Mesoporous TiO₂ Beads Offer Improved Mass Transport for Cobalt‐Based Redox Couples Leading to High Efficiency Dye‐Sensitized Solar Cells

Overcoming ionic diffusion limitations is essential for the development of high‐efficiency dye‐sensitized solar cells based on cobalt redox mediators. Here, improved mass transport is reported for photoanodes composed of mesoporous TiO₂ beads of varying pore sizes and porosities in combination with the high extinction YD2‐o‐C8 porphyrin dye. Compared to a photoanode made of 20 nm‐sized TiO₂ particles, electrolyte diffusion through these films is greatly improved due to the large interstitial pores between the TiO₂ beads, resulting in up to 70% increase in diffusion‐limited current. Simultaneously, transient photocurrent measurements reveal no mass transport limitations for films of up to 10 μm thickness. In contrast, standard photoanodes made of 20 nm‐sized TiO₂ particles show non‐linear behavior in photocurrent under 1 sun illumination for a film thickness as low as 7 μm. By including a transparent thin mesoporous TiO₂ underlayer in order to reduce optical losses at the fluorine‐doped tin oxide (FTO)‐TiO₂ interface, an efficiency of 11.4% under AM1.5G 1 sun illumination is achieved. The combination of high surface area, strong scattering behavior, and high porosity makes these mesoporous TiO₂ beads particularly suitable for dye‐sensitized solar cells using bulky redox couples and/or viscous electrolytes.