spectroscopy demonstrates that the synthesized Cu_(2)Se exhibits a band gap of 0.78 eV.Furthermore,the calculated density of states and band structure demonstrate that the isolated Cu_(2)Se is a semiconductor with an indirect band gap of-0.8 eV,which agrees quite well with the experimental results.Our study provides a simple pathway varying toward the synthesis of novel layered 2D transition chalcogenides materials.
基金financially supported by the National Natural Science Foundation of China(Nos.52271011,52102291,52101251)。
文摘Three-dimentional(3D)transition metal selenides with sufficient channels could produce significant superiority on enhancing reaction kinetics for sodium-ion batteries.However,the thorough exploration of 3D architecture with a facile strategy is still challenging.Here we report that a polycrystalline Cu_(2-x)Se film was epitaxial grown on(220)facets-exposed Cu by direct selenization of a nanoporous Cu skeleton,which is obtained by dealloying rolled Cu Mn@Cu alloy foil.Density functional theory calculation result shows strong adsorption energy for Se atoms on Cu(220)planes during selenization reaction,rendering a low energy consumption.By virtue of this core-shell 3D nanoporous architecture to offer abundant active sites and endow fast electron/ion transportation,the nanoporous Cu_(2-x)Se@Cu-0.15 composite electrode exhibits remarkable sodium-ion storage properties with high reversible capacity of 950.6μAh/cm^(2)at 50μA/cm^(2),suprior rate capability of 457.6μAh/cm^(2)at 500μA/cm^(2),as well as an ultra-long stability at a high current density.Mechanism investigation reveals that the electrochemical reaction is a typical conversion-type reaction with different intermediates.This novel electrode synthetic strategy provides useful instructions to design the high-performance anode material for sodium-ion batteries.
