Advanced Energy Materials

Donor-acceptor (D-A) type copolymers show great potential for the application in the active layer of organic solar cells. Nevertheless the nature of the excited states, the coupling mechanism and the relaxation pathways following photoexcitation are yet to be clarified. We carried out comparative measurements of the steady state absorption and photoluminescence (PL) on the copolymer poly[N-(1-octylnonyl)-2,7-carbazole] -alt-5,5-[4',7' -di(thien-2-yl)-2',1',3' -benzothiadiazole] (PCDTBT), its building blocks as well as on the newly synthesized N-(1-octylnonyl)-2,7-bis-[(5-phenyl)thien-2-yl)carbazole (BPT-carbazole) (see Figure 1). The high-energy absorption band (HEB) of PCDTBT was identified with absorption of carbazoles with adjacent thiophene rings while the low-energy band (LEB) originates instead from the charge transfer (CT) state delocalized over the aforementioned unit with adjacent benzothiadiazole group. Photoexcitation of the HEB is followed by internal relaxation prior the radiative decay to the ground state. Adding PC70BM results in the efficient PL quenching within the first 50 ps after excitation. From the PL excitation experiments no evidence for a direct electron transfer from the HEB of PCDTBT towards the fullerene acceptor was found, therefore the internal relaxation mechanisms within PCDTBT can be assumed to precede. Our findings indicate that effective coupling between copolymer building blocks governs the photovoltaic performance of the blends.

The trap states in three fullerene derivatives, namely PC61BM ([6,6]-phenyl C61 butyric acid methyl ester), bisPC61BM (bis[6,6]-phenyl C61 butyric acid methyl ester) and PC71BM ([6,6]-phenyl C71 butyric acid methyl ester), are investigated by thermally stimulated current measurements (TSC). Thereby, the lower limit of the trap densities for all studied methanofullerenes exhibits values in the order of 10^22 m^-3 with the highest trap density in bisPC61BM and the lowest in PC61BM. Fractional TSC measurements on PC61BM reveal a broad trap distribution instead of discrete trap levels with activation energies ranging from 15 meV to 270 meV and the maximum at about 75 meV. The activation energies of the most prominent traps in the other two fullerene derivatives are significantly higher, being at 96 meV and 223 meV for PC71BM and 184 meV for bisPC61BM, respectively. The influence of these findings on the performance of organic solar cells is discussed.

Encapsulation of electronic devices based on organic materials that are prone to degradation even under normal atmospheric conditions with hermetic barriers is crucial for increasing their lifetime. A challenge is to develop 'ultrabarriers' that are impermeable, flexible, and preferably transparent. Another important requirement is that they must be compatible with organic electronics fabrication schemes (i.e. must be solution processable, deposited at room temperature and be chemically inert). Here, we report lifetime increase of 1,300 hours for poly(3-hexylthiophene) (P3HT) films encapsulated by uniform and continuous thin (~10 nm) films of reduced graphene oxide (rGO). This level of protection against oxygen and water vapor diffusion is substantially better than conventional polymeric barriers such as CytopTM, which degrades after only 350 hours despite being 400 nm thick. Analysis using atomic force microscopy, x-ray photoelectron spectroscopy and high resolution transmission electron microscopy suggest that the superior oxygen gas/moisture barrier property of rGO is due to the close interlayer distance packing and absence of pinholes within the impermeable sheets. These material properties can be correlated to the enhanced lag time of 500 hours. Our results provide new insight for the design of high performance and solution processable transparent 'ultrabarriers' for a wide range of encapsulation applications.

Adding a small amount of single walled carbon nanotubes (SWCNTs) greatly improves graphene oxide (GO)'s performance as the anode modifying layer for polymer solar cells, putting it on par with the commonly used PEDOT:PSS. The high red/infrared transparency and water processability should make GO:SWCNTs an attractive interfacial layer material for high performance polymer solar cells with low bandgap polymers.

An effective antireflection coating of syringelike ZnO NRAs is demonstrated for GaAs solar cells. Energy conversion efficiency is significantly enhanced by up to 32%. GaAs is focussed on as a model system, but the hydrothermal growth of syringelike ZnO nanostructures is readily compatible with the existing processes in the photovoltaic industry, and highly applicable for various types of solar cells.

Research on the luminescent solar concentrator (LSC) over the past thirty-odd years is reviewed. The LSC is a simple device at its heart, employing a polymeric or glass waveguide and luminescent molecules to generate electricity from sunlight when attached to a photovoltaic cell. The LSC has the potential to find extended use in an area traditionally difficult for effective use of regular photovoltaic panels: the built environment. The LSC is a device very flexible in its design, with a variety of possible shapes and colors. The primary challenge faced by the devices is increasing their photon-to-electron conversion efficiencies. A number of laboratories are working to improve the efficiency and lifetime of the LSC device, with the ultimate goal of commercializing the devices within a few years. The topics covered here relate to the efforts for reducing losses in these devices. These include studies of novel luminophores, including organic fluorescent dyes, inorganic phosphors, and quantum dots. Ways to limit the surface and internal losses are also discussed, including using organic and inorganic-based selective mirrors which allow sunlight in but reflect luminophore-emitted light, plasmonic structures to enhance emissions, novel photovoltaics, alignment of the luminophores to manipulate the path of the emitted light, and patterning of the dye layer to improve emission efficiency. Finally, some possible ‘glimpses of the future’ are offered, with additional research paths that could result in a device that makes solar energy a ubiquitous part of the urban setting, finding use as sound barriers, bus-stop roofs, awnings, windows, paving, or siding tiles.

3DM-LiMnPO 4 balls and flakes are prepared via an impregnation method using a PMMA template. Both 3DM ball and flake structures demonstrated superior capacity retention to previously reported LiMnPO 4 prepared by various methods.

Chemical etching concurrently modifies pristine to layer-by-layer 3D-LiCoO 2 with a Co 3O 4 coating. Not only can the layered morphology affect the high electrochemical performance, but also the coating effect reduces the structure instability of the LiCoO 2 during cycling. This process can be applied to design other compounds to enhance their performance in Li-ion batteries.

CuS, CoS, and CuS/CoS onto fluorine-doped tin oxide glass substrates were deposited to function as counter electrodes for polysulfide redox reactions in CdS/CdSe quantum dot–sensitized solar cells (QDSSCs). Relative to a Pt electrode, the CuS, CoS, and CuS/CoS electrodes provide greater electrocatalytic activity, higher reflectivity, and lower charge-transfer resistance. Measurements of fill factor and short-current density reveal that the electrocatalytic activities, reflectivity, and internal resistance of counter electrodes play strong roles in determining the energy-conversion efficiency (η) of the QDSSCs. Because the CuS/CoS electrode has a smaller internal resistance and higher reflectivity relative to those of the CuS and CoS electrodes, it exhibits a higher fill factor and short-circuit current density. As a result, the QDSSC featuring a CuS/CoS electrode provides a higher value of η. Under illumination of one sun (100 mW cm−2), the QDSSCs incorporating Pt, CuS, CoS, and CuS/CoS counter electrodes provide values of η of 3.0 ± 0.1, 3.3 ± 0.3, 3.8 ± 0.2, and 4.1 ± 0.2%, respectively.

An integrated computational and experimental study of FeS₂ pyrite reveals that phase coexistence is an important factor limiting performance as a thin-film solar absorber. This phase coexistence is suppressed with the ternary materials Fe₂SiS₄ and Fe₂GeS₄, which also exhibit higher band gaps than FeS₂. Thus, the ternaries provide a new entry point for development of thin-film absorbers and high-efficiency photovoltaics.

A high electron mobility polymer, poly{[N,N’-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5’-(2,2’-bithiophene) (P(NDI2OD-T2)) is investigated for use as an electron acceptor in all-polymer blends. Despite the high bulk electron mobility, near-infrared absorption band and compatible energy levels, bulk heterojunction devices fabricated with poly(3-hexylthiophene) (P3HT) as the electron donor exhibit power conversion efficiencies of only 0.2%. In order to understand this disappointing photovoltaic performance, systematic investigations of the photophysics, device physics and morphology of this system are performed. Ultra-fast transient absorption spectroscopy reveals a two-stage decay process with an initial rapid loss of photoinduced polarons, followed by a second slower decay. This second slower decay is similar to what is observed for efficient P3HT:PCBM ([6,6]-phenyl C61-butyric acid methyl ester) blends, however the initial fast decay that is absent in P3HT:PCBM blends suggests rapid, geminate recombination of charge pairs shortly after charge transfer. X-ray microscopy reveals coarse phase separation of P3HT:P(NDI2OD-T2) blends with domains of size 0.2 to 1 micrometer. P3HT photoluminescence, however, is still found to be efficiently quenched indicating intermixing within these mesoscale domains. This hierarchy of phase separation is consistent with the transient absorption, whereby localized confinement of charges on isolated chains in the matrix of the other polymer hinders the separation of interfacial electron-hole pairs. These results indicate that local, interfacial processes are the key factor determining the overall efficiency of this system and highlight the need for improved morphological control in order for the potential benefit of high-mobility electron accepting polymers to be realized.

Organic bulk heterojunction photovoltaic devices predominantly use the fullerene derivatives [C60]PCBM and [C70]PCBM as the electron accepting component. This report presents a new organic electron accepting small molecule 2-[{7-(9,9-di-n-propyl-9H-fluoren-2-yl)benzo[c][1,2,5]thiadiazol-4-yl}methylene]malononitrile (K12) for organic solar cell applications. It can be processed by evaporation under vacuum or by solution processing to give amorphous thin films and can be annealed at a modest temperature to give films with much greater order and enhanced charge transport properties. The molecule can efficiently quench the photoluminescence of the donor polymer poly(3-n-hexylthiophene-2,5-diyl) (P3HT) and time resolved microwave conductivity measurements show that mobile charges are generated indicating that a truly charge separated state is formed. The power conversion efficiencies of the photovoltaic devices are found to depend strongly on the acceptor packing. Optimized K12:P3HT bulk heterojunction devices have efficiencies of 0.73±0.01% under AM1.5G simulated sunlight. The efficiencies of the devices are limited by the level of crystallinity and nanoscale morphology that was achievable in the blend with P3HT.

By tuning the frontier orbital energies through selective halogenation of the periphery of the organic framework, new light harvesting electron acceptors based on boron subphthalocyanine chloride (SubPc) have been made. Planar heterojunction organic photovoltaics made using a Cl 6-SubPc acceptor deliver an exceptionally high open-circuit voltage (∼1.3 V), good power conversion efficiency (∼2.7%) and improved operational stability in comparison to similar devices made using C 60 as the acceptor material.

An advanced multifuelled solid oxide fuel cell (ASOFC) with a functional nanocomposite was developed and tested for use in a polygeneration system. Several different types of fuel, for example, gaseous (hydrogen and biogas) and liquid fuels (bio-ethanol and bio-methanol), were used in the experiments. Maximum power densities of 1000, 300, 600, 550 mW cm−2 were achieved using hydrogen, bio-gas, bio-methanol, and bio-ethanol, respectively, in the ASOFC. Electrical and total efficiencies of 54% and 80% were achieved using the single cell with hydrogen fuel. These results show that the use of a multi-fuelled system for polygeneration is a promising means of generating sustainable power.

Thermoelectric materials can be optimized by tuning the carrier concentration with chemical doping. However, because the optimum dopant concentration typically increases with temperature, the optimum efficiency can not normally be achieved for a uniform material in a temperature gradient. Here, we show Ag-doped PbTe/Ag2Te composites exhibit high thermoelectric performance (∼50% greater than La-doped composites) because of a temperature induced gradient in the doping concentration caused by the temperature-dependent solubility of Ag in the PbTe matrix. This demonstrates a new mechanism to achieve a higher thermoelectric efficiency afforded by a given material system, and should be applicable to other thermoelectric materials.

Some cations of ionic liquids (ILs) of interest for high-energy electrochemical storage devices, such as lithium batteries and supercapacitors, have a structure similar to that of surfactants. For such, it is very important to understand if these IL cations tend to aggregate like surfactants since this would affect the ion mobility and thus the ionic conductivity. The aggregation behaviour of ILs consisting of the bis(trifluoromethanesulfonyl)imide anion and different N-alkyl-N-methyl-pyrrolidinium cations, with the alkyl chain varied from C3H7 to C8H17, was extensively studied with NMR and Raman methods, also in the presence of Li+ cations. 2H NMR spin-lattice and spin-spin relaxation rates were analyzed by applying the “two step” model of surfactant dynamics. Here we show that, indeed, the cations in these ILs tend to form aggregates surrounded by the anions. The effect is even more pronounced in the presence of dissolved lithium cations.

In the past decade, there have been exciting developments in the field of lithium ion batteries as energy storage devices, resulting in the application of lithium ion batteries in areas ranging from small portable electric devices to large power systems such as hybrid electric vehicles. However, the maximum energy density of current lithium ion batteries having topatactic chemistry is not sufficient to meet the demands of new markets in such areas as electric vehicles. Therefore, new electrochemical systems with higher energy densities are being sought, and metal-air batteries with conversion chemistry are considered a promising candidate. More recently, promising electrochemical performance has driven much research interest in Li-air and Zn-air batteries. This review provides an overview of the fundamentals and recent progress in the area of Li-air and Zn-air batteries, with the aim of providing a better understanding of the new electrochemical systems.

(VACNTs) are grown directly on a freestanding graphene paper (GP). The desirable carrier transport ability of the VACNTs, good conductivity and mechanical properties of the GP, and strong bonding between the VACNTs and the GP endow the hybrid structure with superior performance when utilized as the electrodes of lithium-ion batteries and dye-sensitized solar cells.

A simple method was developed to prepare ultra-low Pt loading membrane electrode assembly (MEA) using vertically aligned carbon nanotubes (VACNTs) as highly ordered catalyst support for PEM fuel cells application. In the method, VACNTs were directly grown on the cheap household aluminum foil by plasma enhanced chemical vapor deposition (PECVD), using Fe/Co bimetallic catalyst. By depositing a Pt thin layer on VACNTs/Al and subsequent hot pressing, Pt/VACNTs can be 100% transferred from Al foil onto polymer electrolyte membrane for the fabrication of MEA. The whole transfer process does not need any chemical removal and destroy membrane. The PEM fuel cell with the MEA fabricated using this method showed an excellent performance with ultra-low Pt loading down to 35 μg cm−2 which was comparable to that of the commercial Pt catalyst on carbon powder with 400 μg cm−2. To the best of our knowledge, for the first time, we identified that it is possible to substantially reduce the Pt loading one order by application of order-structured electrode based on VACNTs as Pt catalysts support, compared with the traditional random electrode at a comparable performance through experimental and mathematical methods.

The photovoltaic parameters, i.e., the short-circuit current, open-circuit voltage and device fill factor, of bulk heterojunction solar cells that use perylene diimide (PDI) derivatives as electron acceptors are often far below the theoretically expected values for reasons still not entirely understood. This article demonstrates that the photovoltaic characteristics of blend films of regioregular poly(3-hexylthiophene) (rr-P3HT) and PDI molecules are improved upon using a core-alkylated PDI derivative instead of the often used N-alkylated PDI molecules. A doubling of the power conversion efficiency of P3HT:PDI solar cells by using the core-alkylated PDI derivative is observed leading to an unprecedented power conversion efficiency of 0.5% for a P3HT:PDI solar cell under AM1.5 solar illumination. Furthermore, the optical properties of the novel PDI derivative are compared to two standard exclusively N-alkylated PDI derivatives by steady-state and time-resolved photoluminescence spectroscopy in solution and solid state. The experiments reveal that aggregation in the solid state determines the photophysics of all PDI derivatives. However, the emission energy and excited state lifetime of the aggregates are clearly influenced by the alkyl-substitution pattern through its effect on the packing of the PDI molecules. X-ray diffraction experiments before and after thermal annealing of PDI:polystyrene and PDI:P3HT blends reveal subtle differences in the packing characteristics of the different PDI derivatives and, problematically, that P3HT ordering is suppressed by all of the PDI derivatives.

We demonstrate a new method for the direct conversion of heat to electricity using the recently discovered multiferroic alloy, Ni45Co5Mn40Sn101. This alloy undergoes a low hysteresis, reversible martensitic phase transformation from a nonmagnetic martensite phase to a strongly ferromagnetic austenite phase upon heating. When biased by a suitably placed permanent magnet, heating through the phase transformation causes a sudden increase of the magnetic moment to a large value. As a consequence of Faraday’s law of induction, this drives a current in a surrounding circuit. Theory predicts that under optimal conditions the performance compares favorably with the best thermoelectrics. Because of the low hysteresis of the alloy, a promising area of application of this concept appears to be energy conversion at small ΔT, suggesting a possible route to the conversion of the vast amounts of energy stored on earth at small temperature difference. We postulate other new methods for the direct conversion of heat to electricity suggested by the underlying theory.

To develop a durable proton-exchange membrane (PEM) for fuel-cell applications, a series of sulfonated poly(benzoxazole thioether sulfone)s ( SPTESBOs) are designed and synthesized, with anticipated good dimensional stability (via acid–base cross linking), improved oxidative stability against free radicals (via incorporation of thioether groups), and enhanced inherent stability (via elimination of unstable end groups) of the backbone. The structures and the degree of sulfonation of the copolymers are characterized using Fourier-transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy (1H NMR and 19F NMR). The electrochemical stabilities of the monomers are examined using cyclic voltammetry in a typical three-electrode cell configuration. The physicochemical properties of the membranes vital to fuel-cell performance are also carefully evaluated under conditions relevant to fuel-cell operation, including chemical and thermal stability, proton conductivity, solubility in different solvents, water uptake, and swelling ratio. The new membranes exhibit low dimensional change at 25°C to 90°C and excellent thermal stability up to 250°C. Upon elimination of unstable end groups, the co-polymers display enhanced chemical resistance and oxidative stability in Fenton's test. Further, the SPTESBO-HFB-60 (HFB-60=hexafluorobenzene, 60 mol% sulfone) membrane displays comparable fuel-cell performance to that of an NRE 212 membrane at 80°C under fully humidified condition, suggesting that the new membranes have the potential to be more durable but less expensive for fuel-cell applications.

This work introduces an effective, inexpensive, and large-scale production approach to the synthesis of a carbon coated, high grain boundary density, dual phase Li4Ti5O12-TiO2 nanocomposite anode material for use in rechargeable lithium-ion batteries. The microstructure and morphology of the Li4Ti5O12-TiO2-C product were characterized systematically. The Li4Ti5O12-TiO2-C nanocomposite electrode yielded good electrochemical performance in terms of high capacity (166 mAh g−1 at a current density of 0.5 C), good cycling stability, and excellent rate capability (110 mAh g−1 at a current density of 10 C up to 100 cycles). The likely contributing factors to the excellent electrochemical performance of the Li4Ti5O12-TiO2-C nanocomposite could be related to the improved morphology, including the presence of high grain boundary density among the nanoparticles, carbon layering on each nanocrystal, and grain boundary interface areas embedded in a carbon matrix, where electronic transport properties were tuned by interfacial design and by varying the spacing of interfaces down to the nanoscale regime, in which the grain boundary interface embedded carbon matrix can store electrolyte and allows more channels for the Li+ ion insertion/extraction reaction. This research suggests that carbon-coated dual phase Li4Ti5O12-TiO2 nanocomposites could be suitable for use as a high rate performance anode material for lithium-ion batteries.

Single-walled carbon nanotubes (SWNTs) sorted by electronic type are employed as organic photovoltaic device anodes. Metal-enriched SWNT films yield device efficiencies that are fifty times greater than their semiconducting counterparts. Through sheet resistance, UV-vis-NIR optical absorbance, and X-ray photoelectron spectroscopy measurements, the OPV charge blocking layer PEDOT:PSS is found to reverse the original chemical doping of the SWNT films. The relative insensitivity of metallic SWNTs to chemical doping thus explains the improved performance of metal-enriched SWNT films as OPV anodes.

Silicon exhibits the largest known capacity for Li insertion in anodes of Li-ion batteries. However, because of large volume expansion/phase changes upon alloying, Si becomes powder-like after a few charge-discharge cycles. Various approaches have been explored in the past to circumvent this problem, including the use of nanomaterials, particularly Si nanowires. However, even though nanowires resist cracking very well, anodes based on Si nanowires still see their original capacity fade away upon cycling, because of wire detachment from the substrate, due to the stress generated at their roots upon alloying with Li. Here, we present a silicon nanowire growth strategy yielding highly interconnected specimens, which prevents them from being individually detached from the substrate. We report a ∼100% charge retention after 40 cycles at C/2 rate, without charging voltage limitation. We also show that our anodes can be cycled at 8C rates without damage and we grow nanowires with a density of 1.2 mg/cm2, yielding anodes delivering a 4.2 mAh/cm2 charge density. Finally, we point out that a better understanding of the interactions of silicon with electrolytes is needed if the field is to progress in the future.