Photoelectrode materials are the heart of photoelectrochemical (PEC) cells, which hold great promise to address global energy and environmental issues by converting solar energy into electricity or chemical fuels. In recent decades, significant research efforts have been devoted to the design and construction of photoelectrodes for the efficient generation and utilization of charge carriers to boost PEC performance. Herein, insights from a literature study on the relationship between the architecture and charge dynamics of photoelectrodes are presented. After briefly introducing the fundamental theories of charge dynamics in nanostructured photoelectrodes, the development of photoelectrode design in 1D polycrystalline nanotube arrays, 1D single‐crystalline nanowire arrays, and hierarchical and mesoporous nanowire arrays is reviewed with a focus on the interplay between architecture and charge transport properties. For each design, commonly used synthetic approaches and the corresponding charge transport properties are discussed. Subsequently, the applications of these photoelectrodes in PEC systems are summarized. In conclusion, future challenges in the rational design of photoelectrode architecture are presented. The basic relationships between the architectures and charge dynamics of photoelectrode materials discussed here are expected to provide pertinent guidance and a reference for future advanced material design targeting improved light energy conversion systems.
Thin film photoelectrodes for solar water splitting
Photoelectrochemical (PEC) water splitting has been intensively studied in the past decades as a promising method for large-scale solar energy storage. Among the various issues that limit the progress of this field, the lack of photoelectrode materials with suitable properties in all aspects of light absorption, charge separation and transport, and charge transfer is a key challenge, which has attracted tremendous research attention. A large variety of compositions, in different forms, have been tested. This review aims to summarize efforts in this area, with a focus on materials-related considerations. Issues discussed by this review include synthesis, optoelectronic properties, charge behaviors and catalysis. In the recognition that thin-film materials are representative model systems for the study of these issues, we elected to focus on this form, so as to provide a concise and coherent account on the different strategies that have been proposed and tested. Because practical implementation is of paramount importance to the eventual realization of using solar fuel for solar energy storage, we pay particular attention to strategies proposed to address the stability and catalytic issues, which are two key factors limiting the implementation of efficient photoelectrode materials. To keep the overall discussion focused, all discussions were presented within the context of water splitting reactions. How the thin-film systems may be applied for fundamental studies of the water splitting chemical mechanisms and how to use the model system to test device engineering design strategies are discussed.
more »
« less
- NSF-PAR ID:
- 10094841
- Date Published:
- Journal Name:
- Chemical Society Reviews
- Volume:
- 48
- Issue:
- 7
- ISSN:
- 0306-0012
- Page Range / eLocation ID:
- 2182 to 2215
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Rational Design of Photoelectrodes with Rapid Charge Transport for Photoelectrochemical Applicationsmore » « less
Abstract -
Conventional lithium-ion batteries are unable to meet the increasing demands for high-energy storage systems, because of their limited theoretical capacity. 1 In recent years, intensive attention has been paid to enhancing battery energy storage capability to satisfy the increasing energy demand in modern society and reduce the average energy capacity cost. Among the candidates for next generation high energy storage systems, the lithium sulfur battery is especially attractive because of its high theoretical specific energy (around 2600 W h kg-1) and potential cost reduction. In addition, sulfur is a cost effective and environmentally friendly material due to its abundance and low-toxicity. 2 Despite all of these advantages, the practical application of lithium sulfur batteries to date has been hindered by a series of obstacles, including low active material loading, poor cycle life, and sluggish sulfur conversion kinetics. 3 Achieving high mass loading cathode in the traditional 2D planar thick electrode has been challenged. The high distorsion of the traditional planar thick electrodes for ion/electron transfer leads to the limited utilization of active materials and high resistance, which eventually results in restricted energy density and accelerated electrode failure. 4 Furthermore, of the electrolyte to pores in the cathode and utilization ratio of active materials. Catalysts such as MnO 2 and Co dopants were employed to accelerate the sulfur conversion reaction during the charge and discharge process. 5 However, catalysts based on transition metals suffer from poor electronic conductivity. Other catalysts such as transition metal dopants are also limited due to the increased process complexities. . In addition, the severe shuttle effects in Li-S batteries may lead to fast failures of the battery. Constructing a protection layer on the separator for limiting the transmission of soluble polysulfides is considered an effective way to eliminate the shuttle phenomenon. However, the soluble sulfides still can largely dissolve around the cathode side causing the sluggish reaction condition for sulfur conversion. 5 To mitigate the issues above, herein we demonstrate a novel sulfur electrode design strategy enabled by additive manufacturing and oxidative vapor deposition (oCVD). Specifically, the electrode is strategically designed into a hierarchal hollow structure via stereolithography technique to increase sulfur usage. The active material concentration loaded to the battery cathode is controlled precisely during 3D printing by adjusting the number of printed layers. Owing to its freedom in geometry and structure, the suggested design is expected to improve the Li ions and electron transport rate considerably, and hence, the battery power density. The printed cathode is sintered at 700 °C at N 2 atmosphere to achieve carbonization of the cathode during which intrinsic carbon defects (e.g., pentagon carbon) as catalytic defect sites are in-situ generated on the cathode. The intrinsic carbon defects equipped with adequate electronic conductivity. The sintered 3D cathode is then transferred to the oCVD chamber for depositing a thin PEDOT layer as a protection layer to restrict dissolutions of sulfur compounds in the cathode. Density functional theory calculation reveals the electronic state variance between the structures with and without defects, the structure with defects demonstrates the higher kinetic condition for sulfur conversion. To further identify the favorable reaction dynamic process, the in-situ XRD is used to characterize the transformation between soluble and insoluble polysulfides, which is the main barrier in the charge and discharge process of Li-S batteries. The results show the oCVD coated 3D printed sulfur cathode exhibits a much higher kinetic process for sulfur conversion, which benefits from the highly tailored hierarchal hollow structure and the defects engineering on the cathode. Further, the oCVD coated 3D printed sulfur cathode also demonstrates higher stability during long cycling enabled by the oCVD PEDOT protection layer, which is verified by an absorption energy calculation of polysulfides at PEDOT. Such modeling and analysis help to elucidate the fundamental mechanisms that govern cathode performance and degradation in Li-S batteries. The current study also provides design strategies for the sulfur cathode as well as selection approaches to novel battery systems. References: Bhargav, A., (2020). Lithium-Sulfur Batteries: Attaining the Critical Metrics. Joule 4 , 285-291. Chung, S.-H., (2018). Progress on the Critical Parameters for Lithium–Sulfur Batteries to be Practically Viable. Advanced Functional Materials 28 , 1801188. Peng, H.-J.,(2017). Review on High-Loading and High-Energy Lithium–Sulfur Batteries. Advanced Energy Materials 7 , 1700260. Chu, T., (2021). 3D printing‐enabled advanced electrode architecture design. Carbon Energy 3 , 424-439. Shi, Z., (2021). Defect Engineering for Expediting Li–S Chemistry: Strategies, Mechanisms, and Perspectives. Advanced Energy Materials 11 . Figure 1more » « less
-
To address the critical issues in solar energy, the current research has focused on developing advanced solar harvesting materials that are low cost, lightweight, and environmentally friendly. Among many organic photovoltaics (PVs), the porphyrin compounds exhibit unique structural features that are responsible for strong ultraviolet (UV) and near infrared absorptions and high average visible transmittance, making them ideal candidates for solar-based energy applications. The porphyrin compounds have also been found to exhibit strong photothermal (PT) effects and recently applied for optical thermal insulation of building skins. These structural and optical properties of the porphyrin compounds enable them to function as a PT or a PV device upon sufficient solar harvesting. It is possible to develop a transparent porphyrin thin film with PT- and PV-dual-modality for converting sunlight to either electricity or thermal energy, which can be altered depending on energy consumption needs. A building skin can be engineered into an active device with the PT- and PV-dual modality for large-scale energy harvesting, saving, and generation. This review provides the current experimental results on the PT and PV properties of the porphyrin compounds such as chlorophyll and chlorophyllin. Their PT and PV mechanisms are discussed in correlations to their electronic structures. Also discussed are the synthesis routes, thin film deposition, and potential energy applications of the porphyrin compounds.more » « less
-
Biomimetic synaptic processes, which are imitated by functional memory devices in the computer industry, are a key focus of artificial intelligence (AI) research. It is critical to developing a memory technology that is compatible with Brain-Inspired Computing in order to eliminate the von Neumann bottleneck that restricts the efficiency of traditional computer designs. Due to restrictions such as high operation voltage, poor retention capacity, and high power consumption, silicon-based flash memory, which presently dominates the data storage devices market, is having difficulty meeting the requirements of future data storage device development. The developing resistive random-access memory (RRAM) has sparked intense investigation because of its simple two-terminal structure: two electrodes and a switching layer. RRAM has a resistive switching phenomenon which is a cycling behavior between the high resistance state and the low resistance state. This developing device type is projected to outperform traditional memory devices. Indium gallium zinc oxide (IGZO) has attracted great attention for the RRAM switching layer because of its high transparency and high atomic diffusion property of oxygen atoms. More importantly, by controlling the oxygen ratio in the sputter gas, its electrical properties can be easily tuned. The IGZO has been applied to the thin-film transistor (TFT), thus, it is very promising to integrate RRAM with TFT. In this work, we proposed IGZO-based RRAMs. ITO was chosen as the bottom electrode towards achieving a fully transparent memristor. And for the IGZO switching layer, we varied the O2/Ar ratio during the deposition to modify the oxygen vacancy of IGZO. Through the XPS measurement, we confirmed that the higher O2/Ar ratio can lower the oxygen vacancy concentration. We also chose ITO as the top electrode, for the comparison, two active metals copper and silver were tested for the top electrode materials. For our IGZO layer, the best ratio of O2/Ar is the middle value. And copper top electrode device has the most stable cycling switching and the silver one is perfect for large memory window, however, it encounters a stability issue. The optical transmission examination was performed using a UV-Vis spectrometer, and the average transmittance of the complete devices in the visible-light wavelength range was greater than 90%, indicating good transparency. 50nm, 100nm, and 150nm RS layers of IGZO RRAM were produced to explore the thickness dependency on the characteristics of the RS layer. Also, because the oxygen vacancy concentration influences the RS and RRAM performance, the oxygen partial pressure during IGZO sputtering was modified to maximize the property. Electrode selection is critical and can have a significant influence on the device's overall performance. As a result, Cu TE was chosen for our second type of device because Cu ion diffusion can aid in the development of conductive filaments (CF). Finally, between the TE and RS layers, a 5 nm SiO2 barrier layer was used to limit Cu penetration into the RS layer. Simultaneously, this SiO2 inserting layer can offer extra interfacial series resistance in the device, lowering the off current and, as a result, improving the on/off ratio and overall performance. In conclusion, transparent IGZO-based RRAMs have been created. The thickness of the RS layer and the sputtering conditions of the RS layer were modified to tailor the property of the RS layer. A series of TE materials and a barrier layer were incorporated into an IGZO-based RRAM and the performance was evaluated in order to design the TE material's diffusion capabilities to the RS layer and the BE. Our positive findings show that IGZO is a potential material for RRAM applications and overcoming the existing memory technology limitation.more » « less
-
more » « less
Abstract The development of rechargeable batteries using K ions as charge carriers has recently attracted considerable attention in the search for cost‐effective and large‐scale energy storage systems. In light of this trend, various materials for positive and negative electrodes are proposed and evaluated for application in K‐ion batteries. Here, a comprehensive review of ongoing materials research on nonaqueous K‐ion batteries is offered. Information on the status of new materials discovery and insights to help understand the K‐storage mechanisms are provided. In addition, strategies to enhance the electrochemical properties of K‐ion batteries and computational approaches to better understand their thermodynamic properties are included. Finally, K‐ion batteries are compared to competing Li and Na systems and pragmatic opportunities and future research directions are discussed.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C8CS00868J
