Influence of solvent on the poly (acrylic acid)-oligo-(ethylene glycol) polymer gel electrolyte and the performance of quasi-solid-state dye-sensitized solar cells

The influence of solvents on the property of poly (acrylic acid)-oligo-(ethylene glycol) polymer gel electrolyte and photovoltaic performance of quasi-solid-state dye-sensitized solar cells (DSSCs) were investigated. Solvents or mixed solvents with large donor number enhance the liquid electrolyte absorbency, which further influences the ionic conductivity of polymer gel electrolyte. A polymer gel electrolyte with ionic conductivity of 4.45 mS cm⁻¹ was obtained by using poly (acrylic acid)-oligo-(ethylene glycol) as polymer matrix, and absorbing 30 vol.% N-methyl pyrrolidone and 70 vol.% γ-butyrolactone with 0.5 M NaI and 0.05 M I₂. By using this polymer gel electrolyte coupling with 0.4 M pyridine additive, a quasi-solid-state dye-sensitized solar cell with conversion efficiency of 4.74% was obtained under irradiation of 100 mW cm⁻² (AM 1.5).     

Influence of ionic additives NaI/I2 on the properties of polymer gel electrolyte and performance of quasi-solid-state dye-sensitized solar cells

The ionic additives NaI/I₂ in polymer gel electrolyte not only provide cations, but also affect the liquid electrolyte absorbency of the poly(acrylic acid)-poly(ethylene glycol) hybrid, which results in the change of ionic conductivity of polymer gel electrolyte and the photovoltaic performance of quasi-solid-state dye-sensitized solar cell. With the optimized components of liquid electrolyte containing 0.5 M NaI, 0.05 M I₂, 0.4 M pyridine, 70 vol.% γ-butyrolactone and 30 vol.% N-methylpyrrolidone, a 4.74% power conversion efficiency of quasi-solid-state dye-sensitized solar cell was obtained under 100 mW cm⁻² (AM 1.5) irradiation.     

Thermal, morphological and rheological characterization of poly(acrylic acid-g-styrene) amphiphilic graft copolymers

A family of amphiphilic poly(acrylic acid-g-styrene), P(AA-g-S), graft copolymers has been prepared by quantitative hydrolysis from poly(tert-butyl acrylate-g-styrene), P(tBA-g-S), precursors and evaluated by ¹H NMR and FTIR. The thermal characterization of these copolymers as a function of the number of grafted repeat units has been performed by thermogravimetric analysis, TGA, differential scanning calorimetry, DSC, and dynamic mechanical experiments. A higher thermal stability of the PAA main chain was observed by TGA as incompatible PS is grafted onto it. Small-angle X-ray scattering, SAXS, measurements have confirmed the existence of phase separation in the graft copolymers and the morphological behavior was analyzed. An increase on microdomains size is observed when the number of grafts diminishes. Moreover, the presence of polar functional groups in the backbone chain leads to the formation of hydrogen bonds giving rise to a substantial modification of the linear viscoelastic response compared with that exhibited by the unhydrolyzed precursory copolymers, as observed by analysis of melt rheological measurements.     

The application of P(MMA-co-MAA)/PEG polyblend gel electrolyte in quasi-solid state dye-sensitized solar cell at higher temperature

A poly(methyl methacrylate-co-methacrylate acid)/poly(ethylene glycol) [P(MMA-co-MAA)/PEG] polyblend with viscoelasticity was synthesized by a copolymerizing reaction between methyl methacrylate (MMA) and methacrylate acid (MAA) using azobisisobutyronitrile (AIBN) as initiator in poly(ethylene glycol) (PEG) methanol solution. Then, a polyblend gel electrolyte was prepared by adding KI and I₂ to P(MMA-co-MAA)/PEG system. The influence of compositions of the polyblend gel electrolyte on the ionic conductivity and the effect of temperature on photoelectronic performance of quasi-solid state dye-sensitized solar cell (QS-DSSC) were discussed. It was found that the polyblend gel electrolyte was a good candidate as high-temperature electrolyte for QS-DSSCs. Under an optimized condition, the highest conductivity of the polyblend gel electrolyte was 2.70 mS/cm² at 30 °C. Based on the polyblend gel electrolyte, a light-to-electricity conversion efficiency of 4.85% for QS-DSSC was achieved under AM 1.5 simulated solar light illumination at 60 °C.     

A quasi solid-state dye-sensitized solar cell made of polypyrrole counter electrodes

Quasi-solid state dye-sensitized solar cells have been constructed using nanocrystalline titania, a Ureasil-based nanocomposite gel electrolyte and polypyrrole-functionalized counter electrode. Polypyrrole was synthesized by potentiostatic electrodeposition using pyrrole monomer as precursor by a simple procedure in aqueous solution. The thus obtained polypyrrole films were very robust. They were characterized by FE-SEM microscopy and electrochemical impedance spectroscopy and they were used for the construction of solar cells. The employment of polypyrrole electrocatalyst was judged satisfactory for the present application since it was only 30% less efficient than the corresponding counter electrodes functionalized with Pt.     

Gel polymer electrolyte based on poly(acrylonitrile-co-styrene) and a novel organic iodide salt for quasi-solid state dye-sensitized solar cell

A gel polymer electrolyte based on poly(acrylonitrile-co-styrene) as polymer matrix and N-methyl pyridine iodide salt as I⁻ source was prepared. Controlling the concentration of polymer matrix of poly(acrylonitrile-co-styrene) at 17.5 wt.%, mixing the binary organic solvents mixture ethylene carbonate and propylene carbonate with 6:4 (w/w), and the concentration of N-methyl pyridine iodide and iodine with 0.5 and 0.05 M, respectively, the gel polymer electrolyte attains the maximum ionic conductivity (at 30 °C) of 4.63 mS cm⁻¹. Based on the gel polymer electrolyte, a quasi-solid state dye-sensitized solar cell was fabricated and its overall energy conversion efficiency of light-to-electricity of 3.10% was achieved under irradiation of 100 mW cm⁻².     

Influence of molecular weight of PEG on the property of polymer gel electrolyte and performance of quasi-solid-state dye-sensitized solar cells

A new kind of polymer gel electrolyte based on poly(acrylic acid)-poly(ethylene glycol) (PAA-PEG) hybrid was synthesized. The factor of molecular weight of PEG in the hybrid plays an important role in determining the liquid electrolyte absorbency of the hybrid and ionic conductivity of the polymer gel electrolyte, sequentially affects the photovoltaic performance of quasi-solid-state dye-sensitized solar cells. Using the hybrid with PEG molecular weight of 20,000, a polymer gel electrolyte with liquid electrolyte absorbency of 6.9 g g⁻¹ and ionic conductivity of 5.35 mS cm⁻¹ was obtained. Based on the polymer gel electrolyte, a quasi-solid-state dye-sensitized solar cell with conversion efficiency of 5.25% was achieved under irradiation of AM 1.5, 100 mW cm⁻².     

Influences of poly(ether urethane) introduction on poly(ethylene oxide) based polymer electrolyte for solvent-free dye-sensitized solar cells

A poly(ether urethane) (PEUR)/poly(ethylene oxide) (PEO)/SiO₂ based nanocomposite polymer is prepared and employed in the construction of high efficiency all-solid-state dye-sensitized nanocrystalline solar cells. The introduction of low-molecular weight PEUR prepolymer into PEO electrolyte has greatly enhance the electrolyte performance by both improving the interfacial contact properties of electrode/electrolyte and decreasing the PEO crystallization, which were confirmed by XRD and SEM characteristics. The effects of polymer composition, nano SiO₂ content on the ionic conductivity and I₃⁻ ions diffusion of polymer-blend electrolyte are investigated. The optimized composition yields an energy conversion efficiency of 3.71% under irradiation by white light (100 mW cm⁻²).     

Novel silane-substituted benzimidazolium iodide as gel electrolyte for dye-sensitized solar cells

A novel ionic electrolyte, 3-(iodohexyl)-1-(3-(triethoxysilyl)propylcarbamoyl)-1H-benzo[d]imidazol-3-ium iodide (SSBI) was prepared through the reaction of N-[3-(triethoxy-4-silyl)propyl]-1H-benzimidazole-1-carboxamide with 1,6-diiodohexane for the quasi-solidification of the electrolytic solution of a dye-sensitized solar cell (DSSC). The SSB-containing electrolyte, the sol electrolyte, in a DSSC was converted to a gel by heating it at 60 °C for 30 min in an oven. The DSSC consisting of the gel electrolyte showed a solar-to-electricity conversion efficiency comparable to that of the cell with the reference liquid electrolyte, and consistently higher stability than that of the reference cell. The performances of the DSSCs containing the reference, sol and gel electrolytes were discussed by scanning electron microscopy (SEM), impedance and chronoamperometric measurements, ionic conductivity, and UV-vis absorption spectroscopy.     

Polyvinyl pyrrolidone aided preparation of TiO2 films used in flexible dye-sensitized solar cells

Polyvinyl pyrrolidone (PVP) is introduced to low temperature preparation of a good quality TiO₂ film used in flexible dye-sensitized solar cells (DSSCs). The samples are characterized by scanning electron microscopy and UV–vis absorption spectra, the photovoltaic performance of the DSSC is measured. It is found that PVP can improve the dispersion of TiO₂ particles and the adherence of TiO₂ particles to flexible substrate, as well as the adsorption of sensitized dye to TiO₂ film. Additionally, ultraviolet light irradiation can eliminate organics remained on the surface the TiO₂ film and improve the surface state of TiO₂ film. Under an optimal condition, a flexible DSSC using TiO₂ film doped PVP and UV irradiation treated achieves a light-to-electric energy conversion efficiency of 3.02% under irradiation with a simulate solar light intensity of 100 mW cm⁻².     

碳纳米管在染料敏化太阳能电池中的应用

染料敏化太阳能电池结合了染料光敏剂和无机半导体的优势,具有较宽的光谱响应范围、对环境友好、制造工艺简单等特点,应用前景广阔。碳纳米管特殊的几何形状和导电性对于提高染料敏化太阳能电池的光电转化效率有显著作用。本文介绍了碳纳米管在有机染料敏化太阳能电池中各个主要工作部分的应用。     

The role of gel electrolyte composition in the kinetics and performance of dye-sensitized solar cells

Gel-type polymer electrolytes based on the copolymer poly(ethylene oxide-co-epichlorohydrin) and the plasticizer γ-butyrolactone (GBL) were optimized and applied in dye-sensitized solar cells. The plasticizer added to the electrolyte allowed the dissolution of a higher concentration of salt, reaching conductivity values close to 1 mS cm⁻¹ for the sample prepared with 30 wt% of LiI. Raman spectroscopy confirmed polyiodide formation in the electrolyte when the salt concentration exceeds 7.5 wt%, introducing a significant contribution of electronic conductivity in the electrolyte. The devices were characterized under AM 1.5 conditions and the I-V curves were fitted using a two diode equation. Increasing the concentration of LiI-I₂ accelerates dye cation regeneration as measured by transient absorption spectroscopy; however, it also contributes to an increase in the dark current of the cell by one order of magnitude. The best performance was achieved for the solar cell prepared with the electrolyte containing 20 wt% of LiI, with efficiencies of 3.26% and 3.49% at 100 and 10 mW cm⁻² of irradiation, respectively.     

The preparation of poly(glycidyl acrylate)-polypyrrole gel-electrolyte and its application in dye-sensitized solar cells

A microporous hybrid of poly(glycidyl acrylate)-polypyrrole (PGA-PPy) was synthesized by a two-step solution polymerization. Using this hybrid as polymer host, a gel-electrolyte with high conductivity of 12.83 mS cm⁻¹ was prepared. The researches by scanning electron microscopy (SEM), Fourier transform infrared spectra (FTIR), and cyclic voltammetry (CV) show that the microporous structure and functional groups for PGA allows the higher absorbency and good ionic salt tolerance for the electrolyte, the introduction of PPy causes a lower charge-transfer resistance and higher electrocatalytic activity for the I₃⁻/I⁻ redox reaction for the electrolyte. Based on the electrolyte, a dye-sensitized solar cell with a light-to-electrical energy conversion efficiency of 5.03% is achieved, under illumination with a simulated solar light of 100 mW cm⁻² (AM 1.5).     

Influence of 2,6 (N-pyrazolyl)isonicotinic acid on the photovoltaic properties of a dye-sensitized solar cell fabricated using poly(vinylidene fluoride) blended with poly(ethylene oxide) polymer electrolyte

A novel method of introducing a synthesized organic nitrogenous compound 2,6 (N-pyrazolyl)isonicotinic acid (BNIN) and its effect on the conduction behavior of poly(vinylidene fluoride) (PVdF)–poly(ethylene oxide) (PEO) polymer-blend electrolyte with potassium iodide (KI) and iodine (I₂) and the corresponding performance of the dye-sensitized solar cells (DSSCs) were studied. A systematic investigation of the blends using FTIR provides evidence of interaction of BNIN with the polymer. Differential scanning calorimetry (DSC) study proves the miscibility of these polymers. Due to the coordinating and plasticizing effects of BNIN, the ionic conductivity of polymer blend electrolytes is enhanced. The efficiency of DSSC using BNIN doped polymer blend electrolyte was 7.3% under an illumination of 60 mW cm⁻² were observed for the best performance of a solar cell in this work.     

The use of 2,6-bis (N-pyrazolyl) pyridine as an efficient dopant in conjugation with poly(ethylene oxide) for nanocrystalline dye-sensitized solar cells

Poly(ethylene oxide) (PEO)/2,6-bis (N-pyrazolyl) pyridine (BNPP) polymer electrolyte based photoelectrochemical cells have been fabricated with [cis-dithiocyanato-N, N-bis (2,2′ bipyridyl-4, 4′ dicarboxylic acid)ruthenium(II)] dihydrate (N3 dye) dye complex as the sensitizer and nanoporous TiO₂ film as photo anode. The introduction of 2,6-bis (N-pyrazolyl) pyridine into the poly (ethylene oxide) matrix reduces the crystallinity of the polymer and enhances the mobility of I⁻/I₃⁻ redox couple resulting in an improved performance with a higher conversion efficiency of 8.8% in terms of light energy to electric energy when compared to that of the corresponding dye-sensitized nanocrystalline TiO₂ solar cell.     

Effects of environmentally benign solvents in the agarose gel electrolytes on dye-sensitized solar cells

The ionic agarose gel electrolytes are prepared by using environmental benign solvents and co-solvents to improve the agarose solubility and capacities of the additives for dye-sensitized solar cells. The effects of single solvents (dimethyl sulfoxide (DMSO), propylene carbonate (PC), propylene glycol, triethylene glycol, and tetraethylene glycol) and DMSO-based co-solvents are examined on the conductivities, diffusion coefficients of triiodide, and energy conversion efficiencies. The highest conductivity, 14.2 mS cm⁻¹, and the highest diffusion coefficient of triiodide, 2.7 × 10⁻⁶ cm² s⁻¹, are achieved for the electrolyte containing the co-solvent of 80 vol.% PC and 20 vol.% DMSO. The environmental benign co-solvent such as DMSO/PC can significantly increase the conversion efficiency to 3.4% with agarose compared to pure MPII with agarose (1.4%), while retaining ∼80% of the energy conversion efficiencies of the reference cell without agarose under the illumination at AM 1.5, 100 mW cm⁻².     

The use of poly(vinylpyridine-co-acrylonitrile) in polymer electrolytes for quasi-solid dye-sensitized solar cells

Poly(vinylpyridine-co-acrylonitrile) (P(VP-co-AN)) was used to form polymer electrolytes for dye-sensitized solar cells (DSSCs). The effects of P(VP-co-AN) on the photovoltaic performances of DSSCs have been investigated with nonaqueous electrolytes containing alkali-iodide and iodine. It was found that the effect of P(VP-co-AN) on V_oc closely related to its amount in the electrolyte. Lower amount of P(VP-co-AN) was benefit for the construction of a solar cell containing P(VP-co-AN) with higher energy conversion efficiency. Chemically crosslinking solidification with backbone polymer P(VP-co-AN) amount of 3% fabricated quasi-solid DSSCs with 10% increased conversion efficiencies with relative to that of the initial liquid DSSCs.     

A study of blending and complexation of poly(acrylic acid)/poly(vinyl pyrrolidone)

Poly(acrylic acid) (PAA) and poly(vinyl pyrrolidone) (PVP) were chosen to prepare polymer complex and blends. The complex was prepared from ethanol solution and the blends were prepared from 1-methyl-2-pyrrolidone solution. DSC results show that the T_gs of the PAA/PVP blends lie between those of the two constituent polymers, whereas T_g of the PAA/PVP complex is higher than both blends and the two constituent polymers. TGA results show that degradation temperature, T_d, of PAA increases upon adding PVP in the blend, but thermal stability of the complex is higher than that of the blends as reflected by the higher T_d. Both FTIR and high-resolution solid state NMR show strong hydrogen bonding between PAA and PVP by showing significant chemical shift. The T_1ρ(H) measurement shows that the homogeneity scale for the blend is at ∼20 Å and that for the complex is ∼15 Å.     

高分子聚合物在太阳能电池电解质中的应用

介绍了高分子聚合物作为电解质在染料敏化纳米晶TiO2太阳能电池中的应用研究进展,按电解质的物理状态不同,分别对高分子聚合物凝胶准固态电解质和导电高分子聚合物固态电解质进行了综述,并对存在的问题和未来的研究方向进行了探讨。     

Synthesis of amphiphilic ethyl cellulose grafting poly(acrylic acid) copolymers and their self-assembly morphologies in water

Amphiphilic ethyl cellulose (EC)-g-poly(acrylic acid) (PAA) copolymers were synthesized by atom transfer radical polymerization (ATRP). Firstly, ethyl cellulose macro-initiators with the degree of the 2-bromoisobutyryl substitution of 0.04 and 0.25 synthesized by the esterification of the hydroxyl groups remained in EC macromolecular chains and the 2-bromoisobutyryl bromides. Secondly, tert-butyl acrylate was polymerized by ATRP with the ethyl cellulose macro-initiator and EC-g-PtBA copolymers were prepared. Finally, the EC-g-PAA copolymers were prepared by hydrolyzing tert-butyl group of the EC-g-PtBA copolymers. The grafting copolymers were characterized by means of GPC, ¹H NMR and FTIR spectroscopies. The molecular weight of graft copolymers increased during the polymerization and the polydispersity was low. A kinetic study showed that the polymerization was first-order. Meanwhile, EC-g-PAA copolymers were self-assembled to micelles or particles with diameters of 5 nm and 100 nm in water (pH = 10) when the concentration was 1.0 mg/ml.