Identifying Current Collectors that Enable Light-Battery Interactions.

In recent years, there has been an increased focus on studying light-battery interactions in the context of operando optical studies and integrated photoelectrochemical energy harvesting. However, there has been little insight into identifying suitable "light-accepting" current collectors for this class of batteries. In this study, fluorine-doped tin oxide, indium-tin oxide, and silver nanowire-graphene films are analyzed along with carbon paper, carbon nanotube paper, and stainless-steel mesh as current collectors for optical batteries. They are categorized into two classes - transmissive and non-transmissive, based on the orientation of the light-electrode interaction. Various methods to prepare the electrode are highlighted, including drop casting and the fabrication of free-standing electrodes. The optical and electrical properties of these current collectors as well as their electrochemical stability are measured using linear sweep voltammetry against zinc and lithium anodes. Finally, the rate performance and long-term cycling stability of lithium manganese oxide (LiMn2O4) cathodes are measured against lithium anodes with these current collectors and their performance is compared. These results show which current collector to choose depends on the application and cell chemistry. These guidelines will assist in the design of future optical cells for in-situ measurements and photoelectrochemical energy storage.

Does Heat Play a Role in the Observed Behavior of Aqueous Photobatteries?

Light-rechargeable photobatteries have emerged as an elegant solution to address the intermittency of solar irradiation by harvesting and storing solar energy directly through a battery electrode. Recently, a number of compact two-electrode photobatteries have been proposed, showing increases in capacity and open-circuit voltage upon illumination. Here, we analyze the thermal contributions to this increase in capacity under galvanostatic and photocharging conditions in two promising photoactive cathode materials, V2O5 and LiMn2O4. We propose an improved cell and experimental design and perform temperature-controlled photoelectrochemical measurements using these materials as photocathodes. We show that the photoenhanced capacities of these materials under 1 sun irradiation can be attributed mostly to thermal effects. Using operando reflection spectroscopy, we show that the spectral behavior of the photocathode changes as a function of the state of charge, resulting in changing optical absorption properties. Through this technique, we show that the band gap of V2O5 vanishes after continued zinc ion intercalation, making it unsuitable as a photocathode beyond a certain discharge voltage. These results and experimental techniques will enable the rational selection and testing of materials for next-generation photo-rechargeable systems.

Influence of the Lithium-Ion Concentration in Electrolytes on the Performance of Dye-Sensitized Photorechargeable Batteries.

Dye-sensitized photorechargeable batteries (DSPBs) have recently gained attention for realizing energy recycling systems under dim light conditions. However, their performance under high storage efficiency (i.e., the capacity charged within a limited time) for practical application remains to be evaluated. Herein, we varied the lithium (Li)-ion concentration, which plays a dual role as energy charging and storage components, to obtain the optimized energy density of DSPBs. Electrochemical studies showed that the Li-ion concentration strongly affected the resistance characteristics of DSPBs. In particular, increasing the Li-ion concentration improved the output capacity and decreased the output voltage. Consequently, the energy density of the finely optimized DSPB improved from 8.73 to 12.64 mWh/cm3 when irradiated by a 1000-lx indoor light-emitting-diode lamp. These findings on the effects of Li-ion concentrations in electrolytes on the performance of DSPBs represent a step forward in realizing the practical application of DSPBs.

Photo-Enhanced Magnesium-Ion Capacitors Using Photoactive Electrodes.

Off-grid power sources are becoming increasingly important for applications ranging from autonomous sensor networks to fighting energy poverty. Interactions of light with certain classes of battery and capacitor materials have recently gained attention to enhance the rate performance or to even charge energy storage devices directly with light. Interestingly, these devices have the potential to reduce the volume and cost of autonomous power sources. Here, a light-enhanced magnesium (Mg)-ion capacitor is shown. The latter is interesting because of the large natural abundance of Mg and its ability to operate in low cost and non-flammable aqueous electrolytes. Photoelectrodes using a combination of vanadium dioxide and reduced graphene oxide can achieve capacitance enhancements of up to 56% under light exposure alongside a 21% higher energy density of 20.5 mAh kg-1 .

Non-destructive Monitoring of Dye Depth Profile in Mesoporous TiO2 Electrodes of Solar Cells with Micro-SORS.

The dye distribution within a photo-electrode is a key parameter in determining the performances of dye-sensitized photon-to-electron conversion devices, such as dye-sensitized solar cells (DSSCs). A traditional, depth profiling investigation by destructive means including cross-sectional sampling is unsuitable for large quality control applications in manufacturing processes. Therefore, a non-destructive monitoring of the dye depth profile is required, which is the first step toward a non-destructive evaluation of the internal degradation of the device in the field. Here, we present a conceptual demonstration of the ability to monitor the dye depth profile within the light active layer of DSSCs by non-destructive means with high chemical specificity using a recently developed non-destructive/non-invasive Raman method, micro-spatially offset Raman spectroscopy (micro-SORS). Micro-SORS is able to probe through turbid materials, providing the molecular identification of compounds located under the surface, without the need of resorting to a cross-sectional analysis. The study was performed on the photo-electrode of DSSCs. This represents the first demonstration of the micro-SORS concept in the solar cell area as well as, more generally, the application of micro-SORS to the thinnest layer to date. A sample set has been prepared with varying concentrations of the dye and the thickness of the matrix consisting of a titanium dioxide layer. The results showed that micro-SORS can unequivocally discriminate between the homogeneous and inhomogeneous dye depth profiles. Moreover, micro-SORS outcomes have been compared with the results obtained with destructive time-of-flight secondary ion mass spectrometry measurements. The results of the two techniques are in good agreement, confirming the reliability of micro-SORS analysis. Therefore, this study is expected to pave the way for establishing a wider and more effective monitoring capability in this important field.

Molecular Engineering for Enhanced Charge Transfer in Thin-Film Photoanode.

We developed three types of dithieno[3,2-b;2',3'-d]thiophene (DTT)-based organic sensitizers for high-performance thin photoactive TiO2 films and investigated the simple but powerful molecular engineering of different types of bonding between the triarylamine electron donor and the conjugated DTT π-bridge by the introduction of single, double, and triple bonds. As a result, with only 1.3 µm transparent and 2.5-µm TiO2 scattering layers, the triple-bond sensitizer (T-DAHTDTT) shows the highest power conversion efficiency (η = 8.4%; VOC = 0.73 V, JSC = 15.4 mA·cm-2, and FF = 0.75) in an iodine electrolyte system under one solar illumination (AM 1.5, 1000 W·m-2), followed by the single-bond sensitizer (S-DAHTDTT) (η = 7.6%) and the double-bond sensitizer (D-DAHTDTT) (η = 6.4%). We suggest that the superior performance of T-DAHTDTT comes from enhanced intramolecular charge transfer (ICT) induced by the triple bond. Consequently, T-DAHTDTT exhibits the most active photoelectron injection and charge transport on a TiO2 film during operation, which leads to the highest photocurrent density among the systems studied. We analyzed these correlations mainly in terms of charge injection efficiency, level of photocharge storage, and charge-transport kinetics. This study suggests that the molecular engineering of a triple bond between the electron donor and the π-bridge of a sensitizer increases the performance of dye-sensitized solar cell (DSC) with a thin photoactive film by enhancing not only JSC through improved ICT but also VOC through the evenly distributed sensitizer surface coverage.

Control and Monitoring of Dye Distribution in Mesoporous TiO2 Film for Improving Photovoltaic Performance.

Dye distribution in a mesoporous TiO2 film is a key factor in the performance of dye-sensitized solar cells, but there has been little research on it. Here we report even dye distribution within the porous TiO2 film achieved by a physical driving force of gas flow. Gas-assisted dye arrangement, gas bubbling soaking (GBS), significantly accelerates the dye infiltration compared to conventional overnight soaking (OS). As a demonstration, we investigated the time-dependent dye infiltration using plasmon sensors. GBS produces an even vertical dispersion throughout the film, as illustrated by time-of-flight secondary ion mass spectrometry depth profiles. For devices using a 7-µm-thick active layer and a ruthenium-based dye (N719), only 15 min of GBS treatment produced better power conversion efficiency (PCE) than the optimal result from OS treatment (15 h), despite a lower dye capacity. Dual-GBS treatment (20 min for N719 and 10 min for YD2, a porphyrin dye) produced the best PCE (9.0%) in the device, which was ∼17% higher than that treated with dual-OS (10 h for N719 and 5 h for YD2). Such improvements are associated with reduced dye-free sites inside the porous TiO2 film after GBS treatment, leading to faster charge transport and slower charge loss.