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Novel Layered Structures Formed by Iodocuprate Clusters Stabilized by Dialkylsulphide Ligands
KTH, Superseded Departments, Chemistry.
KTH, Superseded Departments, Chemistry.
KTH, Superseded Departments, Chemistry.
KTH, Superseded Departments, Chemistry.
2004 (English)In: Zeitschrift für Anorganische und Allgemeines Chemie, ISSN 0044-2313, E-ISSN 1521-3749, Vol. 630, no 3, 413-416 p.Article in journal (Refereed) Published
Abstract [en]

From solutions of copper iodide and dodecyldimethyl-sulphonium iodide in acetonitrile, single crystals of [Cu4I4-(DodecylMeS) 4] (1) and [Cu3I4(DodecylMeS) 3](DodecylMe2S) (2) could be obtained. Both compounds crystallize in the triclinic crystal system, space group P1 (1: a = 957.23(1), b = 967.25(2), c = 3818.38(6) pm, α = 90.3837(6)°, β = 86.4687(7)°, γ = 75.0996(7)°; 2: a = 874.23(1), b = 979.29(1), c = 4388.75(4) pm, α = 90.4472(3)°, β = 94.7088(3)°, γ = 116.1162(3)°). 1 consists of tetrahedral Cu4 clusters, which are capped by four iodide ions over the tetrahedral faces. 2 contains trigonal Cu3 clusters, which are coordinated by four iodide ions, one centered over the plane, three bridging over the edges of the Cu3 triangle. In both compounds, the S atoms of (DodecylMeS) ligands coordinate to the Cu atoms. In 2, a (DodecylMe2S) cation is also present.

Place, publisher, year, edition, pages
2004. Vol. 630, no 3, 413-416 p.
Keyword [en]
copper, iodide, cluster, crystal structure
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-6712DOI: 10.1002/zaac.200300379ISI: 000220405300015Scopus ID: 2-s2.0-4644265939OAI: oai:DiVA.org:kth-6712DiVA: diva2:11499
Note
QC 20100924Available from: 2005-09-22 Created: 2005-09-22 Last updated: 2011-10-27Bibliographically approved
In thesis
1. Ionic Liquid Electrolytes for Photoelectrochemical Solar Cells
Open this publication in new window or tab >>Ionic Liquid Electrolytes for Photoelectrochemical Solar Cells
2005 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

Potential electrolytes for dye-sensitized photoelectrochemical solar cells have been synthesized and their applicability has been investigated. Different experimental techniques were used in order to characterize the synthesized electrolytes, such as elemental analysis, electrospray ionisation/mass spectrometry, cyclic voltammetry, dynamic viscosity measurements, as well as impedance, Raman and NMR spectroscopy. Some crystal structures were characterized by using single crystal X-ray diffraction.

In order to verify the eligibility of the ionic compounds as electrolytes for photoelectrochemical solar cells, photocurrent density/photovoltage and incident photon-to-current conversion efficiency measurements were performed, using different kinds of light sources as solar simulators. In electron kinetic studies, the electron transport times in the solar cells were investigated by using intensitymodulated photocurrent and photovoltage spectroscopy. The accumulated charge present in the semiconductor was studied in photocurrent transient measurements.

The ionic liquids were successfully used as solar cell electrolytes, especially those originating from the diethyl and dibutyl-alkylsulphonium iodides. The highest overall conversion efficiency of almost 4 % was achieved by a dye-sensitized, nanocrystalline solar cell using (Bu2MeS)I:I2 (100:1) as electrolyte (Air Mass 1.5 spectrum at 100 W m-2), quite compatible with the standard efficiencies provided by organic solvent-containing cells. Several solar cells with iodine-doped metal-iodidebased electrolytes reached stable efficiencies over 2 %. The (Bu2MeS)I:I2-containing cells showed better long-term stabilities than the organic solvent-based cells, and provided the fastest electron transports as well as the highest charge accumulation.

Several polypyridyl-ruthenium complexes were tested as solar cell sensitizers. No general improvements could be observed according to the addition of amphiphilic co-adsorbents to the dyes or nanopartices of titanium dioxide to the electrolytes. For ionic liquid-containing solar cells, a saturation phenomena in the short-circuit current densities emerged at increased light intensities, probably due to inherent material transport limitation within the systems.

Some iodoargentates and -cuprates were structurally characterized, consisting of monomeric or polymeric entities with anionic networks or layers. A system of metal iodide crownether complexes were employed and tested as electrolytes in photoelectrochemical solar cells, though with poorer results. Also, the crystal structure of a copper-iodide-(12-crown-4) complex has been characterized

Place, publisher, year, edition, pages
Stockholm: KTH, 2005. xii, 121 p.
Series
Trita-OOK, ISSN 0348-825X ; 1081
Keyword
Ionic liquid electrolytes, Photoelectrochemical solar cells
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-426 (URN)91-7178-122-6 (ISBN)
Public defence
2005-09-30, D2, KTH, Lindstedtsvägen 5, Stockholm, 13:00
Opponent
Supervisors
Note
QC 20101013Available from: 2005-09-22 Created: 2005-09-22 Last updated: 2010-10-13Bibliographically approved

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