A flexible counter electrode(CE) for dye-sensitized solar cells(DSCs) has been fabricated using a micro-porous polyvinylidene fluoride membrane as support media and sputtered Pt as the catalytic material.Non-conventio...A flexible counter electrode(CE) for dye-sensitized solar cells(DSCs) has been fabricated using a micro-porous polyvinylidene fluoride membrane as support media and sputtered Pt as the catalytic material.Non-conventional structure DSCs have been developed by the fabricated CEs. The Pt metal was sputtered onto one surface of the membrane as the catalytic material. DSCs were assembled by attaching the Ti O2 electrode to the membrane surface without Pt coating. The membrane was with cylindrical pore geometry. It served not only as a substrate for the CE but also as a spacer for the DSC. The fabricated DSC with the flexible membrane CE showed higher photocurrent density than the conventional sandwich devices based on chemically deposited Pt/FTO glass, achieving a photovoltaic conversion efficiency of 4.43%. The results provides useful information in investigation and development of stable, low-cost, simple-design, flexible and lightweight DSCs.展开更多
Dye-sensitized solar cell （DSC） consists a combination of several different materials： photoanodes with nanoparticulated semiconductors, sensitizers, electrolytes and counter electrodes （CEs）. Each materials perf...Dye-sensitized solar cell （DSC） consists a combination of several different materials： photoanodes with nanoparticulated semiconductors, sensitizers, electrolytes and counter electrodes （CEs）. Each materials performs specific task for the conversion of solar energy into electricity. The main function of CE is to transfer electrons to the redox electrolyte and regenerate iodide ion. The work of CE is mainly focused on the studies of the kinetic performance and stability of the traditional CEs to improve the overall efficiency of DSC, seeking novel design concepts or new materials. In this review, the development and research progress of different CE materials and their electrochemical performance, and the problems are discussed.展开更多
The electroactive materials used in the counter electrode(CE)are of great concern as they influence the photovoltaic performances of dye-sensitized solar cells.The main functions of CE materials are collecting electro...The electroactive materials used in the counter electrode(CE)are of great concern as they influence the photovoltaic performances of dye-sensitized solar cells.The main functions of CE materials are collecting electrons from the external circuit and transferring them to the electrolyte and realizing the catalytic reduction of the redox species(I3^– or Co^3+)present in the electrolyte.The research hotspot of CE materials is seeking functional materials that display high efficiency,low cost,and good electrochemical stability and can substitute the benchmark platinum electrode.Chalcogen compounds of cobalt,nickel,and iron have been widely applied as CE materials and exhibit excellent electrocatalytic performances owing to their unique electrical properties,similar energies of adsorption of I atoms as platinum,excellent catalytic activities,and good chemical stabilities.In this review,we trace the developments and performances of chalcogen compounds of iron,cobalt,and nickel as CE materials and present the latest research directions for improving the electrocatalytic performances.We then highlight the optimization strategies for further improving their performances,such as fabrication of architectures,regulation of the components,synthesis of composites containing carbon materials,and elemental doping.展开更多
The effect of transition metal ions(M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)) on the chemical synthesis of polyaniline(PANI) used as a platinum-free counter electrode(CE) in dye-sensitized solar cells(DSSCs) was investi...The effect of transition metal ions(M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)) on the chemical synthesis of polyaniline(PANI) used as a platinum-free counter electrode(CE) in dye-sensitized solar cells(DSSCs) was investigated.PANI was synthesized by co-polymerization of aniline in the presence of different transition metal ions by using potassium dichromate in acidic medium. It was found that the ion doping of PANI showed a certain catalytic activity for the regeneration of traditional iodide/triiodide(I^-/I_3^-) redox couples. The power conversion efficiency(η) of PANI CEs doped with Mn^(2+),Ni^(2+),Co^(2+) (4.41%, 2.36% and 2.10%, respectively) were higher than 1.94%, the value measured for PANI CE without doping. Doping with Cu^(2+)decreased the power conversion efficiency of PANI CE(PANI-Cu^(2+) η = 1.41%). The electrical properties of the PANI, PANI-Ni^(2+), PANI-Co^(2+),PANI-Mn^(2+) and PANI-Cu^(2+) were studied by cyclic voltammetry(CV), impedance(EIS), and Tafel polarization curve. The experimental results confirmed that PANI was affected by the doping of different transition metal ions(M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)). These results indicate a potential application of ion doped PANI as counter electrode in cost-effective DSSCs.展开更多
We explore a simple and eco-friendly approach for preparing CZTS powders and a screen-printing process for Cu_2ZnSn(S,Se)_4(CZTSSe) counter electrodes(CEs) in dye-sensitized solar cells(DSCs). Cu_2ZnSnS_4(CZTS) nanopa...We explore a simple and eco-friendly approach for preparing CZTS powders and a screen-printing process for Cu_2ZnSn(S,Se)_4(CZTSSe) counter electrodes(CEs) in dye-sensitized solar cells(DSCs). Cu_2ZnSnS_4(CZTS) nanoparticles have been synthesized via a hydrazine-free solvothermal approach without the assistance of organic ligands. CZTS has been prepared by directly drop-casting the CZTS ink on the cleaned FTO glass, while CZTSSe CEs have been fabricated by screen-printing CZTS pastes, followed by post selenization using Se vapor obtained from elemental Se pellets. The crystal structure, composition and morphology of the as-deposited CZTS nanoparticles and CZTSSe electrodes are characterized by X-ray diffractometer, energy dispersive spectrometer, field emission scanning electron microscopy and transmission electron microscopy.The electrochemical properties of CZTS, CZTSSe and Pt CE based DSCs are examined and analyzed by electrochemical impedance spectroscopy. The prepared CZTS and CZTSSe CEs exhibit a cellular structure with high porosity. DSCs fabricated with CZTSSe CEs achieve a power conversion efficiency of 5.75% under AM 1.5 G illumination with an intensity of 100 m W/cm^2, which is higher than that(3.22%) of the cell using the CZTS CE. The results demonstrate that the CZTSSe CE possesses good electrocatalytic activity for the reduction of charge carriers in electrolyte. The comprehensive CZTSSe CE process is cheap and scalable. It can make large-scale electro-catalytic film fabrication cost competitive for both energy harvesting and storage applications.展开更多
Morphology-controllable Cu2SnS3 thin films on solvothermal process and used in dye-sensitized solar cells as Mo-glass were prepared via a facile in situ one-step counter electrodes. The effects of different solvents ...Morphology-controllable Cu2SnS3 thin films on solvothermal process and used in dye-sensitized solar cells as Mo-glass were prepared via a facile in situ one-step counter electrodes. The effects of different solvents on the morphology of films were investigated. DSC based on the porous net-like Cu2SnS3 thin film as counter electrodes showed a power conversion efficiency of 2.30%, which was improved to 3.35% after annealing.展开更多
MOS2/Co3S4 composite films were prepared via a facile one-step hydrothermal method, and used as efficient and low-cost Pt-free counter electrodes （CEs） for dye-sen- sitized solar cells （DSSCs）. Characterizations r...MOS2/Co3S4 composite films were prepared via a facile one-step hydrothermal method, and used as efficient and low-cost Pt-free counter electrodes （CEs） for dye-sen- sitized solar cells （DSSCs）. Characterizations revealed that Co3S4 and MoS2 were obtained simultaneously during the facile hydrothermal process. The composites afforded a promising synergistic effect on the catalyzing of triiodide reduction. Enhanced electrocatalytic performance of the resultant composite films was confirmed through cyclic voltammetry （CV） and electrochemical impedance spec- troscopy （EIS） analyses. DSSCs using MoS2/Co3S4 composite CEs outperform the devices with pristine MoS2 or Co3S4 CEs in power conversion efficiency （PCE）. Furthermore, a PCE of 6.77% is obtained for the optimized devices using MoS2/Co3S4 composite CEs measured under standard 1 sun illumination （100 mW cm-2, AM 1.5G）, which is comparable to that of the devices fabricated under the same conditions with conventional thermally deposited Pt CEs （7.14%）. The results demonstrate that MoS2/Co3S4 composites are promis- ing alternatives to Pt to be applied as CEs for DSSCs,展开更多
Pt-free counter electrode(CE) composed of La2 MoO(LaO-MoO) was successfully synthesized by simple pyrolysis of lanthanum acetate(CHOLa·xHO) and hexaammonium heptamolybdate tetrahydrate((NH4)6 MoO·4 HO). Furt...Pt-free counter electrode(CE) composed of La2 MoO(LaO-MoO) was successfully synthesized by simple pyrolysis of lanthanum acetate(CHOLa·xHO) and hexaammonium heptamolybdate tetrahydrate((NH4)6 MoO·4 HO). Furthermore,three proportions composites catalysts of La2 MoO@MWCNTs based on La2 MoOand multiwall carbon nanotubes(MWCNTs) were prepared and characterized as Ptfree catalyst for CE in dye-sensitized solar cells(DSSCs). The morphology and structure of La2 MoO@MWCNTs composites were determined by scanning electron microscopy, transmission electron microscope and X-ray diffraction. The electrochemical performance of La2 MoO@MWCNTs composite catalysts for CEs was determined by photocurrent-voltage measurements, cyclic voltammetry,electrochemical impedance spectroscopy, and Tafel polarization. The power conversion efficiencies of4.68%, 4.87% and 5.06% are obtained for La2 MoO:MWCNTs with the mass ratios of 5:1, 3:1 and 1:1 towards the reduction of I~-to I~-under the same conditions,respectively,which are superior to those of MWCNTs(3,94%) and La2 MoO(1.71%) electrodes. The experimental results reveal that the presence of MWCNTs results in an augmented active catalytic surface area and enhanced charge transfer from CE to the electrolyte.展开更多
Sulfuric acid-treated poly（3,4-ethylenedioxythiophene）：poly（styrenesulfonate）/less-defective reduced graphene oxide （ST-PEDOT：PSS/L-rGO） composite films were prepared via a solution-processing route and used a...Sulfuric acid-treated poly（3,4-ethylenedioxythiophene）：poly（styrenesulfonate）/less-defective reduced graphene oxide （ST-PEDOT：PSS/L-rGO） composite films were prepared via a solution-processing route and used as the counter electrodes of dye sensitized solar cells （DSSCs）. These platinum （Pt）- and transparent conductive oxide （TCO）-free counter electrodes exhibited strong catalytic activity and excellent flexibility, showing no obvious change in their sheet resistances after 10000 cycles of bending. The integrated quasi-solid-state DSSC device with a TiO2 nanotube/Ti mesh photoanode and a ST-PEDOT：PSS/L-rGO counter electrode exhibited an energy conversion efficiency （~/） of about 1.8%. It also displayed an excellent mechanical stability and durability after bending for 1000 cycles at a small curvature radius of 10 mm. The high flexibility, low cost and efficient catalytic activity make ST-PEDOT：PSS/L-rGO composite films promising counter electrodes for flexible DSSCs.展开更多
Developing efficient counter electrodes(CEs)and quantum dots made of earth-abundant and non-toxic elements is essential but still challenging for quantum dot-sensitized solar cells(QDSSCs).Here,we report a facile stra...Developing efficient counter electrodes(CEs)and quantum dots made of earth-abundant and non-toxic elements is essential but still challenging for quantum dot-sensitized solar cells(QDSSCs).Here,we report a facile strategy to prepare self-supported and robust CoS_2and NiS nanocrystals-assembled nanosheets directly grown on carbon paper(MS_xNS@CP)as efficient counter electrodes for QDSSCs.Such CEs integrate the merits of fast electron transfer from interconnected conductive scaffold,efficient mass transfer from hierarchically vertical nanosheet on 3D open substrate,as well as abundant highly active catalytic sites from metal sulphide nanocrystal units.As a result,QDDSCs based on such CoS_2NS@CP and NiS NS@CP CEs achieve a PCE of8.88%and 7.53%,respectively.The detailed analyses suggest that CoS_2NS@CP has the highest catalytic activity and shows the lowest charger transfer resistance,leading to the highest PCE.These findings may inspire the design and exploration of other self-supported efficient CEs by integrating highly active catalysts onto 3D conductive networks for efficient QDSSCs.展开更多
Carbon nitride(CN_x) films supported on fluorine-doped tin oxide(FTO) glass are prepared by radio frequency magnetron sputtering, in which the film thicknesses are 90-100 nm, and the element components in the CNX film...Carbon nitride(CN_x) films supported on fluorine-doped tin oxide(FTO) glass are prepared by radio frequency magnetron sputtering, in which the film thicknesses are 90-100 nm, and the element components in the CNX films are in the range of x = 0.15-0.25. The as-prepared CN_x is for the first time used as counter electrode for dye-sensitized solar cells(DSSCs), and show a preparation-temperature dependent electrochemical performance. X-ray photoelectron spectroscopy(XPS) demonstrates that there is a higher proportion of sp^2 C=C and sp^3 C-N hybridized bonds in CN_x-500(the sample treated at 500 ℃) than in CNX-RT(the sample without a heat treatment). It is proposed that the sp^2 C=C and sp^3 C-N hybridized bonds in the CN_x films are helpful for improving the electrocatalytic activities in DSSCs. Meanwhile, Raman spectra also prove that CN_x-500 has a relatively high graphitization level that means an increasing electrical conductivity. This further explains why the sample after the heat treatment has a higher electrochemical performance in DSSCs. In addition, the as-prepared CN_x counter electrodes have a good light transmittance in the visible light region. The results are meaningful for developing low-cost metal-free transparent counter electrodes for DSSCs.展开更多
Unique ZnS nanobuns decorated with reduced graphene oxide （ROO） was synthesized and found to exhibit a synergetic effect as a highly efficient and low-cost counter electrode （CE） in dye-sensitized solar cells （D...Unique ZnS nanobuns decorated with reduced graphene oxide （ROO） was synthesized and found to exhibit a synergetic effect as a highly efficient and low-cost counter electrode （CE） in dye-sensitized solar cells （DSCs）. Using this ZnS-ROO CE, a power conversion efficiency （PCE） of 7.03% was achieved. This value was 53% and 41 % higher than those of pure ZnS and ROO CEs, respectively. The ZnS-ROO nanocomposite is indeed an efficient and cost-effective Pt-like alternative for iodine reduction reaction.展开更多
We applied the reduced graphene oxide/multi-walled carbon nanotubes/nickel oxide(RGO/MWCNTs/Ni O)nanocomposite as the counter electrode(CE) in dye-sensitized solar cells(DSSCs) on fluorine-doped tin oxide substrates b...We applied the reduced graphene oxide/multi-walled carbon nanotubes/nickel oxide(RGO/MWCNTs/Ni O)nanocomposite as the counter electrode(CE) in dye-sensitized solar cells(DSSCs) on fluorine-doped tin oxide substrates by blade doctor method. Power conversion efficiency(PCE) of 8.13 % was achieved for this DSSCs device, which is higher than that of DSSCs devices using Ni O, RGO, and RGO/Ni O-CE(PCE = 2.71 %, PCE = 6.77 % and PCE = 7.63 %). Also, the fill factor of the DSSCs devices using the RGO/MWCNTs/Ni O-CE was better than that of other CEs. The electron transfer measurement of cyclic voltammetry and electrochemical impedance spectroscopy showed that RGO/MWCNTs/Ni O film could provide fast electron transfer between the CE and the electrolyte, and high electrocatalytic activity for the reduction of triiodide in a CE based on RGO/MWCNTs/Ni O in a DSSC.展开更多
A novel low temperature method was used to prepare the mesoporous carbon（MC） counter electrode（CE） on indium-doped tin oxide coated polyethylene naphthalate（ITO-PEN） for flexible dye-sensitized solar cells（DSSC...A novel low temperature method was used to prepare the mesoporous carbon（MC） counter electrode（CE） on indium-doped tin oxide coated polyethylene naphthalate（ITO-PEN） for flexible dye-sensitized solar cells（DSSCs）.The obtained flexible MC CEs with carbon loading of 280μg cm^（-2） were characterized by SEM,XRD and electrochemical impedance.The light-to-electricity conversion efficiency of the DSSC fabricated with the prepared flexible MC CE was 86%of that of DSSC based on the decomposited Pt CE.展开更多
Commercial application of the dye-sensitized solar cells（DSCs） depends on great improvement of the power conversion efficiency and reduction of the fabrication cost. Generally, developing low cost counter electrode ...Commercial application of the dye-sensitized solar cells（DSCs） depends on great improvement of the power conversion efficiency and reduction of the fabrication cost. Generally, developing low cost counter electrode catalysts to replace the expensive Pt counter electrode is a feasible path to reduce the production cost of DSCs. In this review article, we summarize the recent progress on the transition metal compound based counter electrode catalysts containing carbides, nitrides, oxides, sulfides, phosphide, selenides, borides, silicide, and telluride toward the regeneration of the traditional iodide redox couple.Moreover, the benefits and drawbacks of each kind of CE catalyst are discussed and the research directions to design new counter electrode catalysts in future research are also proposed.展开更多
Molybdenum selenide is a potential alternative to counter electrode of a platinum-free dye-sensitized solar cell(DSSC). In this work, an in situ magnetron sputtering method is developed to prepare MoSe2 electrodes. Th...Molybdenum selenide is a potential alternative to counter electrode of a platinum-free dye-sensitized solar cell(DSSC). In this work, an in situ magnetron sputtering method is developed to prepare MoSe2 electrodes. The MoSe2 electrodes obtained at various temperatures from 300 and 550 ℃ are used as counter electrode for a dye-sensitized solar cell. Photovoltaic measurement results indicate that the MoSe2 electrodes prepared at 400 ℃ has the optimized performance, and the corresponding DSSCs provide an energy conversion efficiency of 6.83% which is comparable than that of the reference DSSC with platinum as counter electrode(6.51%). With further increasing the preparation temperature of the MoSe2 electrodes, the corresponding DSSCs decrease gradually to 5.96% for 550 ℃. Electrochemical impedance spectra(EIS) reveal that charge transfer resistance(Rct) of MoSe2 electrodes is rising with increase of the temperature from 400 to 500 ℃, suggesting a downward electrocatalytic activity. Though the MoSe2 electrode prepared at 550 ℃ show a reduced Rct, its series resistance(Rs) and diffusion resistance(Zw) increase obviously. Considering that MoSe2 phase cannot be formed at 300 ℃, it can be concluded that the prepared temperature as low as possible is favored for its final electrochemical performance. The results are very significant for developing low-cost and responsible counter electrodes for dye-sensitized solar cells.展开更多
For some specific catalytic reaction, how to construct active sites on two dimensional materials is of great scientific significance. Dye-sensitized solar cells（DSCs） can be viewed as one representative photovoltaic...For some specific catalytic reaction, how to construct active sites on two dimensional materials is of great scientific significance. Dye-sensitized solar cells（DSCs） can be viewed as one representative photovoltaics because in which liquid electrolyte with triiodide/iodide（I;/I;） as redox couples are involved. In this study, amino-functionalized graphene（AFG） has been designed according to theoretically analyzing iodine reduction reaction（IRR） processes and rationally screening the volcanic plot. Then, such AFG has been successfully synthesized by a simple hydrothermal method and shows high electrocatalytic activity towards IRR when serving as counter electrode in DSCs. Finally, a high conversion efficiency of 7.39% by AFG-based DSCs was obtained, which is close to that using Pt as counter electrode.展开更多
A dye-sensitized nanocrystalline TiO 2 solar cell(DYSC) was assembled, of which counter electrode was modified already by platinum, nickel and carbon. It was found that the DYSC had better photoelectric performanc...A dye-sensitized nanocrystalline TiO 2 solar cell(DYSC) was assembled, of which counter electrode was modified already by platinum, nickel and carbon. It was found that the DYSC had better photoelectric performance when the electrode was modified by platinum than by nickel and carbon. The influence of the incidence light wavelength on the incidence monochromatic photoelectric conversion efficiency(IPCE) was investigated. The result shows that the IPCE mainly depends on the short-circuit current density(I SC) of a DYSC, and the IPCE reaches 48.32% under the irradiation with the wavelength of 560 nm when the counter electrode of a DYSC was modified by platinum. The influence of incident light intensity on the photoelectric properties of a DYSC was also investigated. It was found that the I SC and open-circuit voltage(V OC) increased and the fill factor(f f) of the DYSC decreased with the increase of the incident light intensity.展开更多
In order to search for the high efficiency and low sheet resistance counter electrode in dye-sensitized solar cell, we used Ti plate as the conducting substrate to prepare the counter electrode by thermal decompositio...In order to search for the high efficiency and low sheet resistance counter electrode in dye-sensitized solar cell, we used Ti plate as the conducting substrate to prepare the counter electrode by thermal decomposition of H2PtCl6. Ti plate counter electrode shows low sheet resistance, good reflecting performance and matching kinetics. The dye-sensitized solar cell with the Ti plate counter electrode shows better photovoltaic performance than that of the cell with the fluorine-doped tin oxide-coated glass counter electrode.展开更多
Ensuring high power conversion efficiency,partially or completely replacing Pt electrodes with inexpensive materials is one of the important development directions of dye-sensitized solar cells(DSSCs).In this work,we ...Ensuring high power conversion efficiency,partially or completely replacing Pt electrodes with inexpensive materials is one of the important development directions of dye-sensitized solar cells(DSSCs).In this work,we have developed a threecomponent(MWCNTs,carbon black and graphite) carbon(tri-carbon) electrode material for DSSC devices combined with the advantages of high electron transfer kinetics of MWCNTs,plentiful catalytic sites in crystal edges of carbon black and superior electrical conductivity and catalytic activity of graphite.Using a tri-carbon electrode,a Pt electrode,and two N719-sensitized photoanodes,a parallel tandem dye-sensitized solar cells are assembled obtaining a high PCE of 10.26%(V_(OC)=0.70 V,J_(SC)=19.99 mA/cm~2,FF=73.33%).It opens up a new avenue for the development of low-cost and highperformance DSSCs.展开更多
基金supported by National Natural Science Foundation of China(No.10774046)Shanghai Municipal Science&Technology Committee(No.09JC1404600+1 种基金No.0852nm06100 and No.08230705400)Singapore Ministry of Education innovation fund(MOE IF Funding MOE2008-IF-1-016)
文摘A flexible counter electrode(CE) for dye-sensitized solar cells(DSCs) has been fabricated using a micro-porous polyvinylidene fluoride membrane as support media and sputtered Pt as the catalytic material.Non-conventional structure DSCs have been developed by the fabricated CEs. The Pt metal was sputtered onto one surface of the membrane as the catalytic material. DSCs were assembled by attaching the Ti O2 electrode to the membrane surface without Pt coating. The membrane was with cylindrical pore geometry. It served not only as a substrate for the CE but also as a spacer for the DSC. The fabricated DSC with the flexible membrane CE showed higher photocurrent density than the conventional sandwich devices based on chemically deposited Pt/FTO glass, achieving a photovoltaic conversion efficiency of 4.43%. The results provides useful information in investigation and development of stable, low-cost, simple-design, flexible and lightweight DSCs.
基金the support of the National Natural Science Foundation of China under grant No. 20673141 the National Basic Research Program of China （973 Program） under grant No. 2006CB202606 the National High Technology Research and Development Program （863 Program） under grant No. 2006AA03Z341 and the 100-Talents Project of Chinese Academy of Sciences.
文摘Dye-sensitized solar cell （DSC） consists a combination of several different materials： photoanodes with nanoparticulated semiconductors, sensitizers, electrolytes and counter electrodes （CEs）. Each materials performs specific task for the conversion of solar energy into electricity. The main function of CE is to transfer electrons to the redox electrolyte and regenerate iodide ion. The work of CE is mainly focused on the studies of the kinetic performance and stability of the traditional CEs to improve the overall efficiency of DSC, seeking novel design concepts or new materials. In this review, the development and research progress of different CE materials and their electrochemical performance, and the problems are discussed.
基金supported by the National Science Fund for Distinguished Young Scholars(21425729)from the National Natural Science Foundation of Chinathe National Special S&T Project on Water Pollution Control and Treatment(2017ZX07107002)+1 种基金China Postdoctoral Science Foundation(2018M640209)the Tianjin Science and Technology Support Key Projects(18YFZCSF00500)~~
文摘The electroactive materials used in the counter electrode(CE)are of great concern as they influence the photovoltaic performances of dye-sensitized solar cells.The main functions of CE materials are collecting electrons from the external circuit and transferring them to the electrolyte and realizing the catalytic reduction of the redox species(I3^– or Co^3+)present in the electrolyte.The research hotspot of CE materials is seeking functional materials that display high efficiency,low cost,and good electrochemical stability and can substitute the benchmark platinum electrode.Chalcogen compounds of cobalt,nickel,and iron have been widely applied as CE materials and exhibit excellent electrocatalytic performances owing to their unique electrical properties,similar energies of adsorption of I atoms as platinum,excellent catalytic activities,and good chemical stabilities.In this review,we trace the developments and performances of chalcogen compounds of iron,cobalt,and nickel as CE materials and present the latest research directions for improving the electrocatalytic performances.We then highlight the optimization strategies for further improving their performances,such as fabrication of architectures,regulation of the components,synthesis of composites containing carbon materials,and elemental doping.
基金Supported by the National Natural Science Foundation of China(21473048,21303039)the Natural Science Foundation of Hebei Province(B2016205161,B2015205163)the 2015 Hebei Province Undergraduate Training Programs for Innovation and Entrepreneurship
文摘The effect of transition metal ions(M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)) on the chemical synthesis of polyaniline(PANI) used as a platinum-free counter electrode(CE) in dye-sensitized solar cells(DSSCs) was investigated.PANI was synthesized by co-polymerization of aniline in the presence of different transition metal ions by using potassium dichromate in acidic medium. It was found that the ion doping of PANI showed a certain catalytic activity for the regeneration of traditional iodide/triiodide(I^-/I_3^-) redox couples. The power conversion efficiency(η) of PANI CEs doped with Mn^(2+),Ni^(2+),Co^(2+) (4.41%, 2.36% and 2.10%, respectively) were higher than 1.94%, the value measured for PANI CE without doping. Doping with Cu^(2+)decreased the power conversion efficiency of PANI CE(PANI-Cu^(2+) η = 1.41%). The electrical properties of the PANI, PANI-Ni^(2+), PANI-Co^(2+),PANI-Mn^(2+) and PANI-Cu^(2+) were studied by cyclic voltammetry(CV), impedance(EIS), and Tafel polarization curve. The experimental results confirmed that PANI was affected by the doping of different transition metal ions(M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)). These results indicate a potential application of ion doped PANI as counter electrode in cost-effective DSSCs.
基金supported by National Natural Science Foundation of China (No. 11274119 and 61275038)Pujiang Talent Program of Shanghai Science and Technology Commission (No. 11PJ1402700)
文摘We explore a simple and eco-friendly approach for preparing CZTS powders and a screen-printing process for Cu_2ZnSn(S,Se)_4(CZTSSe) counter electrodes(CEs) in dye-sensitized solar cells(DSCs). Cu_2ZnSnS_4(CZTS) nanoparticles have been synthesized via a hydrazine-free solvothermal approach without the assistance of organic ligands. CZTS has been prepared by directly drop-casting the CZTS ink on the cleaned FTO glass, while CZTSSe CEs have been fabricated by screen-printing CZTS pastes, followed by post selenization using Se vapor obtained from elemental Se pellets. The crystal structure, composition and morphology of the as-deposited CZTS nanoparticles and CZTSSe electrodes are characterized by X-ray diffractometer, energy dispersive spectrometer, field emission scanning electron microscopy and transmission electron microscopy.The electrochemical properties of CZTS, CZTSSe and Pt CE based DSCs are examined and analyzed by electrochemical impedance spectroscopy. The prepared CZTS and CZTSSe CEs exhibit a cellular structure with high porosity. DSCs fabricated with CZTSSe CEs achieve a power conversion efficiency of 5.75% under AM 1.5 G illumination with an intensity of 100 m W/cm^2, which is higher than that(3.22%) of the cell using the CZTS CE. The results demonstrate that the CZTSSe CE possesses good electrocatalytic activity for the reduction of charge carriers in electrolyte. The comprehensive CZTSSe CE process is cheap and scalable. It can make large-scale electro-catalytic film fabrication cost competitive for both energy harvesting and storage applications.
基金financially supported by the National Natural Science Foundation of China (No. 21203226)
文摘Morphology-controllable Cu2SnS3 thin films on solvothermal process and used in dye-sensitized solar cells as Mo-glass were prepared via a facile in situ one-step counter electrodes. The effects of different solvents on the morphology of films were investigated. DSC based on the porous net-like Cu2SnS3 thin film as counter electrodes showed a power conversion efficiency of 2.30%, which was improved to 3.35% after annealing.
基金supported by the National Natural Science Foundation of China(11574060,51272049 and 21103032)the support from Shaanxi Provincial Natural Science Foundation(2016JM2008)the Key Laboratory of Applied Surface and Colloid Chemistry,MOE(Shaanxi Normal University)
文摘MOS2/Co3S4 composite films were prepared via a facile one-step hydrothermal method, and used as efficient and low-cost Pt-free counter electrodes （CEs） for dye-sen- sitized solar cells （DSSCs）. Characterizations revealed that Co3S4 and MoS2 were obtained simultaneously during the facile hydrothermal process. The composites afforded a promising synergistic effect on the catalyzing of triiodide reduction. Enhanced electrocatalytic performance of the resultant composite films was confirmed through cyclic voltammetry （CV） and electrochemical impedance spec- troscopy （EIS） analyses. DSSCs using MoS2/Co3S4 composite CEs outperform the devices with pristine MoS2 or Co3S4 CEs in power conversion efficiency （PCE）. Furthermore, a PCE of 6.77% is obtained for the optimized devices using MoS2/Co3S4 composite CEs measured under standard 1 sun illumination （100 mW cm-2, AM 1.5G）, which is comparable to that of the devices fabricated under the same conditions with conventional thermally deposited Pt CEs （7.14%）. The results demonstrate that MoS2/Co3S4 composites are promis- ing alternatives to Pt to be applied as CEs for DSSCs,
基金Project supported by the National Natural Science Foundation of China(21473048 and 21303039)the Natural Science Foundation of Hebei Province(B2015205163,B2016205161)the 2015 Hebei Province Undergraduate Training Programs for Innovation and Entrepreneurship
文摘Pt-free counter electrode(CE) composed of La2 MoO(LaO-MoO) was successfully synthesized by simple pyrolysis of lanthanum acetate(CHOLa·xHO) and hexaammonium heptamolybdate tetrahydrate((NH4)6 MoO·4 HO). Furthermore,three proportions composites catalysts of La2 MoO@MWCNTs based on La2 MoOand multiwall carbon nanotubes(MWCNTs) were prepared and characterized as Ptfree catalyst for CE in dye-sensitized solar cells(DSSCs). The morphology and structure of La2 MoO@MWCNTs composites were determined by scanning electron microscopy, transmission electron microscope and X-ray diffraction. The electrochemical performance of La2 MoO@MWCNTs composite catalysts for CEs was determined by photocurrent-voltage measurements, cyclic voltammetry,electrochemical impedance spectroscopy, and Tafel polarization. The power conversion efficiencies of4.68%, 4.87% and 5.06% are obtained for La2 MoO:MWCNTs with the mass ratios of 5:1, 3:1 and 1:1 towards the reduction of I~-to I~-under the same conditions,respectively,which are superior to those of MWCNTs(3,94%) and La2 MoO(1.71%) electrodes. The experimental results reveal that the presence of MWCNTs results in an augmented active catalytic surface area and enhanced charge transfer from CE to the electrolyte.
基金Acknowledgement This work was supported by the National Basic Research Program of China （973 Program, No. 2012CB933402） and the Natural Science Foundation of China （Nos. 51433005, 21274074）.
文摘Sulfuric acid-treated poly（3,4-ethylenedioxythiophene）：poly（styrenesulfonate）/less-defective reduced graphene oxide （ST-PEDOT：PSS/L-rGO） composite films were prepared via a solution-processing route and used as the counter electrodes of dye sensitized solar cells （DSSCs）. These platinum （Pt）- and transparent conductive oxide （TCO）-free counter electrodes exhibited strong catalytic activity and excellent flexibility, showing no obvious change in their sheet resistances after 10000 cycles of bending. The integrated quasi-solid-state DSSC device with a TiO2 nanotube/Ti mesh photoanode and a ST-PEDOT：PSS/L-rGO counter electrode exhibited an energy conversion efficiency （~/） of about 1.8%. It also displayed an excellent mechanical stability and durability after bending for 1000 cycles at a small curvature radius of 10 mm. The high flexibility, low cost and efficient catalytic activity make ST-PEDOT：PSS/L-rGO composite films promising counter electrodes for flexible DSSCs.
基金supported by the National Natural Science Foundation of China (21573249, 51732004)the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB12020100)
文摘Developing efficient counter electrodes(CEs)and quantum dots made of earth-abundant and non-toxic elements is essential but still challenging for quantum dot-sensitized solar cells(QDSSCs).Here,we report a facile strategy to prepare self-supported and robust CoS_2and NiS nanocrystals-assembled nanosheets directly grown on carbon paper(MS_xNS@CP)as efficient counter electrodes for QDSSCs.Such CEs integrate the merits of fast electron transfer from interconnected conductive scaffold,efficient mass transfer from hierarchically vertical nanosheet on 3D open substrate,as well as abundant highly active catalytic sites from metal sulphide nanocrystal units.As a result,QDDSCs based on such CoS_2NS@CP and NiS NS@CP CEs achieve a PCE of8.88%and 7.53%,respectively.The detailed analyses suggest that CoS_2NS@CP has the highest catalytic activity and shows the lowest charger transfer resistance,leading to the highest PCE.These findings may inspire the design and exploration of other self-supported efficient CEs by integrating highly active catalysts onto 3D conductive networks for efficient QDSSCs.
基金Financial support from the 973 Program (2015CB251100)NSFC (51001063)MOE Innovation Team (IRT13022)
文摘Carbon nitride(CN_x) films supported on fluorine-doped tin oxide(FTO) glass are prepared by radio frequency magnetron sputtering, in which the film thicknesses are 90-100 nm, and the element components in the CNX films are in the range of x = 0.15-0.25. The as-prepared CN_x is for the first time used as counter electrode for dye-sensitized solar cells(DSSCs), and show a preparation-temperature dependent electrochemical performance. X-ray photoelectron spectroscopy(XPS) demonstrates that there is a higher proportion of sp^2 C=C and sp^3 C-N hybridized bonds in CN_x-500(the sample treated at 500 ℃) than in CNX-RT(the sample without a heat treatment). It is proposed that the sp^2 C=C and sp^3 C-N hybridized bonds in the CN_x films are helpful for improving the electrocatalytic activities in DSSCs. Meanwhile, Raman spectra also prove that CN_x-500 has a relatively high graphitization level that means an increasing electrical conductivity. This further explains why the sample after the heat treatment has a higher electrochemical performance in DSSCs. In addition, the as-prepared CN_x counter electrodes have a good light transmittance in the visible light region. The results are meaningful for developing low-cost metal-free transparent counter electrodes for DSSCs.
基金supported by the National Natural Science Foundation of China(Grant No.51172102,51302125 and 51303076)
文摘Unique ZnS nanobuns decorated with reduced graphene oxide （ROO） was synthesized and found to exhibit a synergetic effect as a highly efficient and low-cost counter electrode （CE） in dye-sensitized solar cells （DSCs）. Using this ZnS-ROO CE, a power conversion efficiency （PCE） of 7.03% was achieved. This value was 53% and 41 % higher than those of pure ZnS and ROO CEs, respectively. The ZnS-ROO nanocomposite is indeed an efficient and cost-effective Pt-like alternative for iodine reduction reaction.
基金supported by the National Basic Research Program(2011CB933300)of Chinathe National Natural Science Foundation of China(11374110,11204093,51371085,and 11304106)
文摘We applied the reduced graphene oxide/multi-walled carbon nanotubes/nickel oxide(RGO/MWCNTs/Ni O)nanocomposite as the counter electrode(CE) in dye-sensitized solar cells(DSSCs) on fluorine-doped tin oxide substrates by blade doctor method. Power conversion efficiency(PCE) of 8.13 % was achieved for this DSSCs device, which is higher than that of DSSCs devices using Ni O, RGO, and RGO/Ni O-CE(PCE = 2.71 %, PCE = 6.77 % and PCE = 7.63 %). Also, the fill factor of the DSSCs devices using the RGO/MWCNTs/Ni O-CE was better than that of other CEs. The electron transfer measurement of cyclic voltammetry and electrochemical impedance spectroscopy showed that RGO/MWCNTs/Ni O film could provide fast electron transfer between the CE and the electrolyte, and high electrocatalytic activity for the reduction of triiodide in a CE based on RGO/MWCNTs/Ni O in a DSSC.
基金supported by the National Nature Science Foundation of China(No.20975012)the 111 Project (B07012)+1 种基金the Major State Basic Research Development Program(No.2006CB202605)the High-Tech Research and Development Program of China(No.2007AA05Z439)
文摘A novel low temperature method was used to prepare the mesoporous carbon（MC） counter electrode（CE） on indium-doped tin oxide coated polyethylene naphthalate（ITO-PEN） for flexible dye-sensitized solar cells（DSSCs）.The obtained flexible MC CEs with carbon loading of 280μg cm^（-2） were characterized by SEM,XRD and electrochemical impedance.The light-to-electricity conversion efficiency of the DSSC fabricated with the prepared flexible MC CE was 86%of that of DSSC based on the decomposited Pt CE.
基金supported by National Natural Science Foundation of China(21303039)Natural Science Foundation of Hebei Province(B2015205163,B2013205171)+1 种基金Support Program for Hundred Excellent Innovation Talents from the Universities of Hebei Province,(BR2-220)supported by Science Foundation of Hebei Normal University(L2016J02)
文摘Commercial application of the dye-sensitized solar cells（DSCs） depends on great improvement of the power conversion efficiency and reduction of the fabrication cost. Generally, developing low cost counter electrode catalysts to replace the expensive Pt counter electrode is a feasible path to reduce the production cost of DSCs. In this review article, we summarize the recent progress on the transition metal compound based counter electrode catalysts containing carbides, nitrides, oxides, sulfides, phosphide, selenides, borides, silicide, and telluride toward the regeneration of the traditional iodide redox couple.Moreover, the benefits and drawbacks of each kind of CE catalyst are discussed and the research directions to design new counter electrode catalysts in future research are also proposed.
基金supported by the National Basic Research Program(973 Program,2015CB251100)Natural Science Foundation of Tianjin(18JCZDJC31000)~~
文摘Molybdenum selenide is a potential alternative to counter electrode of a platinum-free dye-sensitized solar cell(DSSC). In this work, an in situ magnetron sputtering method is developed to prepare MoSe2 electrodes. The MoSe2 electrodes obtained at various temperatures from 300 and 550 ℃ are used as counter electrode for a dye-sensitized solar cell. Photovoltaic measurement results indicate that the MoSe2 electrodes prepared at 400 ℃ has the optimized performance, and the corresponding DSSCs provide an energy conversion efficiency of 6.83% which is comparable than that of the reference DSSC with platinum as counter electrode(6.51%). With further increasing the preparation temperature of the MoSe2 electrodes, the corresponding DSSCs decrease gradually to 5.96% for 550 ℃. Electrochemical impedance spectra(EIS) reveal that charge transfer resistance(Rct) of MoSe2 electrodes is rising with increase of the temperature from 400 to 500 ℃, suggesting a downward electrocatalytic activity. Though the MoSe2 electrode prepared at 550 ℃ show a reduced Rct, its series resistance(Rs) and diffusion resistance(Zw) increase obviously. Considering that MoSe2 phase cannot be formed at 300 ℃, it can be concluded that the prepared temperature as low as possible is favored for its final electrochemical performance. The results are very significant for developing low-cost and responsible counter electrodes for dye-sensitized solar cells.
基金Financial support provided by the National Natural Science Foundation of China (Grant No. 51402036, 21373042)International Science & Technology Cooperation Program of China (Grant No. 2013DFA51000)+1 种基金the Fundamental Research Funds for the Central Universities (Grant No. DUT15YQ109)supported by the State Key Laboratory of Fine Chemicals of China
文摘For some specific catalytic reaction, how to construct active sites on two dimensional materials is of great scientific significance. Dye-sensitized solar cells（DSCs） can be viewed as one representative photovoltaics because in which liquid electrolyte with triiodide/iodide（I;/I;） as redox couples are involved. In this study, amino-functionalized graphene（AFG） has been designed according to theoretically analyzing iodine reduction reaction（IRR） processes and rationally screening the volcanic plot. Then, such AFG has been successfully synthesized by a simple hydrothermal method and shows high electrocatalytic activity towards IRR when serving as counter electrode in DSCs. Finally, a high conversion efficiency of 7.39% by AFG-based DSCs was obtained, which is close to that using Pt as counter electrode.
基金Supported by the National Natural Science Foundation of China(No. 5 0 0 82 0 0 3,5 0 372 0 2 2 ) and the Natural ScienceFoundation of Fujian Province,China(No. 2 0 0 1I0 0 6,E0 2 10 0 2 3)
文摘A dye-sensitized nanocrystalline TiO 2 solar cell(DYSC) was assembled, of which counter electrode was modified already by platinum, nickel and carbon. It was found that the DYSC had better photoelectric performance when the electrode was modified by platinum than by nickel and carbon. The influence of the incidence light wavelength on the incidence monochromatic photoelectric conversion efficiency(IPCE) was investigated. The result shows that the IPCE mainly depends on the short-circuit current density(I SC) of a DYSC, and the IPCE reaches 48.32% under the irradiation with the wavelength of 560 nm when the counter electrode of a DYSC was modified by platinum. The influence of incident light intensity on the photoelectric properties of a DYSC was also investigated. It was found that the I SC and open-circuit voltage(V OC) increased and the fill factor(f f) of the DYSC decreased with the increase of the incident light intensity.
文摘In order to search for the high efficiency and low sheet resistance counter electrode in dye-sensitized solar cell, we used Ti plate as the conducting substrate to prepare the counter electrode by thermal decomposition of H2PtCl6. Ti plate counter electrode shows low sheet resistance, good reflecting performance and matching kinetics. The dye-sensitized solar cell with the Ti plate counter electrode shows better photovoltaic performance than that of the cell with the fluorine-doped tin oxide-coated glass counter electrode.
基金supported financially by the National Natural Science Foundation of China(Nos.21788102,22075083)the Open Foundation of the Key Laboratory of Functional Inorganic Material Chemistry+1 种基金the Ministry of Education National Key R&D Program of China(No.2017YFB0309603)the Programme of Introducing Talents of Discipline to Universities(No.B16017)。
文摘Ensuring high power conversion efficiency,partially or completely replacing Pt electrodes with inexpensive materials is one of the important development directions of dye-sensitized solar cells(DSSCs).In this work,we have developed a threecomponent(MWCNTs,carbon black and graphite) carbon(tri-carbon) electrode material for DSSC devices combined with the advantages of high electron transfer kinetics of MWCNTs,plentiful catalytic sites in crystal edges of carbon black and superior electrical conductivity and catalytic activity of graphite.Using a tri-carbon electrode,a Pt electrode,and two N719-sensitized photoanodes,a parallel tandem dye-sensitized solar cells are assembled obtaining a high PCE of 10.26%(V_(OC)=0.70 V,J_(SC)=19.99 mA/cm~2,FF=73.33%).It opens up a new avenue for the development of low-cost and highperformance DSSCs.
