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Nanomaterials
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Nanostructured Materials for Energy Storage and Conversion
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Nanostructured Materials for Energy Storage and Conversion

A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Energy and Catalysis".

Deadline for manuscript submissions: closed (31 May 2021) | Viewed by 34993

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editor

Dr. Luca Pasquini

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Guest Editor
Department of Physics and Astronomy, University of Bologna, Via Zamboni, 33, 40126 Bologna, BO, Italy
Interests: nanoparticles; alloys; grain boundaries; nanostructured materials; hydrogen storage; magnesium; material characterization; X-ray diffraction; microstructure
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The conversion and storage of renewable energy sources is an urgent challenge we have to confront in order to transition from a fossil fuel based economy to a low-carbon society. The development of new materials with improved characteristics is a key issue to enable this epochal transformation. Nanostructured materials, by virtue of their high surface-to volume ratio and short migration distances, are an attractive solution to achieve higher conversion efficiencies as well as enhanced power and energy density.

The aim of this special issue is to collect state-of-the-art contributions related to various applications of nanomaterials in the field of energy conversion and storage. Examples include, but are not limited to, electrode and electrolyte materials for batteries, supercapacitors, solid-state hydrogen storage, nanostructured solar cells, heterogeneous catalysts, artificial photosynthesis, and plasmonics. Nanoscale features should be central to the properties of materials discussed in the manuscripts. The authors are encouraged to highlight the advantageous features of nanomaterials as well as to address their current limitations and challenges.

Prof. Luca Pasquini
Guest Editor

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Keywords

  • energy storage
  • energy conversion
  • nanostructures
  • interfaces
  • size effects
  • (photo)electrochemistry
  • hydrogen
  • solar fuels
  • nanocatalysts
  • plasmonics

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Published Papers (11 papers)

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Editorial

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3 pages, 191 KiB  
Editorial
Nanostructured Materials for Energy Storage and Conversion
by Luca Pasquini
Nanomaterials 2022, 12(9), 1583; https://doi.org/10.3390/nano12091583 - 7 May 2022
Cited by 8 | Viewed by 1712
Abstract
The conversion and storage of renewable energy sources is an urgent challenge that we need to tackle to transition from a fossil fuel-based economy to a low-carbon society [...] Full article
(This article belongs to the Special Issue Nanostructured Materials for Energy Storage and Conversion)

Research

Jump to: Editorial, Other

9 pages, 2210 KiB  
Article
Highly Ordered SnO2 Nanopillar Array as Binder-Free Anodes for Long-Life and High-Rate Li-Ion Batteries
by Liyufen Dai, Xiangli Zhong, Juan Zou, Bi Fu, Yong Su, Chuanlai Ren, Jinbin Wang and Gaokuo Zhong
Nanomaterials 2021, 11(5), 1307; https://doi.org/10.3390/nano11051307 - 15 May 2021
Cited by 14 | Viewed by 2611
Abstract
SnO2, a typical transition metal oxide, is a promising conversion-type electrode material with an ultrahigh theoretical specific capacity of 1494 mAh g−1. Nevertheless, the electrochemical performance of SnO2 electrode is limited by large volumetric changes (~300%) during the [...] Read more.
SnO2, a typical transition metal oxide, is a promising conversion-type electrode material with an ultrahigh theoretical specific capacity of 1494 mAh g−1. Nevertheless, the electrochemical performance of SnO2 electrode is limited by large volumetric changes (~300%) during the charge/discharge process, leading to rapid capacity decay, poor cyclic performance, and inferior rate capability. In order to overcome these bottlenecks, we develop highly ordered SnO2 nanopillar array as binder-free anodes for LIBs, which are realized by anodic aluminum oxide-assisted pulsed laser deposition. The as-synthesized SnO2 nanopillar exhibit an ultrahigh initial specific capacity of 1082 mAh g−1 and maintain a high specific capacity of 524/313 mAh g−1 after 1100/6500 cycles, outperforming SnO2 thin film-based anodes and other reported binder-free SnO2 anodes. Moreover, SnO2 nanopillar demonstrate excellent rate performance under high current density of 64 C (1 C = 782 mA g−1), delivering a specific capacity of 278 mAh g−1, which can be restored to 670 mAh g−1 after high-rate cycling. The superior electrochemical performance of SnO2 nanoarray can be attributed to the unique architecture of SnO2, where highly ordered SnO2 nanopillar array provided adequate room for volumetric expansion and ensured structural integrity during the lithiation/delithiation process. The current study presents an effective approach to mitigate the inferior cyclic performance of SnO2-based electrodes, offering a realistic prospect for its applications as next-generation energy storage devices. Full article
(This article belongs to the Special Issue Nanostructured Materials for Energy Storage and Conversion)
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17 pages, 4177 KiB  
Article
Structural and Electrochemical Analysis of CIGS: Cr Crystalline Nanopowders and Thin Films Deposited onto ITO Substrates
by Suzan Saber, Bernabé Marí, Andreu Andrio, Jorge Escorihuela, Nagwa Khattab, Ali Eid, Amany El Nahrawy, Mohamed Abo Aly and Vicente Compañ
Nanomaterials 2021, 11(5), 1093; https://doi.org/10.3390/nano11051093 - 23 Apr 2021
Cited by 6 | Viewed by 2421
Abstract
A new approach for the synthesis of nanopowders and thin films of CuInGaSe2 (CIGS) chalcopyrite material doped with different amounts of Cr is presented. The chalcopyrite material CuInxGa1 − xSe2 was doped using Cr to form a [...] Read more.
A new approach for the synthesis of nanopowders and thin films of CuInGaSe2 (CIGS) chalcopyrite material doped with different amounts of Cr is presented. The chalcopyrite material CuInxGa1 − xSe2 was doped using Cr to form a new doped chalcopyrite with the structure CuInxCryGa1 − x − ySe2, where x = 0.4 and y = 0.0, 0.1, 0.2, or 0.3. The electrical properties of CuInx CryGa1 − x − ySe2 are highly dependent on the Cr content and results show these materials as promising dopants for the fabrication thin film solar cells. The CIGS nano-precursor powder was initially synthesized via an autoclave method, and then converted into thin films over transparent substrates. Both crystalline precursor powders and thin films deposited onto ITO substrates following a spin-coating process were subsequently characterized using XRD, SEM, HR-TEM, UV–visible and electrochemical impedance spectroscopy (EIS). EIS measurement was performed to evaluate the dc-conductivity of these novel materials as conductive films to be applied in solar cells. Full article
(This article belongs to the Special Issue Nanostructured Materials for Energy Storage and Conversion)
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11 pages, 3544 KiB  
Article
On Tailoring Co-Precipitation Synthesis to Maximize Production Yield of Nanocrystalline Wurtzite ZnS
by Radenka Krsmanović Whiffen, Amelia Montone, Loris Pietrelli and Luciano Pilloni
Nanomaterials 2021, 11(3), 715; https://doi.org/10.3390/nano11030715 - 12 Mar 2021
Cited by 15 | Viewed by 2394
Abstract
Pyroelectric materials can harvest energy from naturally occurring ambient temperature changes, as well as from artificial temperature changes, notably from industrial activity. Wurtzite- based materials have the advantage of being cheap, non-toxic, and offering excellent opto-electrical properties. Due to their non-centrosymmetric nature, all [...] Read more.
Pyroelectric materials can harvest energy from naturally occurring ambient temperature changes, as well as from artificial temperature changes, notably from industrial activity. Wurtzite- based materials have the advantage of being cheap, non-toxic, and offering excellent opto-electrical properties. Due to their non-centrosymmetric nature, all wurtzite crystals have both piezoelectric and pyroelectric properties. Nanocrystalline wurtzite ZnS, being a room temperature stable material, by contrast to its bulk counterpart, is interesting due to its still not well-explored potential in piezoelectric and pyroelectric energy harvesting. An easy synthesis method—a co-precipitation technique—was selected and successfully tailored for nanocrystalline wurtzite ZnS production. ZnS nanopowder with nanoparticles of 3 to 5 nm in size was synthesized in ethyl glycol under medium temperature conditions using ZnCl2 and thiourea as the sources of Zn and S, respectively. The purified and dried ZnS nanopowder was characterized by conventional methods (XRD, SEM, TEM, TG and FTIR). Finally, a constructed in-house pilot plant that is able to produce substantial amounts of wurtzite ZnS nanopowder in an environmentally friendly and cost-effective way is introduced and described. Full article
(This article belongs to the Special Issue Nanostructured Materials for Energy Storage and Conversion)
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14 pages, 3315 KiB  
Article
Impact of Surface Chemistry of Silicon Nanoparticles on the Structural and Electrochemical Properties of Si/Ni3.4Sn4 Composite Anode for Li-Ion Batteries
by Tahar Azib, Claire Thaury, Fermin Cuevas, Eric Leroy, Christian Jordy, Nicolas Marx and Michel Latroche
Nanomaterials 2021, 11(1), 18; https://doi.org/10.3390/nano11010018 - 24 Dec 2020
Cited by 4 | Viewed by 3139
Abstract
Embedding silicon nanoparticles in an intermetallic matrix is a promising strategy to produce remarkable bulk anode materials for lithium-ion (Li-ion) batteries with low potential, high electrochemical capacity and good cycling stability. These composite materials can be synthetized at a large scale using mechanical [...] Read more.
Embedding silicon nanoparticles in an intermetallic matrix is a promising strategy to produce remarkable bulk anode materials for lithium-ion (Li-ion) batteries with low potential, high electrochemical capacity and good cycling stability. These composite materials can be synthetized at a large scale using mechanical milling. However, for Si-Ni3Sn4 composites, milling also induces a chemical reaction between the two components leading to the formation of free Sn and NiSi2, which is detrimental to the performance of the electrode. To prevent this reaction, a modification of the surface chemistry of the silicon has been undertaken. Si nanoparticles coated with a surface layer of either carbon or oxide were used instead of pure silicon. The influence of the coating on the composition, (micro)structure and electrochemical properties of Si-Ni3Sn4 composites is studied and compared with that of pure Si. Si coating strongly reduces the reaction between Si and Ni3Sn4 during milling. Moreover, contrary to pure silicon, Si-coated composites have a plate-like morphology in which the surface-modified silicon particles are surrounded by a nanostructured, Ni3Sn4-based matrix leading to smooth potential profiles during electrochemical cycling. The chemical homogeneity of the matrix is more uniform for carbon-coated than for oxygen-coated silicon. As a consequence, different electrochemical behaviors are obtained depending on the surface chemistry, with better lithiation properties for the carbon-covered silicon able to deliver over 500 mAh/g for at least 400 cycles. Full article
(This article belongs to the Special Issue Nanostructured Materials for Energy Storage and Conversion)
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16 pages, 28691 KiB  
Article
On the Formation of Black Silicon Features by Plasma-Less Etching of Silicon in Molecular Fluorine Gas
by Bishal Kafle, Ahmed Ismail Ridoy, Eleni Miethig, Laurent Clochard, Edward Duffy, Marc Hofmann and Jochen Rentsch
Nanomaterials 2020, 10(11), 2214; https://doi.org/10.3390/nano10112214 - 6 Nov 2020
Cited by 11 | Viewed by 3223
Abstract
In this paper, we study the plasma-less etching of crystalline silicon (c-Si) by F2/N2 gas mixture at moderately elevated temperatures. The etching is performed in an inline etching tool, which is specifically developed to lower costs for products needing a [...] Read more.
In this paper, we study the plasma-less etching of crystalline silicon (c-Si) by F2/N2 gas mixture at moderately elevated temperatures. The etching is performed in an inline etching tool, which is specifically developed to lower costs for products needing a high volume manufacturing etching platform such as silicon photovoltaics. Specifically, the current study focuses on developing an effective front-side texturing process on Si(100) wafers. Statistical variation of the tool parameters is performed to achieve high etching rates and low surface reflection of the textured silicon surface. It is observed that the rate and anisotropy of the etching process are strongly defined by the interaction effects between process parameters such as substrate temperature, F2 concentration, and process duration. The etching forms features of sub-micron dimensions on c-Si surface. By maintaining the anisotropic nature of etching, weighted surface reflection (Rw) as low as Rw < 2% in Si(100) is achievable. The lowering of Rw is mainly due to the formation of deep, density grade nanostructures, so-called black silicon, with lateral dimensions that are smaller to the major wavelength ranges of interest in silicon photovoltaics. Full article
(This article belongs to the Special Issue Nanostructured Materials for Energy Storage and Conversion)
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17 pages, 2890 KiB  
Article
Turning Waste into Useful Products by Photocatalysis with Nanocrystalline TiO2 Thin Films: Reductive Cleavage of Azo Bond in the Presence of Aqueous Formate
by Michele Mazzanti, Stefano Caramori, Marco Fogagnolo, Vito Cristino and Alessandra Molinari
Nanomaterials 2020, 10(11), 2147; https://doi.org/10.3390/nano10112147 - 28 Oct 2020
Cited by 11 | Viewed by 2504
Abstract
UV-photoexcitation of TiO2 in contact with aqueous solutions of azo dyes does not imply only its photocatalytic degradation, but the reaction fate of the dye depends on the experimental conditions. In fact, we demonstrate that the presence of sodium formate is the [...] Read more.
UV-photoexcitation of TiO2 in contact with aqueous solutions of azo dyes does not imply only its photocatalytic degradation, but the reaction fate of the dye depends on the experimental conditions. In fact, we demonstrate that the presence of sodium formate is the switch from a degradative pathway of the dye to its transformation into useful products. Laser flash photolysis experiments show that charge separation is extremely long lived in nanostructured TiO2 thin films, making them suitable to drive both oxidation and reduction reactions. ESR spin trapping and photoluminescence experiments demonstrate that formate anions are very efficient in intercepting holes, thereby inhibiting OH radicals formation. Under these conditions, electrons promoted in the conduction band of TiO2 and protons deriving from the oxidation of formate on photogenerated holes lead to the reductive cleavage of N=N bonds with formation and accumulation of reduced intermediates. Negative ion ESI–MS findings provide clear support to point out this new mechanism. This study provides a facile solution for realizing together wastewater purification and photocatalytic conversion of a waste (discharged dye) into useful products (such as sulfanilic acid used again for synthesis of new azo dyes). Moreover, the use of TiO2 deposited on an FTO (Fluorine Tin Oxide) glass circumvents all the difficulties related to the use of slurries. The obtained photocatalyst is easy to handle and to recover and shows an excellent stability allowing complete recyclability. Full article
(This article belongs to the Special Issue Nanostructured Materials for Energy Storage and Conversion)
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17 pages, 3975 KiB  
Article
Highly Porous Free-Standing rGO/SnO2 Pseudocapacitive Cathodes for High-Rate and Long-Cycling Al-Ion Batteries
by Timotheus Jahnke, Leila Raafat, Daniel Hotz, Andrea Knöller, Achim Max Diem, Joachim Bill and Zaklina Burghard
Nanomaterials 2020, 10(10), 2024; https://doi.org/10.3390/nano10102024 - 14 Oct 2020
Cited by 12 | Viewed by 2897
Abstract
Establishing energy storage systems beyond conventional lithium ion batteries requires the development of novel types of electrode materials. Such materials should be capable of accommodating ion species other than Li+, and ideally, these ion species should be of multivalent nature, such [...] Read more.
Establishing energy storage systems beyond conventional lithium ion batteries requires the development of novel types of electrode materials. Such materials should be capable of accommodating ion species other than Li+, and ideally, these ion species should be of multivalent nature, such as Al3+. Along this line, we introduce a highly porous aerogel cathode composed of reduced graphene oxide, which is loaded with nanostructured SnO2. This binder-free hybrid not only exhibits an outstanding mechanical performance, but also unites the pseudocapacity of the reduced graphene oxide and the electrochemical storage capacity of the SnO2 nanoplatelets. Moreover, the combination of both materials gives rise to additional intercalation sites at their interface, further contributing to the total capacity of up to 16 mAh cm−3 at a charging rate of 2 C. The high porosity (99.9%) of the hybrid and the synergy of its components yield a cathode material for high-rate (up to 20 C) aluminum ion batteries, which exhibit an excellent cycling stability over 10,000 tested cycles. The electrode design proposed here has a great potential to meet future energy and power density demands for advanced energy storage devices. Full article
(This article belongs to the Special Issue Nanostructured Materials for Energy Storage and Conversion)
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13 pages, 2609 KiB  
Article
CuCrO2 Nanoparticles Incorporated into PTAA as a Hole Transport Layer for 85 °C and Light Stabilities in Perovskite Solar Cells
by Bumjin Gil, Jinhyun Kim, Alan Jiwan Yun, Kimin Park, Jaemin Cho, Minjun Park and Byungwoo Park
Nanomaterials 2020, 10(9), 1669; https://doi.org/10.3390/nano10091669 - 26 Aug 2020
Cited by 36 | Viewed by 4742
Abstract
High-mobility inorganic CuCrO2 nanoparticles are co-utilized with conventional poly(bis(4-phenyl)(2,5,6-trimethylphenyl)amine) (PTAA) as a hole transport layer (HTL) for perovskite solar cells to improve device performance and long-term stability. Even though CuCrO2 nanoparticles can be readily synthesized by hydrothermal reaction, it is difficult [...] Read more.
High-mobility inorganic CuCrO2 nanoparticles are co-utilized with conventional poly(bis(4-phenyl)(2,5,6-trimethylphenyl)amine) (PTAA) as a hole transport layer (HTL) for perovskite solar cells to improve device performance and long-term stability. Even though CuCrO2 nanoparticles can be readily synthesized by hydrothermal reaction, it is difficult to form a uniform HTL with CuCrO2 alone due to the severe agglomeration of nanoparticles. Herein, both CuCrO2 nanoparticles and PTAA are sequentially deposited on perovskite by a simple spin-coating process, forming uniform HTL with excellent coverage. Due to the presence of high-mobility CuCrO2 nanoparticles, CuCrO2/PTAA HTL demonstrates better carrier extraction and transport. A reduction in trap density is also observed by trap-filled limited voltages and capacitance analyses. Incorporation of stable CuCrO2 also contributes to the improved device stability under heat and light. Encapsulated perovskite solar cells with CuCrO2/PTAA HTL retain their efficiency over 90% after ~900-h storage in 85 °C/85% relative humidity and under continuous 1-sun illumination at maximum-power point. Full article
(This article belongs to the Special Issue Nanostructured Materials for Energy Storage and Conversion)
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12 pages, 1327 KiB  
Article
CO2 Hydrogenation over Unsupported Fe-Co Nanoalloy Catalysts
by Marco Calizzi, Robin Mutschler, Nicola Patelli, Andrea Migliori, Kun Zhao, Luca Pasquini and Andreas Züttel
Nanomaterials 2020, 10(7), 1360; https://doi.org/10.3390/nano10071360 - 11 Jul 2020
Cited by 20 | Viewed by 3694
Abstract
The thermo-catalytic synthesis of hydrocarbons from CO2 and H2 is of great interest for the conversion of CO2 into valuable chemicals and fuels. In this work, we aim to contribute to the fundamental understanding of the effect of alloying on [...] Read more.
The thermo-catalytic synthesis of hydrocarbons from CO2 and H2 is of great interest for the conversion of CO2 into valuable chemicals and fuels. In this work, we aim to contribute to the fundamental understanding of the effect of alloying on the reaction yield and selectivity to a specific product. For this purpose, Fe-Co alloy nanoparticles (nanoalloys) with 30, 50 and 76 wt% Co content are synthesized via the Inert Gas Condensation method. The nanoalloys show a uniform composition and a size distribution between 10 and 25 nm, determined by means of X-ray diffraction and electron microscopy. The catalytic activity for CO2 hydrogenation is investigated in a plug flow reactor coupled with a mass spectrometer, carrying out the reaction as a function of temperature (393–823 K) at ambient pressure. The Fe-Co nanoalloys prove to be more active and more selective to CO than elemental Fe and Co nanoparticles prepared by the same method. Furthermore, the Fe-Co nanoalloys catalyze the formation of C2-C5 hydrocarbon products, while Co and Fe nanoparticles yield only CH4 and CO, respectively. We explain this synergistic effect by the simultaneous variation in CO2 binding energy and decomposition barrier as the Fe/Co ratio in the nanoalloy changes. With increasing Fe content, increased activation temperatures for the formation of CH4 (from 440 K to 560 K) and C2-C5 hydrocarbons (from 460 K to 560 K) are observed. Full article
(This article belongs to the Special Issue Nanostructured Materials for Energy Storage and Conversion)
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Other

Jump to: Editorial, Research

20 pages, 11386 KiB  
Perspective
Single Particle Approaches to Plasmon-Driven Catalysis
by Ruben F. Hamans, Rifat Kamarudheen and Andrea Baldi
Nanomaterials 2020, 10(12), 2377; https://doi.org/10.3390/nano10122377 - 29 Nov 2020
Cited by 20 | Viewed by 3969
Abstract
Plasmonic nanoparticles have recently emerged as a promising platform for photocatalysis thanks to their ability to efficiently harvest and convert light into highly energetic charge carriers and heat. The catalytic properties of metallic nanoparticles, however, are typically measured in ensemble experiments. These measurements, [...] Read more.
Plasmonic nanoparticles have recently emerged as a promising platform for photocatalysis thanks to their ability to efficiently harvest and convert light into highly energetic charge carriers and heat. The catalytic properties of metallic nanoparticles, however, are typically measured in ensemble experiments. These measurements, while providing statistically significant information, often mask the intrinsic heterogeneity of the catalyst particles and their individual dynamic behavior. For this reason, single particle approaches are now emerging as a powerful tool to unveil the structure-function relationship of plasmonic nanocatalysts. In this Perspective, we highlight two such techniques based on far-field optical microscopy: surface-enhanced Raman spectroscopy and super-resolution fluorescence microscopy. We first discuss their working principles and then show how they are applied to the in-situ study of catalysis and photocatalysis on single plasmonic nanoparticles. To conclude, we provide our vision on how these techniques can be further applied to tackle current open questions in the field of plasmonic chemistry. Full article
(This article belongs to the Special Issue Nanostructured Materials for Energy Storage and Conversion)
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