Yu Bai,†,‡ Ivań Mora-Sero,́ Filippo De Angelis, Juan Bisquert, and Peng Wang*,† †State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China ‡Institute of Chemistry and Energy Material Innovation, Academy of Fundamental Interdisciplinary Sciences, Harbin Institute of Technology, Harbin 150080, China Photovoltaic and Optoelectronic Devices Group, Departament de Física, Universitat Jaume I, 12071 Castello,́ Spain Istituto CNR di Scienze e Tecnologie Molecolari, c/o Dipartimento di Chimica, Universita ̀ di Perugia, via Elce di Sotto 8, I-06123 Perugia, Italy

Titanium Dioxide Nanomaterials for Photovoltaic Applications

Dye-sensitized solar cells (DSSCs) are regarded as prospective solar cells for the next generation of photovoltaic technologies and have become research hotspots in the PV field. The counter electrode, as a crucial component of DSSCs, collects electrons from the external circuit and catalyzes the redox reduction in the electrolyte, which has a significant influence on the photovoltaic performance, long-term stability and cost of the devices. Solar cells, dye-sensitized solar cells, as well as the structure, principle, preparation and characterization of counter electrodes are mentioned in the introduction section. The next six sections discuss the counter electrodes based on transparency and flexibility, metals and alloys, carbon materials, conductive polymers, transition metal compounds, and hybrids, respectively. The special features and performance, advantages and disadvantages, preparation, characterization, mechanisms, important events and development histories of various counter electrodes are presented. In the eighth section, the development of counter electrodes is summarized with an outlook. This article panoramically reviews the counter electrodes in DSSCs, which is of great significance for enhancing the development levels of DSSCs and other photoelectrochemical devices.

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Counter electrodes in dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs) have attracted widespread attention in recent years as potential cost-effective alternatives to silicon-based and thin-film solar cells. Within typical DSSCs, the counter electrode (CE) is vital to collect electrons from the external circuit and catalyze the I3- reduction in the electrolyte. Careful design of the CEs can improve the catalytic activity and chemical stability associated with the liquid redox electrolyte used in most cells. In this Progress Report, advances made by our groups in the development of CEs for DSSCs are reviewed, highlighting important contributions that promise low-cost, efficient, and robust DSSC systems. Specifically, we focus on the design of novel Pt-free CE catalytic materials, including design ideas, fabrication approaches, characterization techniques, first-principle density functional theory (DFT) calculations, ab-initio Car-Parrinello molecular dynamics (CPMD) simulations, and stability evaluations, that serve as practical alternatives to conventional noble metal Pt electrodes. We stress the merits and demerits of well-designed Pt-free CEs, such as carbon materials, conductive polymers, transition metal compounds (TMCs) and their corresponding hybrids. Also, the prospects and challenges of alternative Pt catalysts for their applications in new-type DSSCs and other catalytic fields are discussed. Â© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pt-free counter electrode for dye-sensitized solar cells with high efficiency

Photoelectrochemical water-splitting devices, which use solar energy to convert water into hydrogen and oxygen, have been investigated for decades. Multijunction designs are most efficient, as they can absorb enough solar energy and provide sufficient free energy for water cleavage. However, a balance exists between device complexity, cost and efficiency. Water splitters fabricated using triple-junction amorphous silicon1,2 or III–V3 semiconductors have demonstrated reasonable efficiencies, but at high cost and high device complexity. Simpler approaches using oxide-based semiconductors in a dual-absorber tandem approach4,5 have reported solar-to-hydrogen (STH) conversion efficiencies only up to 0.3% (ref. 4). Here, we present a device based on an oxide photoanode and a dye-sensitized solar cell, which performs unassisted water splitting with an efficiency of up to 3.1% STH. The design relies on carefully selected redox mediators for the dye-sensitized solar cell6,7 and surface passivation techniques8 and catalysts9 for the oxide-based photoanodes. A photoelectrochemical cell made from combining a dye sensitized solar cell with a semiconductor-oxide photoanode is demonstrated to perform water splitting with an efficiency of up to 3.1%. As the scheme uses relatively inexpensive materials and fabrication techniques it could provide a cost effective approach to hydrogen production.

Highly efficient water splitting by a dual-absorber tandem cell

The air electrode, which reduces oxygen (O2), is a critical component in energy generation and storage applications such as fuel cells and metal/air batteries. The highest current densities are achieved with platinum (Pt), but in addition to its cost and scarcity, Pt particles in composite electrodes tend to be inactivated by contact with carbon monoxide (CO) or by agglomeration. We describe an air electrode based on a porous material coated with poly(3,4-ethylenedioxythiophene) (PEDOT), which acts as an O2 reduction catalyst. Continuous operation for 1500 hours was demonstrated without material degradation or deterioration in performance. O2 conversion rates were comparable with those of Pt-catalyzed electrodes of the same geometry, and the electrode was not sensitive to CO. Operation was demonstrated as an air electrode and as a dissolved O2 electrode in aqueous solution.

High Rates of Oxygen Reduction over a Vapor

Poly (3,4-ethylenedioxythiophene) (PEDOT) nanoporous layers were prepared with electro-oxidative polymerization using room temperature hydrophobic ionic liquids as a medium. The synthesized highly porous PEDOT films exhibit room temperature conductivity value of 195 S cm−1 along with reproducible high cycling life. These films were used as counter electrodes in dye-sensitized solar cells yielding ∼8% power conversion efficiency, which is close to the classical platinum coated counter electrode (8.7%). The photovoltaic performance increases as we lower the PEDOT film thickness as the thin films has reasonably high catalytic properties.

Dye-sensitized solar cells based on poly (3,4-ethylenedioxythiophene) counter electrode derived from ionic liquids

The first examples of di-branched di-anchoring organic sensitizers were synthesized and used in dye-sensitized solar cells leading to red-shifted IPCE maxima and increased photocurrent when compared to the corresponding mono-branched mono-anchoring dye, yielding power conversion efficiency of 5.7% (4.9% with ionic liquid electrolyte) with enhanced stability under 1 sun conditions from the di-anchoring groups.

Zhang Xianxi

Papers

Dye-sensitized solar cells based on poly (3,4-ethylenedioxythiophene) counter electrode derived from ionic liquids

Di-branched di-anchoring organic dyes for dye-sensitized solar cells