Showing papers in "Energy and Environmental Science in 2016"
TL;DR: In this paper, the triple cation perovskite photovoltaics with inorganic cesium were shown to be thermally more stable, contain less phase impurities and are less sensitive to processing conditions.
Abstract: Today's best perovskite solar cells use a mixture of formamidinium and methylammonium as the monovalent cations. With the addition of inorganic cesium, the resulting triple cation perovskite compositions are thermally more stable, contain less phase impurities and are less sensitive to processing conditions. This enables more reproducible device performances to reach a stabilized power output of 21.1% and ∼18% after 250 hours under operational conditions. These properties are key for the industrialization of perovskite photovoltaics.
3,470 citations
TL;DR: In this paper, the causes of failure and associated mechanisms of device degradation, approaches to improve stability, and methods and protocols are discussed in detail and form the main focus of the review article.
Abstract: Organometal halide perovskite solar cells have evolved in an exponential manner in the two key areas of efficiency and stability. The power conversion efficiency (PCE) reached 20.1% late last year. The key disquiet was stability, which has been limiting practical application, but now the state of the art is promising, being measured in thousands of hours. These improvements have been achieved through the application of different materials, interfaces and device architecture optimizations, especially after the investigation of hole conductor free mesoporous devices incorporating carbon electrodes, which promise stable, low cost and easy device fabrication methods. However, this work is still far from complete. There are various issues associated with the degradation of Omh-perovskite, and the interface and device instability which must be addressed to achieve good reproducibility and long lifetimes for Omh-PSCs with high conversion efficiencies. A comprehensive understanding of these issues is required to achieve breakthroughs in stability and practical outdoor applications of Omh-PSCs. For successful small and large scale applications, besides the improvement of the PCE, the stability of Omh-PSCs has to be improved. The causes of failure and associated mechanisms of device degradation, followed by the origins of degradation, approaches to improve stability, and methods and protocols are discussed in detail and form the main focus of this review article.
1,403 citations
TL;DR: In this article, a review describes recent advances in the fundamental understanding of CO2 photoreduction on the surface of heterogeneous catalysts and particularly provides an overview of enhancing the adsorption/activation of CO 2 molecules.
Abstract: Large amounts of anthropogenic CO2 emissions associated with increased fossil fuel consumption have led to global warming and an energy crisis. The photocatalytic reduction of CO2 into solar fuels such as methane or methanol is believed to be one of the best methods to address these two problems. In addition to light harvesting and charge separation, the adsorption/activation and reduction of CO2 on the surface of heterogeneous catalysts remain a scientifically critical challenge, which greatly limits the overall photoconversion efficiency and selectivity of CO2 reduction. This review describes recent advances in the fundamental understanding of CO2 photoreduction on the surface of heterogeneous catalysts and particularly provides an overview of enhancing the adsorption/activation of CO2 molecules. The reaction mechanism and pathways of CO2 reduction as well as their dependent factors are also analyzed and discussed, which is expected to enable an increase in the overall efficiency of CO2 reduction through minimizing the reaction barriers and controlling the selectivity towards the desired products. The challenges and perspectives of CO2 photoreduction over heterogeneous catalysts are presented as well.
1,315 citations
TL;DR: A review of the most relevant chemical routes for converting furfural to chemicals, bio-fuels, and additives is presented in this article, focusing not only on industrially produced chemicals derived from fur, but also on other not yet commercialised products that have a high potential for commercialisation as commodities.
Abstract: The production of future transportation fuels and chemicals requires the deployment of new catalytic processes that transform biomass into valuable products under competitive conditions. Furfural has been identified as one of the most promising chemical platforms directly derived from biomass. With an annual production close to 300 kTon, furfural is currently a commodity chemical, and the technology for its production is largely established. The aim of this review is to discuss the most relevant chemical routes for converting furfural to chemicals, biofuels, and additives. This review focuses not only on industrially produced chemicals derived from furfural, but also on other not yet commercialised products that have a high potential for commercialisation as commodities. Other chemicals that are currently produced from oil but can also be derived from furfural are also reviewed. The chemical and engineering aspects such as the reaction conditions and mechanisms, as well as the main achievements and the challenges still to come in the pursuit of advancing the furfural-based industry, are highlighted.
1,079 citations
TL;DR: In this paper, the optoelectronic properties of mixed A-cation perovskites and the underlying reasons for their excellent performance and high stability were analyzed using first principle computations.
Abstract: ABX3-type organic lead halide perovskites currently attract broad attention as light harvesters for solar cells due to their high power conversion efficiency (PCE). Mixtures of formamidinium (FA) with methylammonium (MA) as A-cations show currently the best performance. Apart from offering better solar light harvesting in the near IR the addition of methylammonium stabilizes the perovskite phase of FAPbI3 which in pure form at room temperature converts to the yellow photovoltaically inactive δ-phase. We observe a similar phenomenon upon adding Cs+ cations to FAPbI3. CsPbI3 and FAPbI3 both form the undesirable yellow phase under ambient condition while the mixture forms the desired black pervoskite. Solar cells employing the composition Cs0.2FA0.8PbI2.84Br0.16 yield high average PCEs of over 17% exhibiting negligible hysteresis and excellent long term stability in ambient air. We elucidate here this remarkable behavior using first principle computations. These show that the remarkable stabilization of the perovskite phase by mixing the A-cations stems from entropic gains and the small internal energy input required for the formation of their solid solution. By contrast, the energy of formation of the delta-phase containing mixed cations is too large to be compensated by this configurational entropy increase. Our calculations reveal for the first time the optoelectronic properties of such mixed A-cation perovskites and the underlying reasons for their excellent performance and high stability.
1,032 citations
TL;DR: A critical review of the factors influencing the volumetric performance of carbon materials from a structural design point of view and an in-depth summary of various promising approaches used to make significant research breakthroughs in recent years.
Abstract: Volumetric performance, a much more reliable and precise parameter for evaluating the charge-storage capacity of supercapacitors compared with gravimetric performance, has aroused more and more interest in recent years owing to the rapid development of miniaturized, portable and wearable electronic devices as well as electric vehicles. Various carbon materials are widely used as electrode materials in supercapacitors. However, their intrinsically low specific capacitance and relatively low bulk density lead to a relatively low volumetric performance, significantly limiting their future application. This critical review points out the crucial importance of volumetric performance and reviews recent achievements of high volumetric performances obtained through the rational design and development of novel carbon-based materials. Particular emphasis is focused on discussing the factors influencing the volumetric performance of carbon materials from a structural design point of view. We then make an in-depth summary of various promising approaches used to make significant research breakthroughs in recent years. Current challenges, future research directions and opportunities in this fascinating field of supercapacitors with high gravimetric and volumetric performances are also discussed.
984 citations
TL;DR: In this article, the authors studied the catalytic reduction of CO2 by H2 using heterogeneous catalysis and found that the stabilization of key reaction intermediates is critically important for controlling catalytic selectivity.
Abstract: Ocean acidification and climate change are expected to be two of the most difficult scientific challenges of the 21st century. Converting CO2 into valuable chemicals and fuels is one of the most practical routes for reducing CO2 emissions while fossil fuels continue to dominate the energy sector. Reducing CO2 by H2 using heterogeneous catalysis has been studied extensively, but there are still significant challenges in developing active, selective and stable catalysts suitable for large-scale commercialization. The catalytic reduction of CO2 by H2 can lead to the formation of three types of products: CO through the reverse water–gas shift (RWGS) reaction, methanol via selective hydrogenation, and hydrocarbons through combination of CO2 reduction with Fischer–Tropsch (FT) reactions. Investigations into these routes reveal that the stabilization of key reaction intermediates is critically important for controlling catalytic selectivity. Furthermore, viability of these processes is contingent on the development of a CO2-free H2 source on a large enough scale to significantly reduce CO2 emissions.
881 citations
TL;DR: In this article, the authors visualize the growth of lithium dendrites in glass capillary cells and demonstrate a change of mechanism from root-growing mossy lithium to tip-growing dendritic lithium at the onset of electrolyte diffusion limitation.
Abstract: Next-generation high-energy batteries will require a rechargeable lithium metal anode, but lithium dendrites tend to form during recharging, causing short-circuit risk and capacity loss, by mechanisms that still remain elusive. Here, we visualize lithium growth in a glass capillary cell and demonstrate a change of mechanism from root-growing mossy lithium to tip-growing dendritic lithium at the onset of electrolyte diffusion limitation. In sandwich cells, we further demonstrate that mossy lithium can be blocked by nanoporous ceramic separators, while dendritic lithium can easily penetrate nanopores and short the cell. Our results imply a fundamental design constraint for metal batteries (“Sand's capacity”), which can be increased by using concentrated electrolytes with stiff, permeable, nanoporous separators for improved safety.
873 citations
TL;DR: In this article, Nitrogen-doped activated carbons (NACs) were prepared through a one-step process, and obtained NACs show high surface areas of up to 2900 m2 g−1 with a moderate N content up to 4 wt.
Abstract: Nitrogen-doped activated carbons (NACs) were prepared through a one-step process. The obtained NACs show high surface areas of up to 2900 m2 g−1 with a moderate N content of up to 4 wt%. Electrochemical evaluation of the NACs shows a high specific capacity of 129 mA h g−1 (185 F g−1) in an organic electrolyte at a current density of 0.4 A g−1, as well as excellent rate capability and cycling stability. The hybrid-type supercapacitor assembled using the NACs and a Si/C electrode exhibits a high material level energy density of 230 W h kg−1 at 1747 W kg−1. The hybrid device achieved 76.3% capacity retention after 8000 cycles tested at 1.6 A g−1.
849 citations
TL;DR: In this paper, a combination of nanoscopic and macroscopic level measurements was used to show that ion migration in polycrystalline perovskites dominates through grain boundary (GBs).
Abstract: The efficiency of perovskite solar cells is approaching that of single-crystalline silicon solar cells despite the presence of a large grain boundary (GB) area in the polycrystalline thin films. Here, by using a combination of nanoscopic and macroscopic level measurements, we show that ion migration in polycrystalline perovskites dominates through GBs. Atomic force microscopy measurements reveal much stronger hysteresis both for photocurrent and dark-current at the GBs than on the grain interiors, which can be explained by faster ion migration at the GBs. The dramatically enhanced ion migration results in the redistribution of ions along the GBs after electric poling, in contrast to the intact grain area. The perovskite single-crystal devices without GBs show negligible current hysteresis and no ion-migration signal. The discovery of dominating ion migration through GBs in perovskites can lead to broad applications in many types of devices including photovoltaics, memristors, and ion batteries.
846 citations
TL;DR: In this paper, the authors reported a drastically improved solar cell efficiency via surface optimization of the TiO2 ETL using a special ionic-liquid (IL) that shows high optical transparency and superior electron mobility.
Abstract: The electron-transport layer (ETL) between the active perovskite material and the cathode plays a critical role in planar perovskite solar cells. Herein, we report a drastically improved solar cell efficiency via surface optimization of the TiO2 ETL using a special ionic-liquid (IL) that shows high optical transparency and superior electron mobility. As a consequence, the efficiency is promoted to as high as 19.62% (the certified efficiency is 19.42%), exceeding the previous highest efficiency recorded for planar CH3NH3PbI3 perovskite solar cells. Surprisingly, the notorious hysteresis is completely eliminated, likely due to the improved ETL quality that has effectively suppressed ion migration in the perovskite layer and charge accumulation at the interfaces, higher electron mobility to balance the hole flux at the anode, and a better growth platform for the high quality perovskite absorber. Both experimental analyses and theoretical calculations reveal that the anion group of the IL bonds to TiO2, leading to a higher electron mobility and a well-matched work function. Meanwhile, the cation group interfaces with adjacent perovskite grains to provide an effective channel for electron transport and a suitable setting to grow low trap-state density perovskite for improved device performance.
TL;DR: In this paper, the authors demonstrate that the operational stability of electronic and optoelectronic devices that exploit the electron transporting properties of MeNH3PbI3 will be critically dependent upon the use of suitable barrier layers and device configurations to mitigate the oxygen sensitivity of this remarkable material.
Abstract: Here, we demonstrate that light and oxygen-induced degradation is the main reason for the low operational stability of methylammonium lead triiodide (MeNH3PbI3) perovskite solar cells exposed to ambient conditions. When exposed to both light and dry air, unencapsulated MeNH3PbI3 solar cells rapidly degrade on timescales of minutes to a few hours. This rapid degradation is also observed under electrically bias driven current flow in the dark in the presence of O2. In contrast, significantly slower degradation is observed when the MeNH3PbI3 devices are exposed to moisture alone (e.g. 85% relative humidity in N2). We show that this light and oxygen induced degradation can be slowed down by the use of interlayers that are able to remove electrons from the perovskite film before they can react with oxygen to form O2−. These observations demonstrate that the operational stability of electronic and optoelectronic devices that exploit the electron transporting properties of MeNH3PbI3 will be critically dependent upon the use of suitable barrier layers and device configurations to mitigate the oxygen sensitivity of this remarkable material.
TL;DR: In this article, a template-engaged strategy was proposed to transform Ni-Ni Prussian blue analogue (PBA) nanoplates into porous carbon coated nickel phosphides nanoprocessors with mixed phases of Ni5P4 and Ni2P. Benefitting from their structural merits and the in situ formed catalytically active oxidized nickel species, the as-derived Nickel phosphides manifest excellent electrocatalytic activity for OER.
Abstract: Electrochemical splitting of water provides an attractive way to produce hydrogen fuel. Unfortunately, the efficient and large-scale H2 production is still hindered by the sluggish kinetics of the oxygen evolution reaction (OER) at the anode side of a water electrolyzer. Starting from metal–organic frameworks (MOFs), we demonstrate a template-engaged strategy to transform Ni–Ni Prussian blue analogue (PBA) nanoplates into porous carbon coated nickel phosphides nanoplates with mixed phases of Ni5P4 and Ni2P. For comparison, NiO and Ni(OH)2 porous nanoplates with the similar morphology have also been synthesized from the same precursor. Benefitting from their structural merits and the in situ formed catalytically active oxidized nickel species, the as-derived nickel phosphides manifest excellent electrocatalytic activity for OER superior to NiO and Ni(OH)2.
TL;DR: In this paper, an assessment on the fundamentals such as feedstock types, the impact of different operating parameters, tar formation and cracking, and modelling approaches for biomass gasification is presented.
Abstract: Biomass gasification is a widely used thermochemical process for obtaining products with more value and potential applications than the raw material itself. Cutting-edge, innovative and economical gasification techniques with high efficiencies are a prerequisite for the development of this technology. This paper delivers an assessment on the fundamentals such as feedstock types, the impact of different operating parameters, tar formation and cracking, and modelling approaches for biomass gasification. Furthermore, the authors comparatively discuss various conventional mechanisms for gasification as well as recent advances in biomass gasification. Unique gasifiers along with multi-generation strategies are discussed as a means to promote this technology into alternative applications, which require higher flexibility and greater efficiency. A strategy to improve the feasibility and sustainability of biomass gasification is via technological advancement and the minimization of socio-environmental effects. This paper sheds light on diverse areas of biomass gasification as a potentially sustainable and environmentally friendly technology.
TL;DR: In this article, the authors review the dynamic field of crystalline silicon photovoltaics from a device-engineering perspective and give an up-to-date summary of promising recent pathways for further efficiency improvements and cost reduction employing novel carrierselective passivating contact schemes, as well as tandem multi-junction architectures, in particular those that combine silicon absorbers with organic-inorganic perovskite materials.
Abstract: With a global market share of about 90%, crystalline silicon is by far the most important photovoltaic technology today. This article reviews the dynamic field of crystalline silicon photovoltaics from a device-engineering perspective. First, it discusses key factors responsible for the success of the classic dopant-diffused silicon homojunction solar cell. Next it analyzes two archetypal high-efficiency device architectures – the interdigitated back-contact silicon cell and the silicon heterojunction cell – both of which have demonstrated power conversion efficiencies greater than 25%. Last, it gives an up-to-date summary of promising recent pathways for further efficiency improvements and cost reduction employing novel carrier-selective passivating contact schemes, as well as tandem multi-junction architectures, in particular those that combine silicon absorbers with organic–inorganic perovskite materials.
TL;DR: In this paper, an advanced bi-functional electrocatalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) was designed by simultaneously etching and doping a cobalt sulfides-graphene hybrid with NH3-plasma.
Abstract: Highly efficient electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have been regarded as the core elements in a wide range of renewable energy technologies. Surface engineering of the electrocatalysts is one of the most popular strategies to improve their catalytic activity. Herein, we, for the first time, designed an advanced bi-functional electrocatalyst for the ORR and OER by simultaneously etching and doping a cobalt sulfides–graphene hybrid with NH3-plasma. The graphene supported Co9S8 nanoparticles were prepared (denoted as Co9S8/G) first, followed by the NH3-plasma treatment, which could not only lead to nitrogen doping into both Co9S8 and graphene, but also partially etch the surface of both Co9S8 and graphene. The heteroatom doping could efficiently tune the electronic properties of Co9S8 and graphene, and the surface etching could expose more active sites for electrocatalysis, which can contribute significantly to the enhanced electrocatalytic performance for ORR and OER. The electrochemical results revealed that the etched and N-doped Co9S8/G shows excellent ORR activity, which is close to that of the commercial Pt/C catalyst, and great OER activity. The strategy developed here provides a novel and efficient approach to prepare hybrid bi-functional electrocatalysts for ORR and OER.
TL;DR: In this article, a ternary hybrid was constructed by in situ growth of cobalt selenide (Co0.85Se) nanosheets vertically oriented on electrochemically exfoliated graphene foil, with subsequent deposition of NiFe layered-double-hydroxide by a hydrothermal treatment.
Abstract: Developing cost-effective electrocatalysts for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in basic media is critical to renewable energy conversion technologies. Here, we report a ternary hybrid that is constructed by in situ growth of cobalt selenide (Co0.85Se) nanosheets vertically oriented on electrochemically exfoliated graphene foil, with subsequent deposition of NiFe layered-double-hydroxide by a hydrothermal treatment. The resulting 3D hierarchical hybrid, possessing a high surface area of 156 m2 g−1 and strong coupling effect, exhibits excellent catalytic activity for OER, which only requires overpotentials of 1.50 and 1.51 V to attain current densities of 150 and 250 mA cm−2, respectively. These overpotentials are much lower than those reported for other non-noble-metal materials and Ir/C catalysts. The hybrid also efficiently catalyzes HER in base with a current density of 10 mA cm−2 at an overpotential of −0.26 V. Most importantly, we achieve a current density of 20 mA cm−2 at 1.71 V by using the 3D hybrid as both a cathode and an anode for overall water splitting, which is well comparable to the integrated performance of Pt/C and Ir/C catalysts.
TL;DR: In this paper, a simple solution-processed technological approach for depositing SnO2 layers in planar PSCs yields a high stabilized power conversion efficiency close to 21%, exhibiting stable performance under real operating conditions for over 60 hours.
Abstract: Perovskite solar cells (PSCs) are one of the most promising lab-scale technologies to deliver inexpensive solar electricity. Low-temperature planar PSCs are particularly suited for large-scale manufacturing. Here, we propose a simple, solution-processed technological approach for depositing SnO2 layers. The use of these layers in planar PSCs yields a high stabilized power conversion efficiency close to 21%, exhibiting stable performance under real operating conditions for over 60 hours. In addition, this method yielded remarkable voltages of 1214 mV at a band gap of 1.62 eV (approaching the thermodynamic limit of 1.32 V) confirming the high selectivity of the solution-processed layers. PSCs aged under 1 sun illumination and maximum power point tracking showed a final PCE of 20.7% after ageing and dark storage, which is slightly higher than the original efficiency. This approach represents an advancement in the understanding of the role of electron selective layers on the efficiency and stability of PSCs. Therefore, the newly proposed approach constitutes a simple, scalable method paving the way for industrialization of perovskite solar cells.
TL;DR: In this article, the authors provide a perspective on solid oxide fuel cells operating at low temperature, defined here to be the range from ∼400 °C to 650 °C, with a focus on materials that have demonstrated good properties and cell performance.
Abstract: This article provides a perspective on solid oxide fuel cells operating at low temperature, defined here to be the range from ∼400 °C to 650 °C. These low-temperature solid oxide fuel cells (LT-SOFCs) have seen considerable research and development and are widely viewed as the “next generation” technology, following the 650–850 °C SOFCs that are currently undergoing commercialization. LT-SOFCs have potential advantages for conventional SOFC applications such as stationary power generation, and may be viable for new portable and transportation power applications, along with electrolytic fuel production and energy storage. The characteristics of electrolyte and electrode materials are reviewed, with a focus on materials that have demonstrated good properties and cell performance at low temperature. Only oxygen-ion-conducting electrolytes are considered here. Anode materials are discussed, primarily the various Ni–cermet anode compositions that yield good low-temperature performance. Mixed ionically and electronically conducting cathode materials are described in detail, reflecting the extensive research activity that has aimed at providing useful oxygen reduction kinetics at low operating temperature. Cell design, materials compatibility, processing methods, and resulting microstructures are discussed, along with their role in determining cell performance. Results from state of the art LT-SOFCs are presented, and future prospects are discussed.
TL;DR: In this article, a comprehensive review of various governing mechanisms and factors affecting the open-circuit voltage (VOC) in OSCs is presented, and a concise synthesis of intricate interdependencies among the factors influencing VOC is provided.
Abstract: Organic solar cells (OSCs) have developed progressively in efficiency over the last two decades. Though it is promising, this technology is still far from realizing its full prospect. One of the most important parameters that determine the efficiency of OSCs is the open-circuit voltage (VOC), which represents the maximum voltage a solar cell can provide to an external circuit. Light harvesting materials employed in OSCs have an optical band gap of around 1.7 to 2.1 eV and yet the VOC barely exceeds 1.0 V, which is approximately just half of the photon's original energy. By contrast, in inorganic counterparts such as Si, CIGS and GaAs, the difference is only 0.3 to 0.45 eV between the material bandgap and VOC. Hence, to achieve higher power conversion efficiencies (PCEs) in OSCs, a detailed understanding of the origins of VOC and the associated energetic loss mechanisms is indispensable. The presented review takes the opportunity to elaborate various governing mechanisms and factors affecting the VOC from a comprehensive yet insightful standpoint. This report also provides a concise synthesis of intricate interdependencies among the factors influencing VOC and highlights the potential research strategies to improve VOC, rendering possible pathways to facilitate the viable commercialization of OSCs.
TL;DR: In this paper, a universal strategy was proposed to directly synthesize single layer graphene encapsulating uniform earth-abundant 3D transition-metal nanoparticles such as Fe, Co, Ni and their alloys in a confined channel of mesoporous silica.
Abstract: The oxygen evolution reaction (OER) is recognized as a key half-reaction in water electrolysis for clean hydrogen energy, which is kinetically not favored and usually requires precious metal catalysts such as IrO2 and RuO2 to reduce the overpotential. The major challenge in using non-precious metals in place of these precious metal catalysts for OER is their low efficiency and poor stability, which urgently demand new concepts and strategies to tackle this issue. Herein, we report a universal strategy to directly synthesize single layer graphene encapsulating uniform earth-abundant 3d transition-metal nanoparticles such as Fe, Co, Ni and their alloys in a confined channel of mesoporous silica. The single atomic thickness of the graphene shell immensely promotes the electron transfer from the encapsulated metals to the graphene surface, which efficiently optimizes the electronic structure of the graphene surface and thereby triggers the OER activity of the inert graphene surface. We investigated a series of non-precious 3d metals encapsulated within single layer graphene, and found that the encapsulated FeNi alloy showed the best OER activity in alkaline solutions with only 280 mV overpotential at 10 mA cm−2, and also possessed a high durability after 10 000 cycles. Both the activity and durability of the non-precious catalyst even exceed that of the commercial IrO2 catalyst, showing great potential to replace precious metal catalysts in the OER.
TL;DR: In this paper, a comparison between photoelectrochemical (PEC) and photovoltaic-electrolytic (PV-E) solar-hydrogen production of 3.65 kilotons H2 per year was performed to assess the economics of each technology, and to provide a basis for comparison within the broader energy landscape.
Abstract: A technoeconomic analysis of photoelectrochemical (PEC) and photovoltaic-electrolytic (PV-E) solar-hydrogen production of 10000 kg H2 day−1 (3.65 kilotons per year) was performed to assess the economics of each technology, and to provide a basis for comparison between these technologies as well as within the broader energy landscape. Two PEC systems, differentiated primarily by the extent of solar concentration (unconcentrated and 10× concentrated) and two PV-E systems, differentiated by the degree of grid connectivity (unconnected and grid supplemented), were analyzed. In each case, a base-case system that used established designs and materials was compared to prospective systems that might be envisioned and developed in the future with the goal of achieving substantially lower overall system costs. With identical overall plant efficiencies of 9.8%, the unconcentrated PEC and non-grid connected PV-E system base-case capital expenses for the rated capacity of 3.65 kilotons H2 per year were $205 MM ($293 per m2 of solar collection area (mS−2), $14.7 WH2,P−1) and $260 MM ($371 mS−2, $18.8 WH2,P−1), respectively. The untaxed, plant-gate levelized costs for the hydrogen product (LCH) were $11.4 kg−1 and $12.1 kg−1 for the base-case PEC and PV-E systems, respectively. The 10× concentrated PEC base-case system capital cost was $160 MM ($428 mS−2, $11.5 WH2,P−1) and for an efficiency of 20% the LCH was $9.2 kg−1. Likewise, the grid supplemented base-case PV-E system capital cost was $66 MM ($441 mS−2, $11.5 WH2,P−1), and with solar-to-hydrogen and grid electrolysis system efficiencies of 9.8% and 61%, respectively, the LCH was $6.1 kg−1. As a benchmark, a proton-exchange membrane (PEM) based grid-connected electrolysis system was analyzed. Assuming a system efficiency of 61% and a grid electricity cost of $0.07 kWh−1, the LCH was $5.5 kg−1. A sensitivity analysis indicated that, relative to the base-case, increases in the system efficiency could effect the greatest cost reductions for all systems, due to the areal dependencies of many of the components. The balance-of-systems (BoS) costs were the largest factor in differentiating the PEC and PV-E systems. No single or combination of technical advancements based on currently demonstrated technology can provide sufficient cost reductions to allow solar hydrogen to directly compete on a levelized cost basis with hydrogen produced from fossil energy. Specifically, a cost of CO2 greater than ∼$800 (ton CO2)−1 was estimated to be necessary for base-case PEC hydrogen to reach price parity with hydrogen derived from steam reforming of methane priced at $12 GJ−1 ($1.39 (kg H2)−1). A comparison with low CO2 and CO2-neutral energy sources indicated that base-case PEC hydrogen is not currently cost-competitive with electrolysis using electricity supplied by nuclear power or from fossil-fuels in conjunction with carbon capture and storage. Solar electricity production and storage using either batteries or PEC hydrogen technologies are currently an order of magnitude greater in cost than electricity prices with no clear advantage to either battery or hydrogen storage as of yet. Significant advances in PEC technology performance and system cost reductions are necessary to enable cost-effective PEC-derived solar hydrogen for use in scalable grid-storage applications as well as for use as a chemical feedstock precursor to CO2-neutral high energy-density transportation fuels. Hence such applications are an opportunity for foundational research to contribute to the development of disruptive approaches to solar fuels generation systems that can offer higher performance at much lower cost than is provided by current embodiments of solar fuels generators. Efforts to directly reduce CO2 photoelectrochemically or electrochemically could potentially produce products with higher value than hydrogen, but many, as yet unmet, challenges include catalytic efficiency and selectivity, and CO2 mass transport rates and feedstock cost. Major breakthroughs are required to obtain viable economic costs for solar hydrogen production, but the barriers to achieve cost-competitiveness with existing large-scale thermochemical processes for CO2 reduction are even greater.
TL;DR: In this article, a simple strategy for fabricating edge site-enriched nickel-cobalt sulfide (Ni-Co-S) nanoparticles decorated on graphene frameworks to form integrated hybrid architectures (NiCo−S/G) via an in situ chemically converted method is reported.
Abstract: Tailor-made edge site-enriched inorganics coupled graphene hybrids hold a promising platform material for high-performance supercapacitors. Herein, we report a simple strategy for fabricating edge site-enriched nickel–cobalt sulfide (Ni–Co–S) nanoparticles decorated on graphene frameworks to form integrated hybrid architectures (Ni–Co–S/G) via an in situ chemically converted method. The Kirkendall effect-involved anion exchange reaction, e.g. the etching-like effort of the S2− ions, plays a crucial role for the formation of the edge site-enriched nanostructure. Density functional theory (DFT) calculations reveal that the Ni–Co–S edge sites have a high electrochemical activity and strong affinity for OH− in the electrolyte, which are responsible for the enhanced electrochemical performance. Benefiting from the integrated structures of Ni–Co–S nanoparticles and conductive graphene substrates, the resultant Ni–Co–S/G hybrid electrodes exhibit a high specific capacitance of 1492 F g−1 at the current density of 1 A g−1, a superior rate capability of 96% when the current density is increased to 50 A g−1, and excellent electrochemical stabilities. An asymmetric supercapacitor fabricated using the edge site-enriched Ni–Co–S/G hybrids as the positive electrode and porous carbon nanosheets (PCNS) as negative electrodes shows a high energy density of 43.3 W h kg−1 at a power density of 0.8 kW kg−1, and an energy density of 28.4 W h kg−1 can be retained even at a high power density of 22.1 kW kg−1.
TL;DR: In this article, a metal-rich form of Ni-selenide, nickel subselenides, Ni3Se2 has been investigated as a potential oxygen evolution electrocatalyst under alkaline conditions for the first time.
Abstract: A metal-rich form of Ni-selenide, nickel subselenide, Ni3Se2 has been investigated as a potential oxygen evolution electrocatalyst under alkaline conditions for the first time. The Ni3Se2 phase has a structure similar to the sulfur mineral heazlewoodite, which contains metal–metal bonding. The electrocatalytic activities of Ni3Se2 towards OER were seen to be at par with or even superior to the transition metal oxide based electrocatalyst in terms of onset overpotential for O2 evolution as well as overpotential to reach a current density of 10 mA cm−2 (observed at 290 mV). The electrocatalytic Ni3Se2 films were grown by electrodeposition on conducting substrates and the deposition parameters including the pH of the electrolytic bath, deposition potential, and substrate composition were seen to have some influence on the catalytic activity. So far, Ni3Se2 films deposited on the Au-coated Si substrate was seen to have the lowest overpotential. Annealing of the as-deposited electrocatalytic films in an inert atmosphere, enhanced their catalytic efficiencies by decreasing the overpotential (@10 mA cm−2) as well as increasing the current density. The structure and morphology of these films has been characterized by powder X-ray diffraction, scanning and transmission electron microscopy, Raman, and X-ray photoelectron spectroscopy. Catalytic activities were investigated through detailed electrochemical studies under alkaline conditions, including linear sweep voltammetry, chronoamperometric studies at constant potential, electrochemical surface area determination and calculation of the Tafel slope. The Faradaic efficiency of this catalyst has been estimated by reducing the evolved O2 in a RRDE set-up which also confirmed that the evolved gas was indeed O2. In addition to low overpotentials, these Ni3Se2 electrodeposited films were seen to be exceptionally stable under conditions of continuous O2 evolution for an extended period (42 h).
TL;DR: In this article, the recent progress in electrolyte additives used to improve performance and other properties, such as safety, is reviewed. But the focus of this paper is on specific electrode materials focusing on electrodes under current development.
Abstract: The need for lighter, thinner, and smaller products makes lithium ion batteries popular power sources for applications such as mobile phones, laptop computers, digital cameras, electric vehicles, and hybrid electric vehicles. For high power applications, the development of high capacity and high voltage electrode materials is in progress. Battery performance and safety issues are also related to the properties of the electrolytes used. To improve the properties of the electrolytes, small amounts of other components, known as electrolyte additives, are incorporated. This paper reviews the recent progress in electrolyte additives used to improve performance and other properties, such as safety. This review classifies the additives based on their functions and their effects on specific electrode materials focusing on electrodes under current development. From anodes: carbonaceous electrodes, silicon, tin and Li4Ti5O12; from layered cathodes: LiCoO2, Li-rich and LiNiyMnyCo1−2yO2 (NMC); from spinel: LiMn2O4, and from olivine: LiFePO4 are selected. We believe that this approach will help readers easily identify and understand the additives suitable for their target materials.
TL;DR: In this article, the authors explored the perovskites in a compositional space and derived the absorption and the emission behavior as well as the crystallographic properties of the pervskites.
Abstract: Lead halide perovskites have attracted considerable interest as photoabsorbers in PV-applications over the last few years. The most studied perovskite material achieving high photovoltaic performance has been methyl ammonium lead iodide, CH3NH3PbI3. Recently the highest solar cell efficiencies have, however, been achieved with mixed perovskites where iodide and methyl ammonium partially have been replaced by bromide and formamidinium. In this work, the mixed perovskites were explored in a systematic way by manufacturing devices where both iodide and methyl ammonium were gradually replaced by bromide and formamidinium. The absorption and the emission behavior as well as the crystallographic properties were explored for the perovskites in this compositional space. The band gaps as well as the crystallographic structures were extracted. Small changes in the composition of the perovskite were found to have a large impact on the properties of the materials and the device performance. In the investigated compositional space, cell efficiencies, for example, vary from a few percent up to 20.7%. From the perspective of applications, exchanging iodide with bromide is especially interesting as it allows tuning of the band gap from 1.5 to 2.3 eV. This is highly beneficial for tandem applications, and an empirical expression for the band gap as a function of composition was determined. Exchanging a small amount of iodide with bromide is found to be highly beneficial, whereas a larger amount of bromide in the perovskite was found to cause intense sub band gap photoemission with detrimental results for the device performance. This could be caused by the formation of a small amount of an iodide rich phase with a lower band gap, even though such a phase was not observed in diffraction experiments. This shows that stabilizing the mixed perovskites will be an important task in order to get the bromide rich perovskites, which has a higher band gap, to reach the same high performance obtained with the best compositions.
TL;DR: In this paper, a review of the advances since 2012 on high permeability polymeric membrane materials for CO2 separations is presented, which includes both polymeric membranes and polymer-inorganic hybrid membranes.
Abstract: Membrane processes have evolved as a competitive approach in CO2 separations compared with absorption and adsorption processes, due to their inherent attributes such as energy-saving and continuous operation. High permeability membrane materials are crucial to efficient membrane processes. Among existing membrane materials for CO2 separations, polymer-based materials have some intrinsic advantages such as good processability, low price and a readily available variety of materials. In recent years, enormous research effort has been devoted to the use of membrane technology for CO2 separations from diverse sources such as flue gas (mainly N2), natural gas (mainly CH4) and syngas (mainly H2). Polymer-based membrane materials occupy the vast majority of all the membrane materials. For large-scale CO2 separations, polymer-based membrane materials with high CO2 permeability and good CO2/gas selectivity are required. In 2012, we published a Perspective review in Energy & Environmental Science on high permeability polymeric membrane materials for CO2 separations. Since then, more rapid progress has been made and the research focus has changed significantly. This review summarises the advances since 2012 on high permeability polymer-based membrane materials for CO2 separations. The major features of this review are reflected in the following three aspects: (1) we cover polymer-based membrane materials instead of purely polymeric membrane materials, which encompass both polymeric membranes and polymer–inorganic hybrid membranes. (2) CO2 facilitated transport membrane materials are presented. (3) Biomimetism and bioinspired membrane concepts are incorporated. A number of representative examples of recent advances in high permeability polymer-based membrane materials is highlighted with some critical analysis, followed by a brief perspective on future research and development directions.
TL;DR: In this paper, a thermal gravimetric and differential thermal analysis (TG-DTA) coupled with quadrupole mass spectrometry (MS) and first principles calculations were employed to elucidate the chemical nature of released gases during the thermal decomposition of CH3NH3PbI3.
Abstract: Thermal gravimetric and differential thermal analysis (TG-DTA) coupled with quadrupole mass spectrometry (MS) and first principles calculations were employed to elucidate the chemical nature of released gases during the thermal decomposition of CH3NH3PbI3. In contrast to the common wisdom that CH3NH3PbI3 is decomposed into CH3NH2 and HI, the major gases were methyliodide (CH3I) and ammonia (NH3). We anticipate that our findings will provide new insights into further formulations of the perovskite active material and device design that can prevent methylammonium decomposition and thus increase the long-term stability of perovskite-based optoelectronic devices.
TL;DR: In this paper, the authors summarize the recent progress of ternary solar cells and try to concise out the scientific issues in preparing high performance TSSs, which is the best candidate due to the cell with a high power conversion efficiency, easy fabrication and low cost.
Abstract: The power conversion efficiency (PCE) of organic solar cells has been constantly refreshed in the past ten years from 4% up to 11% due to the contribution from the chemists on novel materials and the physicists on device engineering. For practical applications, a single bulk heterojunction structure may be the best candidate due to the cell with a high PCE, easy fabrication and low cost. Recently, ternary solar cells have attracted much attention due to enhanced photon harvesting by using absorption spectral or energy level complementary materials as the second donor or acceptor based on a single bulk heterojunction structure. For better promoting the development of ternary solar cells, we summarize the recent progress of ternary solar cells and try our best to concise out the scientific issues in preparing high performance ternary solar cells.
TL;DR: In this paper, the structural advantages of hollow host materials for high-performance Li-S batteries, together with a summary of recent advances in the design and synthesis of various hollow micro-/nanostructures with controlled shapes, tailored shell structures and designed chemical compositions are discussed.
Abstract: Lithium–sulfur (Li–S) batteries have attracted much attention in the field of electrochemical energy storage and conversion. As a vital part of the cathode electrode, the host materials of sulfur usually have a strong impact on the capacity, energy density, cycle life and Coulombic efficiency of Li–S batteries. With their unique physical and chemical properties, the rationally designed hollow nanostructures show conspicuous advantages as sulfur hosts, and have significantly improved the overall performance of Li–S cells. The scope of this review considers the unique structural advantages of hollow host materials for high-performance Li–S batteries, together with a summary of recent advances in the design and synthesis of various hollow micro-/nanostructures with controlled shapes, tailored shell structures and designed chemical compositions. Finally, we propose some emerging requirements of sulfur hosts which we hope will shed some light on the future development trend of hollow structures for advanced Li–S batteries.