Synthesis of various carbon incorporated flower-like MoS2 microspheres as counter electrode for dye-sensitized solar cells

Journal of Solid State Electrochemistry - A flower-like molybdenum disulfide microspheres and various carbon materials (acetylene black, vulcan carbon, multi-walled carbon nanotubes, carbon...     

Modification of TiO<Subscript>2</Subscript> electrode films in dye-sensitized solar cells with PMMA

Nanocrystalline porous TiO₂ electrodes for dye-sensitized solar cells (DSC) are modified by adding polymethyl methacrylate (PMMA). The result shows that large holes are formed in the TiO₂ films, and the short circuit photocurrent density and photoelectric conversion efficiency of DSCs are obviously enhanced compared with those without adding the PMMA. The relationship between the photoelectric conversion efficiency and the amount of PMMA is presented. In particular, the highest conversion efficiency was obtained with TiO₂ electrode films of adding 7.5 wt% PMMA, increasing the conversion efficiency by 27.5%.     

Nickel phosphide-embedded graphene as counter electrode for dye-sensitized solar cells

Nickel phosphide-embedded graphene, prepared by the hydrothermal reaction of red phosphorus, nickel chloride, and graphene oxide in a mixture of ethylene glycol-water, is investigated as the counter electrode of DSSCs. It is demonstrated that the DSSC with the nickel phosphide-embedded graphene as the new counter electrode presents an excellent performance competing with that of the Pt electrode.     

Hydrothermal synthesis of brookite TiO<Subscript>2</Subscript> nanoparticles for dye-sensitized solar cell

We obtained Tannin-4-azobenzoic acid (azo dye) by the conventional method of diazotization and coupling of aromatic amines. The properties of the azo dye were characterized via ultraviolet-visible (UV–vis), infrared (IR), and nuclear magnetic resonance (NMR) spectroscopy. Nanocrystalline titanium dioxide (TiO₂) thin films were deposited by hydrothermal method onto fluorine-doped tin (IV) oxide (FTO)-coated glass substrate at 353 K for 4 h. The as-deposited and annealed films were characterized for structural, morphological, optical, thickness, and wettability properties. The synthesized metal free azo dye was used to sensitize the prepared TiO₂ thin film with thickness of 26 μm. The photoelectrochemical (PEC) performance of TiO₂ sensitized with the azo dye was evaluated in polyiodide (0.1 M KI + 0.01 M I₂ + 0.1 M KCl) electrolyte at 40 mW cm^?2 illumination intensity. The cell yielded a short circuit current of 2.82 mA, open circuit voltage of 314.3 mV, a fill factor of 0.30, and a photovoltaic conversion efficiency value of 0.64%.

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N-doped TiO<Subscript>2</Subscript> applied in low-temperature-based dye-sensitized solar cells

With urea as nitrogen source, N-doped TiO₂ powders were synthesized and fabricated for low-temperature dye-sensitized solar cells (DSSCs) by the method of doctor-blade, and the highest temperature of the whole process was 120 °C. SEM, TEM, XRD, DRS, and XPS were used to analyze the microstructure of the N-doped TiO₂ powders. EIS, Bode plot, UV–Vis and I–V were employed to measure the photovoltaic performance of the DSSCs. The maximum photoelectric conversion efficiency (η) was 5.18 % when the amount of the doped nitrogen was 4 %, and, when compared with the η of 4.22 % for pure TiO₂, the short circuit current was increased by 22.2 % and the efficiency was increased by 22.7 %. It has been shown that the doped nitrogen could effectively suppress TiO₂ crystal phase transition from anatase to rutile, and decrease the size of particles. Therefore, the increased photoelectric conversion efficiency of the N-doped TiO₂-based DSSC was ascribed to the more suitable crystal phase, sizes and inner structure.     

Photoelectrochemical properties of MWCNT-TiO2 hybrid materials as a counter electrode for dye-sensitized solar cells

The MWCNT-Ti02 hybrid materials were prepared by a simply mixing method and used as a counter electrode （CE） for dye-sensitized solar cells. Compared with the platinum CE, MWCNT-TiO2 CE has the similar redox voltage and current response in the cyclic voltammetry. The electrochemical catalytic activity was characterized by the electrochemical impedance spectroscopy and Tafel curve, including the equivalent circuit, the exchange current density, the limiting diffusion current density, and the diffusion coefficient of triiodide/iodide redox species. The results indicate that the reduction process from triiodide to iodide is determined by the kinetic-controlled and diffusion-limited processes. The device performance is optimal based on the MWCNT-TiO2 （mass ratio of 2：1） CE, such as the open-circuit voltage of 0.72 V, the short-circuit photocurrent density of 15.71 mA/cm2, the fill factor of 0.68, and the photon-to-electron conversion efficiency of 7.69%.     

Copper doped manganese dioxide as counter electrode for dye-sensitized solar cells

Many materials have been tried as the counter electrode (CE) material as a substitute to the noble metal Pt in dye-sensitized solar cells (DSSCs). The CE property is critical to the operation of a DSSC as it catalyzes the reduction of I₃^- ions and retrieves the electrons from the photoanode. Here we have explored the application of manganese dioxide (MnO₂) and copper-doped manganese dioxide (Cu-MnO₂) nanoparticles as CE candidates for DSSCs mainly as low-cost alternatives to Pt. A simple hydrothermal method was followed to synthesize α-MnO2 and Cu-MnO2 nanoparticles at a temperature of 140 °C for 14 h. The nanoparticles were characterized to prove its electrocatalytic abilities for DSSCs. DSSC devices fabricated with 10 wt% Cu-MnO₂ as CE showed the best V_OC of 781 mV, I_SC of 3.69 mA/cm², FF of 0.50, and %PCE of 1.7 whereas Pt as CE showed V_OC of 780 mV, I_SC of 14.8 mA/cm², FF of 0.43, and %PCE of 5.83 under 0.85 Sun. The low-cost feature of using Cu-MnO₂ is encouraging to further study the factors that can improve the efficiency of DSSCs with alternative CEs to conventional Pt electrodes.     

Polypyrrole-cobalt-carbon nanocomposites as efficient counter electrode materials for dye-sensitized solar cells

In this work, we demonstrate a new kind of Pt-free counter electrode for dye-sensitized solar cells(DSCs). Polypyrrole-cobalt-carbon(PPY-Co-C) nanocomposites, with the advantages of low cost and simple preparation, show favorable catalytic activity in promoting tri-iodide reduction. The DSC composed of the PPY-Co-C nanocomposite electrode exhibits an acceptable energy conversion efficiency of 6.01%, a considerable short-circuit photocurrent of 15.33 mA cm-2, and a low charge-transfer resistance of 1.5 Ω cm2. The overall performance of PPY-Co-C is superior to the carbon counterparts and comparable with the platinum reference, rendering them efficient and promising counter electrode materials for DSCs.     

Inverse opal carbons for counter electrode of dye-sensitized solar cells

We investigated the fabrication of inverse opal carbon counter electrodes using a colloidal templating method for DSSCs. Specifically, bare inverse opal carbon, mesopore-incoporated inverse opal carbon, and graphitized inverse opal carbon were synthesized and stably dispersed in ethanol solution for spray coating on a FTO substrate. The thickness of the electrode was controlled by the number of coatings, and the average relative thickness was evaluated by measuring the transmittance spectrum. The effect of the counter electrode thickness on the photovoltaic performance of the DSSCs was investigated and analyzed by interfacial charge transfer resistance (R(CT)) under EIS measurement. The effect of the surface area and conductivity of the inverse opal was also investigated by considering the increase in surface area due to the mesopore in the inverse opal carbon and conductivity by graphitization of the carbon matrix. The results showed that the FF and thereby the efficiency of DSSCs were increased as the electrode thickness increased. Consequently, the larger FF and thereby the greater efficiency of the DSSCs were achieved for mIOC and gIOC compared to IOC, which was attributed to the lower R(CT). Finally, compared to a conventional Pt counter electrode, the inverse opal-based carbon showed a comparable efficiency upon application to DSSCs.     

Interpretation of the difference of optimal Mo density in MoS<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and MoS<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> HDS catalysts

The first part of this paper deals with the morphology of the MoS₂ phase and its oxide precursor, the MoO₃ phase, mainly from a geometrical point of view. After giving a brief review of the literature describing the structure of these compounds, Mo densities in both phases were calculated along various crystallographic planes. Further, using structural models recently proposed by others, Mo densities in MoS₂ were also calculated in the case of an epitactic growth on γ-Al₂O₃ and TiO₂ model surfaces. Then, the calculated Mo densities were compared with experimental results (Mo density when HDS activity is maximal) previously obtained for catalysts constituted of MoS₂ supported on a low SSA TiO₂, a high SSA TiO₂ and a conventional γ-alumina. It was suggested that either on alumina or titania the MoS₂ phase is growing as (100) MoS₂ planes. However, while on the alumina the optimal MoS₂ phase might be constituted of dispersed MoS₂ slabs covering only a part of the alumina surface (2.9–3.9 Mo atoms/nm²), on titania the optimal MoS₂ phase might be constituted of a uniform MoS₂ monolayer (5.2 atoms/nm² for the high SSA titania, which is equal to the Mo density of a perfect MoS₂ (100) plane). This difference may originate in the creation of a 'TiMoS' phase enhancing the S atoms mobility over Mo/TiO₂-sulfided catalysts. Indeed, while in the case of a γ-alumina carrier the active sites (labile S atoms) are located on the edge of MoS₂ slabs making the ratio Mo_edge/Mo_total a crucial parameter for the catalytic performances, in the case of a titania carrier the labile sulfur atoms might be statistically distributed all over the TiMoS active phase. Further, the higher Mo density observed over the high SSA titania (5.2 atoms/nm²) when compared to that over the low SSA titania (4.2 atoms/nm²) was supposedly due to the pH-swing method advantageously used to prepare the former carrier. Indeed, this method allows giving a solid with enhanced mechanical properties providing a good stability to the derived catalysts under experimental conditions. In addition, this TiO₂ carrier exhibits a great homogeneity, with a surface structure substantially uniform, which might be adequate for a long-range growth of (100) MoS₂ slabs.     

Facile synthesis of Fe@Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> core-shell nanowires as O<Subscript>2</Subscript> electrode for high-energy Li-O<Subscript>2</Subscript> batteries

Fe@Fe₂O₃ core-shell nanowires were synthesized via the reduction of Fe³⁺ ions by sodium borohydride in an aqueous solution with a subsequent heat treatment to form Fe₂O₃ shell and employed as a cathode catalyst for non aqueous Li-air batteries. The synthesized core-shell nanowires with an average diameter of 50–100 nm manifest superior catalytic activity for oxygen evolution reaction (OER) in Li-O₂ batteries with the charge voltage plateau reduced to ～3.8 V. An outstanding performance of cycling stability was also achieved with a cutoff specific capacity of 1000 milliampere hour per gram over 40 cycles at a current density of 100 mA g^?1. The excellent electrochemical properties of Fe@Fe₂O₃ as an O₂ electrode are ascribed to the high surface area of the nanowires’ structure and high electron conductivity. This study indicates that the resulting iron-containing nanostructures are promising catalyst in Li-O₂ batteries.     

Pechini based titanium sol as a matrix in TiO<Subscript>2</Subscript> pastes for dye-sensitized solar cell application

The influence that the degree of polyesterification has on a titanium sol (Ti-sol) prepared via the Pechini method that acts as a matrix in TiO₂ pastes used for dye sensitized solar cells is reported. The different content of the polyester in the Ti-sol was realized by varying the heating time of the Ti-sol. Titanium dioxide pastes were prepared by introducing a commercial TiO₂ nanopowder into the Ti-sols. The TiO₂ layers were tested as photoanodes in dye-sensitized solar cells (DSSCs). The most appropriate degree of polyesterification was achieved by heating the Ti-sol for 0.5 and 1 h, while longer heating deteriorates the TiO₂ layer morphology. The highest efficiency of the DSSCs based on an ionic liquid electrolyte was 6.3% measured under standard test conditions (100 mW/cm², AM 1.5, 25 °C).     

Theoretical design and experimental synthesis of counter electrode for dye-sensitized solar cells: Amino-functionalized graphene

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_3~-/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.     

Study of quasi-solid electrolyte in dye-sensitized solar cells using surfactant as pore-forming materials in TiO<Subscript>2</Subscript> photoelectrodes

A novel polymer gel electrolyte was used to improve the performance and long-term stability in dye-sensitized solar cells (DSSCs). The polymer gel electrolyte (PGE) was prepared by mixing 5 wt% poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and 2 % TiO₂ nanoparticles. The conductivity of PGE with P25 reached 9.98 × 10^?3 S/cm, which increased by 34.9 % compared with 7.40 × 10^?3 S/cm of PGE without P25, and the diffusion coefficient was also increased by 19.0 %. Different photoelectrodes were obtained by using three kinds of surfactants (cetylamine, octadecylamine, and P123) as pore-forming materials, and their morphologies were contrasted through scanning electron microscopy (SEM). The results showed that gel electrolyte can increase the short-circuit current density (J _sc) from 11.01 to 12.99 mA/cm² in DSSCs. Moreover, unlike the liquid electrolyte, the gel electrolyte is more conducive to the TiO₂ photoelectrodes with larger pores. In conclusion, the efficiency of DSSC with gel electrolyte and P123 as pore-forming material was 6.73 %, which was 12 % higher than the liquid electrolyte in the same test condition. In addition, the sealed gel electrolyte DSSCs showed better stability than did liquid electrolyte DSSCs during nearly 600 h.     

A double-layered photoanode made of ZnO/TiO<Subscript>2</Subscript> composite nanoflowers and TiO<Subscript>2</Subscript> nanorods for high efficiency dye-sensitized solar cells

We present a simple sol-gel hydrothermal process for the fabrication of a double-layered structure composed of a TiO₂ nanorod overlayer and TiO₂ nanoparticle-embedded ZnO nanoflower (ZNFs@TNPs-TNRs) underlayer. The ZNFs@TNPs-TNRs was used as a photoanode in dye-sensitized solar cells (DSSCs) and their photovoltaic performance was analyzed. The ZNFs@TNPs-TNRs can enhance the adsorption of N719 dyes, charge transport, and light scattering. The cell performances can be maximized by optimizing thickness ratio and total thickness of the double-layered photoanode, and the preliminary results demonstrate that a promising power conversion efficiency (PCE) of 8.01% is determined on the DSSC with ZNFs@TNPs-TNRs anode, yielding a 28.9% enhancement in the PCE in comparison to pristine TiO₂–P25 nanoparticle-based DSSC.     

High-performance supercapacitor electrode based on a nanocomposite of polyaniline and chemically exfoliated MoS<Subscript>2</Subscript> nanosheets

In this study, MoS₂ nanosheets were first prepared by exfoliating its bulk material in HCl/LiNO₃ solution with a yield of 45%, and then a facile strategy was developed to synthesize polyaniline/MoS₂ (PANI/MoS₂) nanocomposite via in situ polymerization. Structural and morphological characterizations of MoS₂ nanosheets and the nanocomposite were investigated by scanning electron microscope (SEM), transmission electron microscope (TEM), and X-ray powder diffraction. The results of SEM illustrated that orderly sawtooth polyaniline (PANI) nanoarrays were formed on the surface of MoS₂ nanosheets. The nanocomposite displayed good electrochemical performance as a supercapacitor electrode material. The specific capacitance reached 560 F/g at a current density of 1.0 A g^?1 in 1.0 M H₂SO₄ solution. Such good performance is because that the MoS₂ nanosheets provided a highly electrolytic accessible surface area for redox-active PANI and a direct path for electrons.