Coupled Solar Battery with 6.9 % Efficiency

Solar-to-electrochemical energy storage in solar batteries is an important solar utilization technology comparable to solar-to-electricity (solar cells) and solar-to-fuel (photocatalytic cells) conversion. Unlike the indirect approach of integrated solar flow batteries combining photoelectrodes with redox-electrodes, coupled solar batteries enable direct solar energy storage, but are hampered by low efficiency due to rapid charge recombination of materials and misaligned energy levels between electrodes. Herein, we propose a design for a coupled solar battery that intercouples two photo-coupled ion transfer (PCIT) reactions through electron-ion transfer upon co-photo-pumping of photoelectrochemical storage cathode and anode. We used a representative covalent organic framework (COF) to achieve efficient charge separation and directional charge transfer between two band-matched photoelectrochemical storage electrodes, with a photovoltage sufficient for COF dual-redox reactions. By pumping these electrodes, the coupled solar battery stores solar energy via two synergistic PCIT reactions of electron-proton-relayed COF oxidation and reduction, and the stored solar energy is released as electrochemical energy during COF regeneration in discharge while interlocking the loops. A breakthrough in efficiency (6.9 %) was achieved, adaptive to a large-area (56 cm²) tandem device. The presented photo-intercoupled electron-ion transfer (PIEIT) mechanism provides expandable paths toward practical solar-to-electrochemical energy storage.     

Enhanced Conversion Efficiency Enabled by Species Migration in Direct Solar Energy Storage

Solar energy can be stored via either an indirect route in which electricity is involved as an intermediate step, or a direct route that utilizes photogenerated charge carriers for direct solar energy conversion. In this study, we investigate the fundamental difference between the direct and indirect routes in solar energy conversion using a new photoelectrochemical energy storage cell (PESC) as a model device. This PESC centers on a liquid junction that utilizes CH₃NH₃PbI₃ perovskite to drive photoelectrochemical reactions of Benzoquinone (BQ) and Ferrocene (Fc) redox species. The experimental studies show that the equilibrium redox potentials are 0.1 V and −0.78 V (vs Ag/AgNO₃) for Fc⁺/Fc and BQ/BQ^.−, respectively, which would produce a theoretical open-circuit voltage of 0.88 V for the storage device. The physics-based computational analysis shows a relatively flat reaction rate distribution in the electrode for the indirect route; however, in the direct route the photoelectrochemical reaction rate is critically affected by electron concentration due to strong light absorption of the perovskite material, which has been shown to vary by at least 10-fold in the transverse direction across the photoelectrode. The drastic variation of reaction rate in the photoelectrode creates an electric field that is 7.5 times stronger than the bulk electrolyte, which causes the photo-converted reaction product (i. e., BQ^.−) to drift away from the photoelectrode thereby creating a constant reaction driving force. As a result, it has been shown that the intrinsic solar to chemical conversion (ISTC) efficiency improves by ∼40 % for the direct route compared to the indirect route at 0.05 mA/cm².     

Engineering Graphdiyne for Solar Photocatalysis

Graphdiyne (GDY) with a direct band gap, excellent carrier mobility and uniform pores, is regarded as a promising photocatalytic material for solar energy conversion, while the research on GDY in photocatalysis is a less developed field. Herein, the distinctive structure, adjustable band gap, and electronic properties of GDY for photocatalysis is firstly summarized. The construction and progress of GDY-based photocatalysts for solar energy conversion, including H₂ evolution reaction (HER), CO₂ reduction reaction (CO₂RR) and N₂ reduction reaction (NRR) are then elaborated. At last, the challenges and perspectives in developing GDY-based photocatalysts for solar fuel production are discussed. It is anticipated that a timely Minireview will be helpful for rapid progress of GDY in solar energy conversion.     

Solar energy absorption in norbornadiene-quadricyclane system through electron donating or withdrawing substituents1

An attempt is made to maximize the solar energy absorption in norbornadiene (1)-quadricyclane (2) system, through direct attachment of substituents at C1, C2, or C7 atoms of 1; calculating the corresponding energies at B3LYP/6-311++G** level of theory. The electron donating and electron withdrawing substituents of 1 _n-X, attached at C2, were suitable for both solar absorption bands and solar energy storage. DFT calculations indicate that the solar absorption bands of 1_2-X were shifted to the visible spectrum region through the electron withdrawing substituents more than through electron donating substituents.     

Semiconductor,molecular and hybrid systems for photoelectrochemical solar fuel production

The paper shortly reviews the basic direct approaches applied in searching for viable solutions to solar fuel production. These are generally distinguished in molecular and semiconductor(non-molecular)systems, however, hybrid strategies, proposed recently, have also been included. The most promising efforts are considered, highlighting key aspects and emerging critical issues. Special attention is paid to aspects such as electrode architecture, device design, and main differences in the scientific vision and challenges to directly produce solar fuels. This overview could be useful to orientate the readers in the wide panorama of research activities concerning water splitting, natural and artificial photosynthesis, and solar fuel production through the identification of common aspects, specialties and potentialities of the many initiatives and approaches that are developing worldwide in this field with the final aim to meet world energy demand.     

Conversion of Solar Energy to Fuels by Inorganic Heterogeneous Systems

Over the last several years,the need to find clean and renewable energy sources has increased rapidly because current fossil fuels will not only eventually be depleted,but their continuous combustion leads to a dramatic increase in the carbon dioxide amount in atmosphere.Utilisation of the Sun’s radiation can provide a solution to both problems.Hydrogen fuel can be generated by using solar energy to split water,and liquid fuels can be produced via direct CO2 photoreduction.This would create an essentially free carbon or at least carbon neutral energy cycle.In this tutorial review,the current progress in fuels’ generation directly driven by solar energy is summarised.Fundamental mechanisms are discussed with suggestions for future research.     

Understanding Surface Recombination Processes Using Intensity-Modulated Photovoltage Spectroscopy on Hematite Photoanodes for Solar Water Splitting

Converting solar energy into hydrogen through photoelectrochemical (PEC) water splitting offers a promising route towards a fully renewable energy economy. A fundamental understanding of photogenerated charge recombination processes in semiconducting photoelectrodes is a key consideration in optimizing solar water splitting cells and intensity-modulated photovoltage spectroscopy (IMVS) has recently emerged as a promising technique for gaining new insight. However, the interpretation of IMVS data under various conditions (that is, when photoelectrodes are in sacrificial electrolytes or employ catalytic overlayers) is not complete. Using IMVS data we present herein an analysis of charge recombination processes under open circuit conditions on a model photoanode system: nanostructured hematite. Employing two sacrificial oxidation conditions compared to standard water oxidation conditions, our IMVS results establish a direct correlation between surface recombination processes and the low frequency IMVS response. We found that surface intermediate states for water oxidation under open circuit condition exhibit a lifetime of 229 ms under standard illumination conditions. Applying a nickel iron oxide overlayer also gives insight into surface passivation effects through IMVS analysis of photoanode system.     

Thermochemical solar hydrogen generation

Solar direct, indirect and hybrid thermochemical processes are presented for the generation of hydrogen and compared to alternate solar hydrogen processes. A hybrid solar thermal/electrochemical process combines efficient photovoltaics and concentrated excess sub-bandgap heat into highly efficient elevated temperature solar electrolysis of water and generation of H2 fuel utilizing the thermodynamic temperature induced decrease of E(H2O) with increasing temperature. Theory and experiment is presented for this process using semiconductor bandgap restrictions and combining photodriven charge transfer, with excess sub-bandgap insolation to lower the water potential, and their combination into highly efficient solar generation of H2 is attainable. Fundamental water thermodynamics and solar photosensitizer constraints determine solar energy to hydrogen fuel conversion efficiencies in the 50% range over a wide range of insolation, temperature, pressure and photosensitizer bandgap conditions.     

Visible‐Light‐Responsive Photoanodes for Highly Active,Stable Water Oxidation

Solar energy is a natural and effectively permanent resource and so the conversion of solar radiation into chemical or electrical energy is an attractive, although challenging, prospect. Photo‐electrochemical (PEC) water splitting is a key aspect of producing hydrogen from solar power. However, practical water oxidation over photoanodes (in combination with water reduction at a photocathode) in PEC cells is currently difficult to achieve because of the large overpotentials in the reaction kinetics and the inefficient photoactivity of the semiconductors. The development of semiconductors that allow high solar‐to‐hydrogen conversion efficiencies and the utilization of these materials in photoanodes will be a necessary aspect of achieving efficient, stable water oxidation. This Review discusses advances in water oxidation activity over photoanodes of n‐type visible‐light‐responsive (oxy)nitrides and oxides.     

Direct Solar‐to‐Electrochemical Energy Storage in a Functionalized Covalent Organic Framework

A covalent organic framework integrating naphthalenediimide and triphenylamine units (NT‐COF) is presented. Two‐dimensional porous nanosheets are packed with a high specific surface area of 1276 m² g^?1. Photo/electrochemical measurements reveal the ultrahigh efficient intramolecular charge transfer from the TPA to the NDI and the highly reversible electrochemical reaction in NT‐COF. There is a synergetic effect in NT‐COF between the reversible electrochemical reaction and intramolecular charge transfer with enhanced solar energy efficiency and an accelerated electrochemical reaction. This synergetic mechanism provides the key basis for direct solar‐to‐electrochemical energy conversion/storage. With the NT‐COF as the cathode materials, a solar Li‐ion battery is realized with decreased charge voltage (by 0.5 V), increased discharge voltage (by 0.5 V), and extra 38.7 % battery efficiency.     

Semiconducting nanocrystals,conjugated polymers,and conjugated polymer/nanocrystal nanohybrids and their usage in solar cells

As one of the major renewable energy sources, solar energy has the potential to become an essential component of future global energy production. With the increasing demand in energy, the harvesting of solar energy using inexpensive materials and manufacturing methods has attracted considerable attention. Organic/inorganic (i.e., conjugated polymer/nanocrystal (CP/NC)) nanohybrid solar cell, including both physically mixed CP/NC composites and covalently linked CP-NC nanocomposites, is one of the several most promising alternative, cost-effective concepts for solar-to-electric energy conversion that has been offered to challenge conventional Si solar cells over the past decade. It has low fabrication cost and capability of large-scale production. However, to date, the highest power conversion efficiency (PCE) of organic/inorganic nanohybrid solar cells has been reported to be only 5.5%, which is still lower than the theoretical prediction of more than 10%. Several problems, i. e., microscopic phase separation of semiconducting CPs and NCs, low charge injection, and low carrier collection, have not been well addressed. More research remains to be done to improve the efficiency of CP/NC nanohybrid solar cells. In this review article, the recent advances in solving these problems were discussed. For the CP/NC solar cells prepared by physically mixing electron donating CP and electron accepting NC (i.e., forming CP/NC composites), methods involving the use of solvent mixtures and ligand modification to control the phase separation at the nanoscale are discussed; the implications of intriguing anisotropic NCs as well as their assemblies (i.e., NC arrays) on improving the charge collection are presented. For newly developed CP/NC solar cells prepared by chemically tethering CP chains on the NC surface (i.e., yielding CP-NC nanocomposites, thereby preventing microscopic phase separation of CP and NC and improving their electronic interaction), recent strategies on the synthesis of such nanocomposites and their photovoltaic performance are discussed.     

TiO_2-based materials for photocatalytic hydrogen production

Hydrogen, the cleanest and most promising energy vector, can be produced by solar into chemical energy conversion, either by the photocatalytic direct splitting of water into H_2 and O_2, or, more efficiently,in the presence of sacrificial reagents, e.g., in the so-called photoreforming of organics. Efficient photocatalytic materials should not only be able to exploit solar radiation to produce electron–hole pairs, but also ensure enough charge separation to allow electron transfer reactions, leading to solar energy driven thermodynamically up-hill processes. Recent achievements of our research group in the development and testing of innovative TiO_2-based photocatalytic materials are presented here, together with an overview on the mechanistic aspects of water photosplitting and photoreforming of organics. Photocatalytic materials were either(i) obtained by surface modification of commercial photocatalysts, or produced(ii) in powder form by different techniques, including traditional sol gel synthesis, aiming at engineering their electronic structure, and flame spray pyrolysis starting from organic solutions of the precursors, or(iii) in integrated form, to produce photoelectrodes within devices, by radio frequency magnetron sputtering or by electrochemical growth of nanotube architectures, or photocatalytic membranes, by supersonic cluster beam deposition.     

Routes to copper zinc tin sulfide Cu2ZnSnS4 a potential material for solar cells

Power generation through photovoltaics (PV) has been growing at an average rate of 40% per year over the last decade; but has largely been fuelled by conventional Si-based technologies. Such cells involve expensive processing and many alternatives use either toxic, less-abundant and or expensive elements. Kesterite Cu(2)ZnSnS(4) (CZTS) has been identified as a solar energy material composed of both less toxic and more available elements. Power conversion efficiencies of 8.4% (vacuum processing) and 10.1% (non-vacuum processing) from cells constructed using CZTS have been achieved to date. In this article, we review various deposition methods for CZTS thin films and the synthesis of CZTS nanoparticles. Studies of direct relevance to solar cell applications are emphasised and characteristic properties are collated.     

Photoinduced Oxygen Reduction Reaction Boosts the Output Voltage of a Zinc–Air Battery

Utilization of solar energy is of great interest for a sustainable society, and its conversion into electricity in a compact battery is challenging. Herein, a zinc–air battery with the polymer semiconductor polytrithiophene (pTTh) as the cathode is reported for direct conversion of photoenergy into electric energy. Upon irradiation, photoelectrons are generated in the conduction band (CB) of pTTh and then injected into the π_2p* orbitals of O₂ for its reduction to HO₂^?, which is disproportionated to OH^? and drives the oxidation of Zn to ZnO at the anode. The discharge voltage was significantly increased to 1.78 V without decay during discharge–charge cycles over 64 h, which corresponds to an energy density increase of 29.0 % as compared to 1.38 V for a zinc–air battery with state‐of‐the‐art Pt/C. The zinc–air battery with an intrinsically different reaction scheme for simultaneous conversion of chemical and photoenergy into electric energy opens a new pathway for utilization of solar energy.     

Synthesis and properties of 3,4-dioxythiophene and 1,4-dialkoxybenzene based copolymers via direct C?H arylation: Dopant-free hole transport material for perovskite solar cells

Direct C H arylation coupling reaction has gained significant importance in synthesis of conjugated polymers for organic electronic applications. We report here a facile and straightforward method called “direct C H arylation” reaction to synthesize conjugated 3,4-dioxythiophene and 1,4-dialkoxybenzene based copolymers as hole transport material (HTM) for perovskite solar cells. Two electron-rich conjugated polymers P1-2 were synthesized, in which 1,4-dibromo-2,5-bis(dodecyloxy)benzene and 3,4-dialkoxy-thiophene units were used for polymerization. The resulting polymers were characterized and exhibited high solubility in organic solvents. Electrochemical and optical characterizations were carried out by cyclic voltammetry and UV–Vis–NIR absorption spectroscopy and found that these polymers show higher-lying HOMO energy levels with wide band gap. Density functional theory calculation was performed on these polymers ( P1-2 ) and correlated with our experimental results. Finally, perovskite solar cells were fabricated by solution-processable deposition of P1-2 as dopant-free HTM with device geometry ITO/SnO₂/Perovskite/HTM( P1 / P2 )/Ag and achieved a maximum power conversion efficiency of 5.28%. This study provides information on designing and simple preparation by direct C H arylation reaction of higher-lying HOMO energy level polymer as HTM for perovskite solar cells.     

Irrungen und Wirrungen um Biokraftstoffe. Biokraftstoffe sind nicht per se nachhaltig

The annual photosynthesis on the Earth exceeds the anthropogenic CO₂ production. This suggests an energetic use of biomass and has greatly promoted the development of biofuels. In many cases, however, the use of biofuels is breaking the rules of sustainability. To meet the world's energy demand from biomass would require the total available agricultural land. This insight has a critical plate or tank discussion triggered. Energetically and environmentally more efficient than the use of biofuels would be the cultivation of fast‐growing timber and its direct use in coal power plants for electricity production. By far the most efficient use of solar energy is provided by photovoltaic and solar heat use. Because of their high energy density liquid second‐generation biofuels will be applied also in future in such cases where electrical mobility has its limits.     

宽光谱太阳能电池

太阳能电池的光谱响应特性和光电转换效率与光伏材料的微观能带结构及其宏观组装方式密切相关。无论使用哪种光伏材料,普通单结或单层太阳能电池都只能对部分波段的太阳光进行有效利用。宽光谱研究的目标是要使太阳能电池更好地利用太阳光谱所覆盖的全部波段范围的能量,从而提高太阳能电池光电转换效率。本文从化学角度综述了实现宽光谱太阳能电池的基本方法和当前的研究进展,其中包括叠层太阳能电池、中间带太阳能电池、量子点太阳能电池、热光伏太阳能电池、上转换和下转换、分子基柔性太阳能电池等方法。     

Solar cells from colloidal nanocrystals: Fundamentals,materials, devices,and economics

Recent advances in colloidal science are having a dramatic impact on the development of next generation low-cost and/or high-efficiency solar cells. Simple and safe solution phase syntheses that yield monodisperse, passivated, non-aggregated semiconductor nanocrystals of high optoelectronic quality have opened the door to several routes to new photovoltaic devices which are currently being explored. In one route, colloidal semiconductor nanocrystal “inks” are used primarily to lower the fabrication cost of the photoabsorbing layer of the solar cell. Nanocrystals are cast onto a substrate to form either an electronically coupled nanocrystal array or are sintered to form a bulk semiconductor layer such that the bandgap of either is optimized for the solar spectrum (1.0–1.6 eV if the photon to carrier quantum yields less than 100%). The sintered devices (and without special efforts, the nanocrystal array devices as well) are limited to power conversion efficiencies less than the Shockley–Queisser limit of 33.7% but may possibly be produced at a fraction of the manufacturing cost of an equivalent process that uses vacuum-based deposition for the absorber layer. However, some quantum confined nanocrystals display an electron-hole pair generation phenomena with greater than 100% quantum yield, called “multiple exciton generation” (MEG) or “carrier multiplication” (CM). These quantum dots are being used to develop solar cells that theoretically may exceed the Shockley–Queisser limit. The optimum bandgap for such photoabsorbers shifts to smaller energy (0.6–1.1 eV), and thus colloidal quantum dots of low bandgap materials such as PbS and PbSe have been the focus of research efforts, although multiple exciton generation has also been observed in several other systems including InAs and Si. This review focuses on the fundamental physics and chemistry of nanocrystal solar cells and on the device development efforts to utilize colloidal nanocrystals as the key component of the absorber layer in next generation solar cells. Development efforts are put into context on a quantitative and up-to-date map of solar cell cost and efficiency to clarify efforts and identify potential opportunities in light of technical limitations and recent advances in existing technology. Key nanocrystal/material selection issues are discussed, and finally, we present four grand challenges that must be addressed along the path to developing low-cost high-efficiency nanocrystal based solar cells.     

太阳能分解水制氢最近进展:光催化、光电催化及光伏-光电耦合途径

能源是人类生存和发展的物质基础,太阳能作为最丰富的清洁可再生能源之一,其开发利用受到了世界范围内的广泛关注.通过光催化分解水制氢将太阳能以化学能的形式储存起来不仅能利用太阳能制取高燃烧值的氢能,同时氢能可与CO2综合利用结合起来,在减少碳排放的同时,生成高附加值的化学品,实现碳氢资源的优化利用.光催化分解水制氢在过去的几年里取得了长足的进步,本综述从三种研究广泛的太阳能光催化分解水制氢途径(即光催化、光电催化以及光伏-光电耦合途径)入手,分别简要介绍了太阳能分解水制氢在近几年取得的最新研究进展.利用纳米粒子悬浮体系进行光催化分解水制氢成本低廉、易于规模化放大,被认为是未来应用最可行的方式之一,但是太阳能转化利用效率还偏低.最新报道的SrTiO3:La,Rh/Au/BiVO4:Mo光催化剂其太阳能到氢能(STH)转化效率已超过了1.0%,相比之前报道的大多数光催化剂体系有了数量级的飞跃,让人们对太阳能光催化分解水制氢未来的规模化应用看到了希望.高效宽光谱响应的光催化剂、高效电荷分离策略、新型高效助催化剂以及气体分离新方法和新材料等,均是粉末光催化剂体系研究最为关键的问题;光电催化分解水在过去2–3年内发展迅速,在一些典型的光阳极半导体材料(如BiVO4和Ta3N5等)体系上太阳能利用效率超过2.0%以上.最新研究发现,在Ta3N5光阳极的研究中,通过在光电极表面合理设计和构筑空穴传输层和电子阻挡层等策略,光电流和电极稳定性均可得到大幅度提升,光电流大小甚至可接近Ta3N5材料的理论极限电流.如果能进一步在过电位和电极稳定性上取得突破,该体系的STH转化效率还会得到大幅度改进.此外,光阴极的研究也越来越受到了研究者的关注;光伏-光电耦合体系在三种途径里面太阳能制氢效率最高,在多个体系上已超过10%以上,最近报道的利用多结GaInP/GaAs/Ge电池与Ni电催化剂耦合,其太阳能制氢效率可达到22.4%.虽然该种制氢途径的效率已超过其工业化应用的要求,但是光伏电池的成本(尤其是多结GaAs太阳电池)极大限制了其大面积规模化应用,同时还要考虑电催化剂的成本和效率等,光伏-光电耦合制氢是成本最高的太阳能制氢途径.需要指出的是,光伏-光电耦合制氢有望在一些特殊的领域最先取得实际应用,如为外太空航天器、远洋航海以及孤立海岛等传统能源无法满足的地方提供能源供给.总之,太阳能分解水制氢研究取得了一系列重要进展,太阳能制氢效率得到了大幅度提升,也是目前世界范围内关注的研究热点之一,不仅具有强的潜在工业应用背景,更为基础科学提供了诸多新的研究课题.这一极具挑战的研究领域,在先进技术快速发展和基础科学问题认识不断提高的基础上,不久的将来,有望在不久的将来在基础科学和应用研究方面取得重大突破.     

Photoinduced Betaine Generation for Efficient Photothermal Energy Conversion

The conversion of solar energy to thermal, chemical, or electrical energy attracts great attention in chemistry and physics. There has been a considerable effort for the efficient extraction of photons throughout the entire solar spectrum. In this work light energy was efficiently harvested by using a long-lived betaine photogenerated from an acridinium-based electron donor–acceptor dyad. The photothermal energy-conversion efficiency of the dyad is significantly enhanced by simultaneous illumination with blue (420–440 nm) and yellow (>480 nm) light in comparison with the sum of the conversion efficiencies for individual illumination with blue or yellow light. The enhanced photothermal effect is due to the photogenerated betaine, which absorbs longer-wavelength light than the dyad, and thus the dyad–betaine combination is promising for efficient photothermal energy conversion. The mechanisms of betaine generation and energy conversion are discussed on the basis of steady-state and transient spectral measurements.