Liquid Alloy Enabled Solid-State Batteries for Conformal Electrode–Electrolyte Interfaces

Recent research efforts on solid-state alkali-metal batteries are pushing the limit of energy density to a higher level. However, the development of solid-state batteries is still hindered by many intrinsic limitations, among which the incompatibility between the solid electrolyte and the metal anode is a critical issue attracting massive research attention. A Na–K liquid alloy electrode is designed to form a conformal electrode–electrolyte interface with a solid electrolyte. Much enhanced electrode–electrolyte interfacial contact electrically and physically is observed with liquid metal anodes than solid alkali metals on solid electrolytes. Symmetric cells of the liquid metal electrolytes show much lower overpotential as well as better cyclability than the alkali-metal electrodes. Excellent cyclability over 500 cycles with reasonable capacity decay and good rate performance of full cells with the sodium rhodizonate and a ferricyanide potassium-ion cathode are both achieved. By adjusting salt and filler species in the polymer electrolyte, the wettability of liquid metal on the electrolyte can be further improved, and the raised ionic conductivity can further improve the battery performance of such a design.     

New interdigital design for large area dye solar modules using a lead‐free glass frit sealing

A new interdigital design for large area dye solar modules is developed for an area of 30×30 cm². This design requires fewer holes in the glass substrate for electrolyte filling, than the conventional strip design. A complete manufacturing process of this module—ranging from screen printed layers to semi‐automated colouring and electrolyte filling—in a laboratory‐scale baseline is illustrated. As primary sealing method, a durable glass frit sealing is used. It is shown, that the lead (Pb) content present in many glass frit powders contaminates the catalytic platinum electrode during the sintering process, resulting in a lowering of the fill factor. A screen printable lead‐free glass frit paste is developed, which solves this problem. Long term stability tests are presented on 2·5 cm² dye solar cells, which have been completely sealed with glass frit. In consecutively performed accelerated ageing tests under 85°C in the dark (about 1400 h) and continuous illumination with visible light (1 sun, about 1700 h), a 2·5 cm² dye solar cell with an electrolyte based on propylmethylimidazolium iodide showed an overall degradation of less than 5% in conversion efficiency. In a subsequently performed thermal cycling test (−40°C to +85°C, 50 cycles) a 2·5 cm² dye solar cell with the same electrolyte composition also showed only a slight degradation of less than 5% in conversion efficiency. Copyright © 2006 John Wiley & Sons, Ltd.     

Pore-filling of Spiro-OMeTAD determined by Rutherford backscattering spectrometry in templated TiO2 photoelectrodes

Liquid-state dye-sensitized solar cells can suffer from electrolyte evaporation and leakage. Therefore solid-state hole transporting materials are investigated as alternative electrolyte materials. However, in solid-state dye-sensitized solar cells, optimal TiO₂ films thickness is limited to a few microns allowing the adsorption of only a low quantity of photoactive dye and thus leading to poor light harvesting and low conversion efficiency. In order to overcome this limitation, high surface area templated films are investigated as alternative to nanocrystalline films prepared by doctor-blade or screen-printing. Moreover, templating is expected to improve the pore accessibility what would promote the solid electrolyte penetration inside the porous network, making possible efficient charge transfers. In this study, films prepared from different structuring agents are discussed in terms of microstructural properties (porosity, crystallinity) as well as impact on the dye loading and Spiro-OMeTAD (2,2′,7,7′-tetrakis-(N,N-di-p-methoxyphenylamine)9,9′-spirobifluorene) solid electrolyte filling. We first report Rutherford backscattering spectrometry as an innovative non-destructive tool to characterize the hole transporting materials infiltration. Templated films show dye loading more than two times higher than nanocrystalline films prepared by doctor-blade or screen-printing and solid electrolyte infiltration up to 88%.     

Non‐Corrosive,Non‐Absorbing Organic Redox Couple for Dye‐Sensitized Solar Cells

A new colorless electrolyte containing an organic redox couple, tetramethylthiourea (TMTU) and its oxidized dimer tetramethylformaminium disulfide dication ([TMFDS]²⁺), is applied to dye‐sensitized solar cells (DSCs). Advantages of this redox couple include its non‐corrosive nature, low cost, and easy handling. More impressively, it operates well with carbon electrodes. The DSCs fabricated with a lab‐made HCS‐CB carbon counter‐electrode can present up to 3.1% power conversion efficiency under AM 1.5 illumination of 100 mW·cm^?2 and 4.5% under weaker light intensities. This result distinctly outperforms the identical DSCs with a Pt electrode. Corrosive experiments reveal that Al and stainless steel (SS) sheets are stable in the [TMFDS]²⁺/TMTU‐based electrolyte. Its electrochemical impedance spectrum (EIS) is used to evaluate the influence of different counter‐electrodes on the cell performance, and preliminary investigations reveal that carbon electrodes with large surface areas and ideal corrosion‐inertness toward the sulfur‐containing [TMFDS]²⁺/TMTU redox couple exhibit promise for application in iodine‐free DSCs.     

A Hybrid Poly(ethylene oxide)/ Poly(vinylidene fluoride)/TiO2 Nanoparticle Solid‐State Redox Electrolyte for Dye‐Sensitized Nanocrystalline Solar Cells

High‐efficiency all‐solid‐state dye‐sensitized nanocrystalline solar cells have been fabricated using a poly(ethylene oxide)/poly(vinylidene fluoride) (PEO/PVDF)/TiO₂‐nanoparticle polymer redox electrolyte, which yields an overall energy‐conversion efficiency of about 4.8 % under irradiation by white light (65.2 mW cm^–2). The introduction of PVDF (which contains the highly electronegative element fluorine) and TiO₂ nanoparticles into the PEO electrolyte increases the ionic conductivity (by about two orders of magnitude) and effectively reduces the recombination rate at the interface of the TiO₂ and the solid‐state electrolyte, thus enhancing the performance of the solar cell.     

The Role of Insulating Oxides in Blocking the Charge Carrier Recombination in Dye‐Sensitized Solar Cells

Electron recombination is one of the major loss factors in dye‐sensitized solar cells (DSC), especially, with single electron outer sphere redox shuttle electrolyte. Insulating sub‐nanometer oxide tunneling layers deposited by atomic layer deposition (ALD) are known to block the electron recombination, thereby leading to an increase in the open‐circuit potential and the collection efficiency of the solar cell. A general perception in the DSC community is that any insulating oxide layer can block the recombination. However, in this work, it is unraveled that the insulating property of oxides alone is not sufficient. In addition, the properties such as the conduction band position and the oxidation state of the insulating oxide, the electronic structural modification induced to the underlying TiO₂ mesoporous film, modification of surface charges (isoelectric point) and charge of the electrolyte species have to be considered. A complete photovoltaic study is done by depositing different cycles (by ALD) of four different insulating oxides (Ga₂O₃, ZrO₂, Nb₂O₅, and Ta₂O₅) and their recombination characteristics, surface electronic properties, transport rate, and injection dynamics are investigated with a standard organic dye and Co²⁺/Co³⁺ redox mediator. A comparison is made with the conventional iodide/triiodide electrolyte.     

A New Ionic Liquid for a Redox Electrolyte of Dye‐Sensitized Solar Cells

A new ionic liquid, 1‐vinyl‐3‐heptylimidazolium iodide (VHpII), was synthesized and applied as a redox electrolyte for dye‐sensitized solar cells. The chemical structure of the synthesized VHpII was confirmed using ¹H NMR. Thermogravimetric analysis showed that the VHpII was stable for thermal stress of up to 250°C. The energy conversion efficiencies of the VHpII‐based dye‐sensitized solar cells were investigated in terms of the effect of a lithium iodide addition. A solar cell containing the redox couple of VHpII and iodine showed a conversion efficiency of 2.63% under 1 sun light intensity at AM 1.5. Adding 0.4 M LiI results in a conversion efficiency of 3.63%, which was an improvement of about 40%. The increased conversion efficiency was ascribed to an increase in external quantum efficiency.     

High‐Power Lithium Metal Batteries Enabled by High‐Concentration Acetonitrile‐Based Electrolytes with Vinylene Carbonate Additive

To enable next‐generation high‐power, high‐energy‐density lithium (Li) metal batteries (LMBs), an electrolyte possessing both high Li Coulombic efficiency (CE) at a high rate and good anodic stability on cathodes is critical. Acetonitrile (AN) is a well‐known organic solvent for high anodic stability and high ionic conductivity, yet its application in LMBs is limited due to its poor compatibility with Li metal anodes even at high salt concentration conditions. Here, a highly concentrated AN‐based electrolyte is developed with a vinylene carbonate (VC) additive to suppress Li⁺ depletion at high current densities. Addition of VC to the AN‐based electrolyte leads to the formation of a polycarbonate‐based solid electrolyte interphase, which minimizes Li corrosion and leads to a very high Li CE of up to 99.2% at a current density of 0.2 mA cm^‐2. Using such an electrolyte, fast charging of Li||NMC333 cells is realized at a high current density of 3.6 mA cm^‐2, and stable cycling of Li||NMC622 cells with a high cathode loading of 4 mAh cm^‐2 is also demonstrated.     

Transparent conductive oxide‐less back contact dye‐sensitized solar cells using cobalt electrolyte

Transparent conductive oxide‐less (TCO‐less) dye‐sensitized solar cells (DSSCs) have been fabricated and characterized using nanoporous TiO₂‐coated stainless steel metal mesh as flexible photoanode and cobalt bipyridyl complex (Co(bpy))‐based one electron redox shuttle electrolyte. Attempts have been made towards enhancing the efficiency of TCO‐less DSSCs to match with their TCO‐based DSSC counterparts. It has been found that surface protection of metal mesh is highly required for enhancing the efficiency of TCO‐less DSSCs specially using cobalt electrolytes as confirmed by dark current–voltage characteristics. Photocurrent action spectra clearly reveal that TCO‐based DSSCs using (Co(bpy)) electrolyte exhibits photon harvesting (incident photon to current conversion efficiency (IPCE) 52%) in the 370–450 nm wavelength region as compared to photon harvesting at peak absorption of the dye (IPCE 56% at 550 nm), which is almost the same (IPCE 47%) in the 400–610 nm wavelength region for TCO‐less DSSCs. Under similar experimental conditions, replacing indoline dye D‐205 to porphyrin‐based dye YD2‐o‐C8 led to the enhancement in the photoconversion efficiency from 3.33% to 4.84% under simulated solar irradiation. Copyright © 2014 John Wiley & Sons, Ltd.     

The monolithic multicell: a tool for testing material components in dye‐sensitized solar cells

A multicell is presented as a tool for testing material components in encapsulated dye‐sensitized solar cells. The multicell is based on a four‐layer monolithic cell structure and an industrial process technology. Each multicell plate includes 24 individual well‐encapsulated cells. A sulfur lamp corrected to the solar spectrum has been used to characterize the cells. Efficiencies up to 6·8% at a light‐intensity of 1000 W/m^su2 (up to 7·5% at 250 W/m²) have been obtained with an electrolyte solution based on γ‐butyrolactone. Additionally, a promising long‐term stability at cell efficiencies close to 5% at 1000 W/m² has been obtained with an electrolyte based on glutaronitrile. The reproducibility of the cell performance before and after exposure to accelerated testing has been high. This means that the multicell can be used as an efficient tool for comparative performance and stability tests. Copyright © 2006 John Wiley & Sons, Ltd.     

Amorphous Zinc Stannate (Zn2SnO4) Nanofibers Networks as Photoelectrodes for Organic Dye‐Sensitized Solar Cells

A new strategy for developing dye‐sensitised solar cells (DSSCs) by combining thin porous zinc tin oxide (Zn₂SnO₄) fiber‐based photoelectrodes with purely organic sensitizers is presented. The preparation of highly porous Zn₂SnO₄ electrodes, which show high specific surface area up to 124 m²/g using electrospinning techniques, is reported. The synthesis of a new organic donor‐conjugate‐acceptor (D‐π‐A) structured orange organic dye with molar extinction coefficient of 44 600 M^?1 cm^?1 is also presented. This dye and two other reference dyes, one organic and a ruthenium complex, are employed for the fabrication of Zn₂SnO₄ fiber‐based DSSCs. Remarkably, organic dye‐sensitized DSSCs displayed significantly improved performance compared to the ruthenium complex sensitized DSSCs. The devices based on a 3 μm‐thick Zn₂SnO₄ electrode using the new sensitizer in conjunction with a liquid electrolyte show promising photovoltaic conversion up to 3.7% under standard AM 1.5G sunlight (100 mW cm^?2). This result ranks among the highest reported for devices using ternary metal oxide electrodes.     

Synergistic Interaction of Dyes and Semiconductor Quantum Dots for Advanced Cascade Cosensitized Solar Cells

A new procedure for the cosensitization with quantum dots (QDs) and dyes for sensitized solar cells is reported here. Cascade cosensitization of TiO₂ electrodes is obtained by the sensitization with CdS QDs and zinc phthalocyanines (ZnPcs), in which ZnPcs containing a sulfur atom are specially designed to produce a cascade injection by direct attachment to QDs. This strategy causes a double synergetic interaction. This is the differentiating point of cascade cosensitization in comparison with other approaches in which dyes with conventional functionalization are anchored to TiO₂ electrodes. Cosensitization produces a panchromatic response from the visible to near‐IR region already observed with other sensitization strategies. However, cascade cosensitization produces in addition a synergistic interaction between QDs and dye, that it is not merely limited to the complementary light absorption, but dye enhances the efficiency of QD sensitization acting as a passivating agent. The cascade cosensitization concept is demonstrated with using [Co(phen)₃]^3+/2+ redox electrolyte. The TiO₂/CdS QD‐ZnPc/[Co(phen)₃]^3+/2+ sensitized solar cell shows a large improvement of short‐circuit photocurrent and open‐circuit voltage in comparison with samples just sensitized with QDs. The advent of such cosensitized QD‐ZnPc solar cells paves the way to extend the absorbance region of the promising QD‐based solar cells and the development of a new family of molecules designed for this purpose.     

Artificial Graphite Paper as a Corrosion-Resistant Current Collector for Long-Life Lithium Metal Batteries

The employment of ultra-thin lithium metal anode with high loading cathode is the key to realizing high-energy-density rechargeable lithium batteries. Ultra-thin lithium foils are routinely loaded on a copper substrate in batteries, however, the close contact of these two metals causes galvanic corrosion in the presence of electrolyte, which results in irreversible consumption of lithium and decomposition of electrolyte. Herein, a lightweight and highly conductive flexible graphite paper (GP) is applied to replace Cu foil as the current collector for lithium metal anode. It is demonstrated that the application of GP prevents galvanic corrosion and maintains intimate and steady contact between Li foil and GP current collector during cycling, thereby improving the electrochemical performance of the battery. A 1.08 Ah pouch cell assembled with Li@GP anode and LiNi_0.8Co_0.1Mn_0.1O₂ cathode exhibits a long lifetime of 240 cycles with a capacity retention of 91.6% under limited Li, high cathode loading and lean electrolyte conditions.     

Transparent,Double‐Sided,ITO‐Free,Flexible Dye‐Sensitized Solar Cells Based on Metal Wire/ZnO Nanowire Arrays

Transparent, double‐sided, flexible, ITO‐free dye‐sensitized solar cells (DSSCs) are fabricated in a simple, facile, and controllable way. Highly ordered, high‐crystal‐quality, high‐density ZnO nanowire arrays are radially grown on stainless steel, Au, Ag, and Cu microwires, which serve as working electrodes. Pt wires serve as the counter electrodes. Two metal wires are encased in electrolyte between two poly(ethylene terephthalate) (PET) films (or polydimethylsiloxane (PDMS) films) to render the device both flexible and highly transparent. The effect of the dye thickness on the photovoltaic performance of the DSSCs as a function of dye‐loading time is investigated systematically. Shorter dye‐loading times lead to thinner dye layers and better device performance. A dye‐loading time of 20 min results in the best device performance. An oxidation treatment of the metal wires is developed effectively to avoid the galvanic‐battery effect found in the experiment, which is crucial for real applications of double‐metal‐wire DSSC configurations. The device shows very good transparency and can increase sunlight use efficiency through two‐sided illumination. The double‐wire DSSCs remain stable for a long period of time and can be bent at large angles, up to 107°, reversibly, without any loss of performance. The double‐wire‐PET, planar solar‐cell configuration can be used as window stickers and can be readily realized for large‐area‐weave roll‐to‐roll processing.     

Optimization of Si NC/P3HT Hybrid Solar Cells

Silicon nanocrystals (Si NCs) are shown to be an electron acceptor in hybrid solar cells combining Si NCs with poly(3‐hexylthiophene) (P3HT). The effects of annealing and different metal electrodes on Si NC/P3HT hybrid solar cells are studied in this paper. After annealing at 150 °C, Si NC/P3HT solar cells exhibit power conversion efficiencies as high as 1.47%. The hole mobility in the P3HT phase extracted from space‐charge‐limited current measurements of hole‐only devices increases from 2.48 × 10^?10 to 1.11 × 10^?9 m² V^?1 s^?1 after annealing, resulting in better transport in the solar cells. A quenching of the open‐circuit voltage and short‐circuit current is observed when high work function metals are deposited as the cathode on Si NC/P3HT hybrid devices.     

Parallel‐connected monolithic dye‐sensitised solar modules

Light‐soaking and high‐temperature storage testing of monolithic dye‐sensitised solar modules with total area module efficiencies above 5% have been performed. Our experiences from the development of a four‐layer monolithic dye‐sensitised solar test cell for comparative testing of material components for dye‐sensitised solar cells have directed our module development to a novel device design consisting of parallel‐connection of individual monolithic cells. The results from the accelerated testing of the modules (total area of 17.0 cm²) with four parallel‐connected cells (active area of 3.38 cm²/cell) are equivalent to those obtained for the monolithic single test cells when using identical device components. The successful transfer from cell to module stability is an important milestone in our ambition to develop a low‐cost Photovoltaic (PV) technology. Moreover, our results indicate that intensified research and development to define the procedures for relevant accelerated testing of dye‐sensitised solar modules is urgently required. Copyright © 2010 John Wiley & Sons, Ltd.     

Effect of Gate Electrode Work‐Function on Source Charge Injection in Electrolyte‐Gated Organic Field‐Effect Transistors

Systematic investigation of the contact resistance in electrolyte‐gated organic field‐effect transistors (OFETs) demonstrates a dependence of source charge injection versus gate electrode work function. This analysis reveals contact‐limitations at the source metal‐semiconductor interface and shows that the contact resistance increases as low work function metals are used as the gate electrode. These findings are attributed to the establishment of a built‐in potential that is high enough to prevent the Fermi‐level pinning at the metal‐organic interface. This results in an unfavorable energetic alignment of the source electrode with the valence band of the organic semiconductor. Since the operating voltage in the electrolyte‐gated devices is on the same order as the variation of the work functions, it is possible to tune the contact resistance over more than one order of magnitude by varying the gate metal.     

A Thiophene‐Based Anchoring Ligand and Its Heteroleptic Ru(II)‐Complex for Efficient Thin‐Film Dye‐Sensitized Solar Cells

A novel heteroleptic Ru^II complex (BTC‐2) employing 5,5′‐(2,2′‐bipyridine‐4,4′‐diyl)‐bis(thiophene‐2‐carboxylic acid) (BTC) as the anchoring group and 4,4′‐ dinonyl‐2,2′‐bipiridyl and two thiocyanates as ligands is prepared. The photovoltaic performance and device stability achieved with this sensitizer are compared to those of the Z‐907 dye, which lacks the thiophene moieties. For thin mesoporous TiO₂ films, the devices with BTC‐2 achieve higher power conversion efficiencies than those of Z‐907 but with a double‐layer thicker film the device performance is similar. Using a volatile electrolyte and a double layer 7 + 5 μm mesoporous TiO₂ film, BTC‐2 achieves a solar‐to‐electricity conversion efficiency of 9.1% under standard global AM 1.5 sunlight. Using this sensitizer in combination with a low volatile electrolyte, a photovoltaic efficiency of 8.3% is obtained under standard global AM 1.5 sunlight. These devices show excellent stability when subjected to light soaking at 60 °C for 1000 h. Electrochemical impedance spectroscopy and transient photovoltage decay measurements are performed to help understand the changes in the photovoltaic parameters during the aging process. In solid state dye‐sensitized solar cells (DSSCs) using an organic hole‐transporting material (spiro‐MeOTAD, 2,2′,7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene), the BTC‐2 sensitizer exhibits an overall power conversion efficiency of 3.6% under AM 1.5 solar (100 mW cm^?2) irradiation.     

Parameters Influencing Charge Separation in Solid‐State Dye‐Sensitized Solar Cells Using Novel Hole Conductors

Solid‐state dye‐sensitized solar cells employing a solid organic hole‐transport material (HTM) are currently under intensive investigation, since they offer a number of practical advantages over liquid‐electrolyte junction devices. Of particular importance to the design of such devices is the control of interfacial charge transfer. In this paper, the factors that determine the yield of hole transfer at the dye/HTM interface and its correlation with solid‐state‐cell performance are identified. To this end, a series of novel triarylamine type oligomers, varying in molecular weight and mobility, are studied. Transient absorption spectroscopy is used to determine hole‐transfer yields and pore‐penetration characteristics. No correlation between hole mobility and cell performance is observed. However, it is found that the photocurrent is directly proportional to the hole‐transfer yield. This hole‐transfer yield depends on the extent of pore penetration in the dye‐sensitized film as well as on the thermodynamic driving force ΔG_dye–HTM for interfacial charge transfer. Future design of alternative solid‐state HTMs should focus on the optimization of pore‐filling properties and the control of interfacial energetics rather than on increasing material hole mobilities.     

Self‐Limiting Galvanic Growth of MnO2 Monolayers on a Liquid Metal—Applied to Photocatalysis

Liquid metals offer unprecedented chemistry. Here it is shown that they can facilitate self‐limiting oxidation processes on their surfaces, which enables the growth of metal oxides that are atomically thin. This claim is exemplified by creating atomically thin hydrated MnO₂ using a Galvanic replacement reaction between permanganate ions and a liquid gallium–indium alloy (EGaIn). The “liquid solution”–“liquid metal” process leads to the reduction of the permanganate ions, resulting in the formation of the oxide monolayer at the interface. It is presented that under mechanical agitation liquid metal droplets are established, and simultaneously, hydrated gallium oxides and manganese oxide sheets delaminate themselves from the interfacial boundaries. The produced nanosheets encapsulate a metallic core, which is found to consist of solid indium only, with the full migration of gallium out of the droplets. This process produces core/shell structures, where the shells are made of stacked atomically thin nanosheets. The obtained core/shell structures are found to be an efficient photocatalyst for the degradation of an organic dye under simulated solar irradiation. This study presents a new research direction toward the modification and functionalization of liquid metals through spontaneous interfacial redox reactions, which has implications for many applications beyond photocatalysis.