Metal chalcogenide complex-mediated fabrication of Cu2S film as counter electrode in quantum dot sensitized solar cells

Cu2S film onto FTO glass substrate was obtained to function as counter electrode for polysulfide redox reactions in CdS/CdSe co-sensitized solar cells by sintering after spraying a metal chalcogenide complex, N4H9Cu7S4 solution. Relative to Pt counter electrode, the Cu2S counter electrode provides greater electrocatalytic activity and lower charge transfer resistance. The prepared Cu2S counter electrode represented nanoflower-like porous film which was composed of Cu2S nanosheets on FTO and had a higher surface area and lower sheet resistance than that of sulfided brass Cu2S counter electrode. An energy conversion efficiency of 3.62% was achieved using the metal chalcogenide complex-mediated fabricated Cu2S counter electrode for CdS/CdSe co-sensitized solar cells under 1 sun, AM 1.5 illumination.     

Platinum–tin complexes as catalysts for the anodic oxidation of borohydride

Platinum–tin complexes were prepared by the reduction of Pt(IV) with Sn(II) in HCl media and studied by light absorption spectrometry, X-ray photoelectron spectroscopy (XPS), and electron microscopy. The formation of three complexes, H₃[Pt(SnCl₃)₅], H₂[Pt(SnCl₃)₂Cl₂], and H₂[Pt₃(SnCl₃)₈], depending on HCl and SnCl₂ concentrations, has been shown. The glassy carbon (GC) electrode modified in the complexes solutions was found to be an electrocatalyst for borohydride oxidation in a 1.0-M NaOH solution. Comparison of BH₄ ⁻ electrooxidation on Pt and on GC modified with platinum–tin complexes has shown that catalytic hydrolysis of BH₄ ⁻ did not proceed in the latter case in contrast to its oxidation on the Pt electrode, and only direct BH₄ ⁻ oxidation has been observed in the positive potentials scan. The activity of Pt–Sn complexes for BH₄ ⁻ oxidation changes with time and eventually decreases due to Sn(II), bound in the complex with Pt(II), oxidation by atmospheric oxygen. The complexes may be renewed by addition of missing amounts of SnCl₂ and HCl.     

Enhanced Electrocatalytic Performance of a Porous g‐C3N4/Graphene Composite as a Counter Electrode for Dye‐Sensitized Solar Cells

A porous graphitic carbon nitride (g‐C₃N₄)/graphene composite was prepared by a simple hydrothermal method and explored as the counter electrode of dye‐sensitized solar cells (DSCs). The obtained g‐C₃N₄/graphene composite was characterized by XRD, SEM, TEM, FTIR spectroscopy, and X‐ray photoelectron spectroscopy. The results show that incorporating graphene nanosheets into g‐C₃N₄ forms a three‐dimensional architecture with a high surface area, porous structure, efficient electron‐transport network, and fast charge‐transfer kinetics at the g‐C₃N₄/graphene interfaces. These properties result in more electrocatalytic active sites and facilitate electrolyte diffusion and electron transport in the porous framework. As a result, the as‐prepared porous g‐C₃N₄/graphene composite exhibits an excellent electrocatalytic activity. In I^?/I₃^? redox electrolyte, the charge‐transfer resistance of the porous g‐C₃N₄/graphene composite electrode is 1.8 Ω cm², which is much lower than those of individual g‐C₃N₄ (70.1 Ω cm²) and graphene (32.4 Ω cm²) electrodes. This enhanced electrocatalytic performance is beneficial for improving the photovoltaic performance of DSCs. By employing the porous g‐C₃N₄/graphene composite as the counter electrode, the DSC achieves a conversion efficiency of 7.13 %. This efficiency is comparable to 7.37 % for a cell with a platinum counter electrode.     

Self-Assembled Graphene/MWCNT Bilayers as Platinum-Free Counter Electrode in Dye-Sensitized Solar Cells

We describe the preparation and properties of bilayers of graphene- and multi-walled carbon nanotubes (MWCNTs) as an alternative to conventionally used platinum-based counter electrode for dye-sensitized solar cells (DSSC). The counter electrodes were prepared by a simple and easy-to-implement double self-assembly process. The preparation allows for controlling the surface roughness of electrode in a layer-by-layer deposition. Annealing under N₂ atmosphere improves the electrode's conductivity and the catalytic activity of graphene and MWCNTs to reduce the I₃⁻ species within the electrolyte of the DSSC. The performance of different counter-electrodes is compared for ZnO photoanode-based DSSCs. Bilayer electrodes show higher power conversion efficiencies than monolayer graphene electrodes or monolayer MWCNTs electrodes. The bilayer graphene (bottom)/MWCNTs (top) counter electrode-based DSSC exhibits a maximum power conversion efficiency of 4.1 % exceeding the efficiency of a reference DSSC with a thin film platinum counter electrode (efficiency of 3.4 %). In addition, the double self-assembled counter electrodes are mechanically stable, which enables their recycling for DSSCs fabrication without significant loss of the solar cell performance.     

TCO-free dye solar cells based on Ti back contact electrode by facile printing method

The back contact dye solar cells (BCDSCs), in which the TCO(Transparent Conductive oxide) is omitted, have a potential for use of intact low-cost general substrates such as glass, metal foil and papers. Herein, we introduce a facile manufacturing method of a Ti back contact electrode (Ti BCE) for the BCDSCs. We found that the polylinkers such as poly(butyl titanate) have a strong binding property to make Ti particles connect one with another. A porous Ti film, which consists of Ti particles of ≤ 10? size connected by a small amount of polylinkers, has an excellent low sheet resistance of 10 Ω sq^-1 for an efficient electron collection for DSCs. This Ti BCE can be prepared by using a facile printing method under normal ambient conditions. Conjugating the new back contact electrode technology with the traditional monolithic structure using the carbon counter electrode, we fabricated TCO-less DSCs. These four-layer structurered DSCs consist of a dye-adsorbed nanocrystalline TiO₂ film on a glass substrate, a porous Ti back contact layer, a ZrO₂ spacer layer and a carbon counter electrode in a layered structure. Under AM 1.5 G and 100 mWcm^?2 simulated sunlight illumination, the four-layer structurered DSCs with N719 dyes and I^-/I₃^-redox electrolytes achieved PCEs up to 5.21 %.     

Etude des systèmes binaires formées par le chlorure de cyanogène et par les tétrachlorures de carbone,de silicium,de germanium et d'étain

Study of binary systems formed by cyanogen chloride and the tetrachlorides of carbon, silicon, germanium and tin. The diagrams of binary mixtures of cyanogene chloride with the tetrachlorides of carbon, silicon, germanium and tin were studied. Only SnCl₄ gives an addition compound: SnCl₄ · 2ClCN. The existence of the complex was confirmed by X-ray diffraction and vapour pressure measurements. This complex gives SnCl₄ · 2NOCl on treatment with nitrosyl chloride.     

Enhancement of the efficiency of dye-sensitized solar cell with multi-wall carbon nanotubes/polythiophene composite counter electrodes prepared by electrodeposition

For the purpose of increasing the energy conversion efficiency of dye-sensitized solar cells (DSSCs), multi-wall carbon nanotube (MWCNT)/polythiophene (PTh) composite film counter electrode has been fabricated by electrophoresis and cyclic voltammetry (CV) in sequence. The morphology and chemical structure have been characterized by transmission electron microscopy (TEM), scanning electron microscope (SEM), and Raman spectroscopy respectively. The overall energy conversion efficiency of the DSSC employing the MWCNT/PTh composite film has reached 4.72%, which is close to that of the DSSC with a platinum (Pt) counter electrode (5.68%). Compared with a standard DSSC with MWCNT counter electrode whose efficiency is 2.68%, the energy conversion efficiency has been increased by 76.12% for the DSSC with MWCNT/PTh counter electrode. These results indicate that the composite film with high conductivity, high active surface area, and good catalytic properties for I₃⁻ reduction can potentially be used as the counter electrode in a high-performance DSSC.     

Na4Mn9O18 as a positive electrode material for an aqueous electrolyte sodium-ion energy storage device

Here we demonstrate Na₄Mn₉O₁₈ as a sodium intercalation positive electrode material for an aqueous electrolyte energy storage device. A simple solid-state synthesis route was used to produce this material, which was then tested electrochemically in a 1 M Na₂SO₄ electrolyte against an activated carbon counter electrode using cyclic voltammetry and galvanostatic cycling. Optimized Na₄Mn₉O₁₈ was documented as having a specific capacity of 45 mAh/g through a voltage range of 0.5 V, or an equivalent specific capacitance of over 300 F/g. With the proper negative:positive electrode mass ratio, energy storage cells capable of being charged to at least 1.7 V without significant water electrolysis are documented. Cycling data and rate studies indicate promising performance for this unexplored low-cost positive electrode material.     

Carbon nanotube-carbon black hybrid counter electrodes for dye-sensitized solar cells and the effect on charge transfer kinetics

In this work, the catalytic activity of carbon nanotubes (CNTs), carbon black (CB), and CNT-CB counter electrodes in the I⁻/I₃⁻ reduction reaction is reported and compared with the Pt counter electrode. The fabricated counter electrodes were evaluated in dye-sensitized solar cells (DSSCs). The results indicate that the best cathodes were made from CNT₁₀ (240 μm) and CB with a charge transfer resistance (R_CT) of 2.70 Ω, and when the complete device shows 19.83 Ω of internal series resistance (R_S), the photovoltaic parameters of these cells were J_SC = 10.47 mA cm⁻²; V_OC = 0.70 V; and FF = 57.90, with an efficiency of 4.29%, indicating a better interaction between the CNT₁₀ in the 3D network of the counter electrode, generating a good charge transfer kinetics, in comparison with only CNT₁₀ or CB.

     

A Modified Sequential Deposition Route for High-Performance Carbon-Based Perovskite Solar Cells under Atmosphere Condition

Carbon-based hole transport material (HTM)-free perovskite solar cells have exhibited a promising commercialization prospect, attributed to their outstanding stability and low manufacturing cost. However, the serious charge recombination at the interface of the carbon counter electrode and titanium dioxide (TiO₂) suppresses the improvement in the carbon-based perovskite solar cells’ performance. Here, we propose a modified sequential deposition process in air, which introduces a mixed solvent to improve the morphology of lead iodide (PbI₂) film. Combined with ethanol treatment, the preferred crystallization orientation of the PbI₂ film is generated. This new deposition strategy can prepare a thick and compact methylammonium lead halide (MAPbI₃) film under high-humidity conditions, which acts as a natural active layer that separates the carbon counter electrode and TiO₂. Meanwhile, the modified sequential deposition method provides a simple way to facilitate the conversion of the ultrathick PbI₂ capping layer to MAPbI₃, as the light absorption layer. By adjusting the thickness of the MAPbI₃ capping layer, we achieved a power conversation efficiency (PCE) of 12.5% for the carbon-based perovskite solar cells.     

介孔碳-碳纳米管-硫化铜复合材料对电极的制备及其在量子点敏化太阳能电池中的应用

首先研究了介孔碳(MC)、碳纳米管(CNT)和不同MC/CNT质量比(m_(MC)/m_(CNT))制备的MC-CNT二元复合材料对电极的光电转换效率(PCE),进一步加入预先水热合成的CuS纳米材料,制备出MC-CNT-CuS三元复合材料对电极,同时探讨了CuS添加量和膜厚对对电极PCE的影响。实验结果表明,当m_(MC)/m_(CNT)=3/2时,2种碳材料能最大程度地发挥协同作用,使电池性能最好,PCE达12.69%。再加入0.4 g CuS时PCE可进一步提高,且对电极印刷5层时最优,此时所组装的电池获得的PCE最高(13.18%)。     

One-Electron Reduction of 2-Mono(2,6-diisopropylphenylimino)acenaphthene-1-one (dpp-mian)

The electrochemical characteristics of 2-mono(2,6-diisopropylphenylimino)acenaphthene-1-one (dpp-mian) have been investigated. One-electron reduction of dpp-mian involves the iminoketone fragment, which is revealed by the EPR spectrum obtained after the electrolysis of the dpp-mian solution in tetrahydrofuran (THF). The reduction of dpp-mian with one equivalent of metallic potassium leads to a similar EPR spectrum. The sodium complex [(dpp-mian)Na(dme)]₂ ( 1 ) produces an EPR signal with hyperfine coupling on the nitrogen atom of the iminoketone fragment of the dpp-mian ligand. Dpp-mian can also be reduced in a one-electron process by SnCl₂×(dioxane). In this case, complex (dpp-mian)₂SnCl₂ ( 2 ) is formed, with the tin atom displaying an oxidation state of +4. Tin(II) chloride dihydrate, SnCl₂×2(H₂O), also reduces dpp-mian, but the two ligands bound to tin in the product form a new carbon–carbon bond between the ketone moieties of the dpp-mian monoanions to form complex (bis-dpp-mian)HSnCl₃ ( 3 ). Metallic tin reduces dpp-mian to form the (bis-dpp-mian)₂Sn ( 4 ) species. Compounds 1 – 4 were characterized by X-ray diffraction.     

High-performance Pt-NiO nanosheet-based counter electrodes for dye-sensitized solar cells

High-performance counter electrodes for dye-sensitized solar cells (DSSCs) are fabricated with platinum-nickel oxide (Pt-NiO) nanosheets as catalytic materials. Firstly, the Pt-Ni nanosheets are synthesized via galvanic replacement reaction between pre-synthesized Ni nanosheets and an aqueous H₂PtCl₆ solution. Secondly, after thermal treatment in air, the Pt-Ni alloys are turned to Pt-NiO nanosheets. The related data of cyclic voltammetry, electrochemical impedance spectroscopy, and Tafel polarization reveal that Pt-NiO counter electrodes show highly catalytic activity and low charge transfer resistance. The DSSC with Pt-NiO counter electrode exhibits power conversion efficiency (PCE) of 8.40 %, which is lower than that of the DSSC containing commercial available Pt counter electrode (9.15 %) under full sunlight illumination (100 mW cm^?2, AM1.5G). However, owing to the extremely high transparency of Pt-NiO counter electrode, when putting an Ag mirror behind the back side of the DSSC, the reflected light can bring great enhanced PCE (11.27 %).     

Quantum dot-sensitized solar cells employing Pt/C60 counter electrode provide an efficiency exceeding 2%

A microporous platinum/fullerenes (Pt/C 60) counter electrode was prepared by using a facile rapid thermal decomposition method,and the quantum-dot sensitized solar cell (QDSSC) of Pt/C 60-TiO 2-CdS-ZnS and Pt/C 60-TiO 2-CdTe-ZnS was fabrication.The technique forms a good contact between QDs and TiO 2 films.The photovoltaic performances of the as-prepared cells were investigated.The QDSSCs with Pt/C 60 counter electrode show high power conversion efficiency of 1.90% and 2.06%,respectively (under irradiation of a simulated solar light with an intensity of 100 mW cm 2),which is comparable to the one fabricated using conventional Pt electrode.     

CoS制备方法研究及在染料敏化电池中应用

通过简单的气-固反应法在氟掺杂的氧化锡导电玻璃(FTO)上成功制备了CoS对电极,并通过优化工艺,进一步确认了制备CoS的最佳浓度。通过扫面电子显微镜(SEM)、X射线衍射(XRD)、拉曼光谱、X射线光电子能谱(XPS)、电化学阻抗谱(EIS)、循环伏安测试(CV)、Tafel极化曲线以及光电流密度-电压特性曲线(J-V)分别研究了其表面形貌、物质结构、电催化性能和光电性能。结果表明20%浓度制备的CoS对电极具有较高的电催化活性,在一个标准太阳光照条件下(100mW.cm_-2),其光电转换效率(PCE)是7.81%,短路电流密度(J_sc)是17.3 mA.cm_?2,开路电压(V_oc)是0.74 V,填充因子(FF)是0.61,显示出与Pt对电极(7.97%)相比拟的性能。说明通过这种气-固反应法采用浓度为20%醋酸钴溶液制备的CoS薄膜具有高催化性、低成本的优点,可代替Pt作为染料敏化电池对电极。、关键词用黑体,及关键词内容用宋体。     

Comparison of electrocatalytic reduction of CO2 to HCOOH with different tin oxides on carbon nanotubes

A comparative study is reported on the electrocatalytic reduction of CO₂ to HCOOH in aqueous alkaline solution with differently prepared tin-oxide particles on multi-walled carbon nanotubes from SnCl₂ or SnCl₄ precursors. The highest faradaic and energy efficiencies of 64% and 27% were obtained at − 1.40 V vs. SCE with particles that were obtained by KBH₄ reduction from a SnCl₂ precursor. At lower potentials, competitive reduction reactions occur. A SnCl₂ versus SnCl₄ precursor favors retention of a Sn(II) valence state in a surface tin oxyhydroxide surface layer. Different morphologies of the particle agglomerates made little difference in the electrocatalytic selectivity and activity. The two SnO_x/CNT electrodes both showed a current density retention of ~ 70% after a 20-h electrolysis.     

One‐Dimensional Carbon Nanotube/SnO2/Noble Metal Nanoparticle Hybrid Nanostructure: Synthesis,Characterization, and Electrochemical Sensing

Herein we report a facile and efficient method for self‐assembling noble‐metal nanoparticles (NPs) to the surface of SnO₂‐coated carbon nanotubes (CNT@SnO₂) to construct CNT@SnO₂/noble metal NP hybrids. By using SnCl₄ as the precursor of the SnO₂ shell on the surface of CNTs, the hydrolysis speed of SnCl₄ was slowed down in ethanol containing a trace amount of urea and water. The coaxial nanostructure of CNT@SnO₂ was confirmed by using X‐ray powder diffraction (XRD) and transmission electron microscopy (TEM). It was found that the coating layer of SnO₂ was homogeneous with the mean thickness of 8 nm. The CNT@SnO₂/noble‐metal NP hybrids were obtained by mixing noble‐metal NPs with as‐prepared CNT@SnO₂ coaxial nanocables by means of a self‐assembly strategy. With the amino group terminated, the CNT@SnO₂ coaxial nanocable can readily adsorb the as‐prepared noble‐metal NPs (Au, Ag, Au? Pt, and Au? Pd NPs). The presence of an amino group at the surface of SnO₂ was proved by use of X‐ray photoelectron spectroscopy (XPS). In addition, H₂O₂ sensing by amperometric methods could serve as detection models for investigating the electrocatalytic ability of as‐prepared hybrid materials. It was found that wide linear ranges and low detection limits were obtained by using the enzyme‐free CNT@SnO₂@Au? Pt modified electrode, which indicated the potential utilizations of the hybrid based on CNT@SnO₂ for electrochemical sensing.     

MALDI‐TOF‐MS analysis of living cationic polymerization of vinyl ethers. III. Polymerization with SnCl4 and TiCl4 in the absence of additives

Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analysis revealed that the precision control (or the living nature) of the cationic polymerization of vinyl ethers with SnCl₄ or TiCl₄ critically depends on the Lewis acid concentration and temperature. Specifically, at an extremely low Lewis acid concentration, for example, the polymerization with the HCl–vinyl ether adduct (an initiator) is living at ?78 °C in CH₂Cl₂ solvent, whereas side reactions occurred at a higher concentration of SnCl₄ or at a higher temperature, ?15 °C. This was more pronounced with SnCl₄ than with TiCl₄, which was due to a stronger Lewis acidity of SnCl₄ as suggested by NMR analysis of the model reactions. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1258–1267, 2001     

Darstellung,Mössbauer- und Schwingungsspektren der Komplexe [SnCl4F]⊖, [SnCl4(NCS)]⊖ und [SnCl4(NCS)2]2⊖

Preparation, Mössbauer and Vibrational Spectra of the Complexes [SnCl₄F]^?, [SnCl₄(NCS)]^?, and [SnCl₄(NCS)₂]^2? N(CH₂)₄F and N(CH₂)₄SCN react in liquid SO₂ with SnCl₄ yielding the adducts [N(CH₃)₄][SnCl₄F] (I), [N(CH₃)₄][SnCl₄(NCS)] (II) and [N(CH₃)₄]₂[SnCl₄(NCS)₂] (III).respectively. Mössbauer and vibrational spectra indicate for the anion of I a fluoro-bridged species, which is probably tetrameric like the isoelectronic SbCl₄F. For II dimeric moieties are proposed with bridging S-atoms, while [SnCl₄(NCS)₂]^2? has an octahedral structure with N-bonded isothiocyanate groups in the trans-positions.     

硫化亚铜对电极在量子点敏化太阳电池中的应用

报道了一种基于硫族金属复合物N₄H₉Cu₇S₄前驱体溶液制备硫化亚铜对电极的新方法. 分别制备了TiO₂纳米颗粒多孔薄膜和TiO₂纳米棒阵列结构的光阳极, 并在此基础上研究了基于硫化亚铜对电极的CdS/CdSe量子点敏化太阳电池的光电性能, 同时结合电化学阻抗技术考察了硫化亚铜对电极的催化性能. 结果表明: 与铂电极相比, 本方法制备的硫化亚铜电极对多硫电解质具有更高的催化活性, 所组装的CdS/CdSe量子点敏化太阳电池具有更优的光伏性能.