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Nanostructured Materials for Electrochemical Energy Storage

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A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Energy Materials".

Deadline for manuscript submissions: closed (10 September 2023) | Viewed by 28671

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Prof. Dr. Christian Julien

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Institut de Minéralogie, Physique des Matériaux et Cosmologie (IMPMC), Sorbonne Université, Paris, France
Interests: energy storage and conversion; solid state ionics; nanomaterials; nanoionics; lithium batteries; energy materials; insertion reactions; vibrational spectrocopy
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Prof. Dr. Boris Markovsky

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Department of Chemistry, Faculty of Exact Sciences, Bar-Ilan University, Ramat-Gan 5290002, Israel
Interests: electrochemistry; energy storage; lithium batteries; electrode materials; nano-materials; electrochemical sensors; Raman spectroscopy
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear colleagues,

Many efforts are currently made to increase the limited capacity of energy storage systems such as Li-ion batteries and supercapacitors using insertion and/or conversion electrodes. The way to reach this goal is to move to nanostructured materials because the larger surface to volume ratio of particles and the reduction of the electron and Li path length imply a larger specific capacity. Additionally, nanoparticles can accommodate such a dilatation/contraction during cycling, resulting in a calendar life compatible with a commercial use. This Special Issue will focus on the advanced nanomaterials for energy storage that are the most promising for practical applications. Both theoretical and experimental papers, communications, and reviews related to nanostructured materials for electrochemical energy storage are all welcome.

Prof. Christian M. Julien
Prof. Boris Markovsky
Guest Editors

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Keywords

Nanostructures
Energy storage
Batteries
Supercapacitors
Conversion mechanism
Advanced electrodes

Published Papers (11 papers)

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Research

11 pages, 3294 KiB

Open AccessArticle

New Scalable Sulfur Cathode Containing Specifically Designed Polysulfide Adsorbing Materials

by Artur M. Suzanowicz, Bianca Turner, Thulitha M. Abeywickrama, Hao Lin, Dana Alramahi, Carlo U. Segre and Braja K. Mandal

Materials 2024, 17(4), 856; https://0-doi-org.brum.beds.ac.uk/10.3390/ma17040856 - 12 Feb 2024

Viewed by 669

Abstract

Because of its considerable theoretical specific capacity and energy density, lithium–sulfur battery technology holds great potential to replace lithium-ion battery technology. However, a versatile, low-cost, and easily scalable bulk synthesis method is essential for translating bench-level development to large-scale production. This paper reports the design and synthesis of a new scalable sulfur cathode, S@CNT/PANI/PPyNT/TiO₂ (BTX). The rationally chosen cathode components suppress the migration of polysulfide intermediates via chemical interactions, enhance redox kinetics, and provide electrical conductivity to sulfur, rendering outstanding long-term cycling performance and strong initial specific capacity in terms of electrochemical performance. This cathode’s cell demonstrated an initial specific capacity of 740 mA h g⁻¹ at 0.2 C (with a capacity decay rate of 0.08% per cycle after 450 cycles). Full article

(This article belongs to the Special Issue Nanostructured Materials for Electrochemical Energy Storage)

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14 pages, 3614 KiB

Open AccessEditor’s ChoiceArticle

Black Liquor and Wood Char-Derived Nitrogen-Doped Carbon Materials for Supercapacitors

by Loreta Tamasauskaite-Tamasiunaite, Jolita Jablonskienė, Dijana Šimkūnaitė, Aleksandrs Volperts, Ance Plavniece, Galina Dobele, Aivars Zhurinsh, Vitalija Jasulaitiene, Gediminas Niaura, Audrius Drabavicius, Mari Juel, Luis Colmenares-Rausseo, Ivar Kruusenberg, Kätlin Kaare and Eugenijus Norkus

Materials 2023, 16(7), 2551; https://0-doi-org.brum.beds.ac.uk/10.3390/ma16072551 - 23 Mar 2023

Cited by 1 | Viewed by 1357

Abstract

Herein, we present a synthesis route for high-efficiency nitrogen-doped carbon materials using kraft pulping residue, black liquor, and wood charcoal as carbon sources. The synthesized nitrogen-doped carbon materials, based on black liquor and its mixture with wood charcoal, exhibited high specific surface areas (SSAs) of 2481 and 2690 m² g⁻¹, respectively, as well as a high volume of mesopores with an average size of 2.9–4.6 nm. The nitrogen content was approximately 3–4 at% in the synthesized nitrogen-doped carbon materials. A specific capacitance of approximately 81–142 F g⁻¹ was achieved in a 1 M Na₂SO₄ aqueous solution at a current density of 0.2 A g⁻¹. In addition, the specific capacitance retention was 99% after 1000 cycles, indicating good electrochemical stability. Full article

(This article belongs to the Special Issue Nanostructured Materials for Electrochemical Energy Storage)

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19 pages, 6596 KiB

Open AccessArticle

Pouch-Type Asymmetric Supercapacitor Based on Nickel–Cobalt Metal–Organic Framework

by Surya. V. Prabhakar Vattikuti, Nguyen To Hoai, Jie Zeng, Rajavaram Ramaraghavulu, Nam Nguyen Dang, Jaesool Shim and Christian M. Julien

Materials 2023, 16(6), 2423; https://0-doi-org.brum.beds.ac.uk/10.3390/ma16062423 - 17 Mar 2023

Cited by 3 | Viewed by 1718

Abstract

Bimetal–organic frameworks (BMOFs) have attracted considerable attention as electrode materials for energy storage devices because of the precise control of their porous structure, surface area, and pore volume. BMOFs can promote multiple redox reactions because of the enhanced charge transfer between different metal ions. Therefore, the electroactivity of the electrodes can be significantly improved. Herein, we report a NiCo-MOF (NCMF) with a three-dimensional hierarchical nanorod-like structure prepared using a facile solvo-hydrothermal method. The as-prepared NCMF was used as the positive electrode in a hybrid pouch-type asymmetric supercapacitor device (HPASD) with a gel electrolyte (KOH+PVA) and activated carbon as the negative electrode. Because of the matchable potential windows and specific capacitances of the two electrodes, the assembled HPASD exhibits a specific capacitance of 161 F·g⁻¹ at 0.5 A·g⁻¹, an energy density of 50.3 Wh·kg⁻¹ at a power density of 375 W·kg⁻¹, and a cycling stability of 87.6% after 6000 cycles. The reported unique synthesis strategy is promising for producing high-energy-density electrode materials for supercapacitors. Full article

(This article belongs to the Special Issue Nanostructured Materials for Electrochemical Energy Storage)

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19 pages, 3826 KiB

Open AccessArticle

Investigation and Optimization of Mxene Functionalized Mesoporous Titania Films as Efficient Photoelectrodes

by Anum Iqbal and Nasser M. Hamdan

Materials 2021, 14(21), 6292; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14216292 - 22 Oct 2021

Cited by 34 | Viewed by 3695

Abstract

Three-dimensional mesoporous TiO₂ scaffolds of anatase phase possess inherent eximious optical behavior that is beneficial for photoelectrodes used for solar energy conversion applications. In this regard; substantial efforts have been devoted to maximizing the UV and/or visible light absorption efficiency; and suppressing the annihilation of photogenerated charged species; in pristine mesoporous TiO₂ structures for improved solar illumination conversion efficiency. This study provides fundamental insights into the use of Mxene functionalized mesoporous TiO₂ as a photoelectrode. This novel combination of Mxene functionalized TiO₂ electrodes with and without TiCl₄ treatment was successfully optimized to intensify the process of photon absorption; charge segregation and photocurrent; resulting in superior photoelectrode performance. The photocurrent measurements of the prepared photoelectrodes were significantly enhanced with increased contents of Mxene due to improved absorption efficiency within the visible region; as verified by UV–Vis absorption spectroscopy. The anatase phase of TiO₂ was significantly augmented due to increased contents of Mxene and postdeposition heat treatments; as evidenced by structural analysis. Consequently; an appreciable coverage of well-developed grains on the FTO surface was observed in SEM images. As such; these newly fabricated conductive mesoporous TiO₂ photoelectrodes are potential candidates for photoinduced energy conversion and storage applications. Full article

(This article belongs to the Special Issue Nanostructured Materials for Electrochemical Energy Storage)

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8 pages, 15596 KiB

Open AccessArticle

Cobalt Oxide-Decorated Silicon Carbide Nano-Tree Array Electrode for Micro-Supercapacitor Application

by Chuan-Pei Lee, Bayu-Tri Murti, Po-Kang Yang, Francesca Rossi, Carlo Carraro and Roya Maboudian

Materials 2021, 14(16), 4514; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14164514 - 11 Aug 2021

Cited by 8 | Viewed by 2335

Abstract

A cobalt oxide (Co₃O₄)-decorated silicon carbide (SiC) nano-tree array (denoted as Co₃O₄/SiC NTA) electrode is synthesized, and it is investigated for use in micro-supercapacitor applications. Firstly, the well-standing SiC nanowires (NWs) are prepared by nickel (Ni)-catalyzed chemical vapor deposition (CVD) method, and then the thin layer of Co₃O₄ and the hierarchical Co₃O₄ nano-flower-clusters are, respectively, fabricated on the side-walls and the top side of the SiC NWs via electrodeposition. The deposition of Co₃O₄ on the SiC NWs benefits the charge transfer at the electrode/aqueous electrolyte interface due to its extremely hydrophilic surface characteristic after Co₃O₄ decoration. Furthermore, the Co₃O₄/SiC NTA electrode provides a directional charge transport route along the length of SiC nanowires owing to their well-standing architecture. By using the Co₃O₄/SiC NTA electrode for micro-supercapacitor application, the areal capacitance obtained from cyclic voltammetry measurement reaches 845 mF cm⁻² at a 10 mV s⁻¹ scan rate. Finally, the capacitance durability is also evaluated by the cycling test of cyclic voltammetry at a high scan rate of 150 mV s⁻¹ for 2000 cycles, exhibiting excellent stability. Full article

(This article belongs to the Special Issue Nanostructured Materials for Electrochemical Energy Storage)

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11 pages, 3576 KiB

Open AccessArticle

Optically Controlled Supercapacitors: Functional Active Carbon Electrodes with Semiconductor Particles

by Haim Grebel

Materials 2021, 14(15), 4183; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14154183 - 27 Jul 2021

Cited by 3 | Viewed by 2276

Abstract

Supercapacitors, S-C—capacitors that take advantage of the large capacitance at the interface between an electrode and an electrolyte—have found many short-term energy applications. The parallel plate cells were made of two transparent electrodes (ITO), each covered with a semiconductor-embedded, active carbon (A-C) layer. While A-C appears black, it is not an ideal blackbody absorber that absorbs all spectral light indiscriminately. In addition to a relatively flat optical absorption background, A-C exhibits two distinct absorption bands: in the near-infrared (near-IR and in the blue. The first may be attributed to absorption by the OH⁻ group and the latter, by scattering, possibly through surface plasmons at the pore/electrolyte interface. Here, optical and thermal effects of sub-μm SiC particles that are embedded in A-C electrodes, are presented. Similar to nano-Si particles, SiC exhibits blue band absorption, but it is less likely to oxidize. Using Charge-Discharge (CD) experiments, the relative optically related capacitance increase may be as large as ~34% (68% when the illuminated area is taken into account). Capacitance increase was noted as the illuminated samples became hotter. This thermal effect amounts to <20% of the overall relative capacitance change using CD experiments. The thermal effect was quite large when the SiC particles were replaced by CdSe/ZnS quantum dots; for the latter, the thermal effect was 35% compared to 10% for the optical effect. When analyzing the optical effect one may consider two processes: ionization of the semiconductor particles and charge displacement under the cell’s terminals—a dipole effect. A model suggests that the capacitance increase is related to an optically induced dipole effect. Full article

(This article belongs to the Special Issue Nanostructured Materials for Electrochemical Energy Storage)

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17 pages, 4856 KiB

Open AccessArticle

Controlled Nanostructuration of Cobalt Oxyhydroxide Electrode Material for Hybrid Supercapacitors

by Ronan Invernizzi, Liliane Guerlou-Demourgues, François Weill, Alexia Lemoine, Marie-Anne Dourges, Isabelle Baraille, Delphine Flahaut and Jacob Olchowka

Materials 2021, 14(9), 2325; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14092325 - 29 Apr 2021

Cited by 7 | Viewed by 2095

Abstract

Nanostructuration is one of the most promising strategies to develop performant electrode materials for energy storage devices, such as hybrid supercapacitors. In this work, we studied the influence of precipitation medium and the use of a series of 1-alkyl-3-methylimidazolium bromide ionic liquids for the nanostructuration of β(III) cobalt oxyhydroxides. Then, the effect of the nanostructuration and the impact of the different ionic liquids used during synthesis were investigated in terms of energy storage performances. First, we demonstrated that forward precipitation, in a cobalt-rich medium, leads to smaller particles with higher specific surface areas (SSA) and an enhanced mesoporosity. Introduction of ionic liquids (ILs) in the precipitation medium further strongly increased the specific surface area and the mesoporosity to achieve well-nanostructured materials with a very high SSA of 265 m²/g and porosity of 0.43 cm³/g. Additionally, we showed that ILs used as surfactant and template also functionalize the nanomaterial surface, leading to a beneficial synergy between the highly ionic conductive IL and the cobalt oxyhydroxide, which lowers the resistance charge transfer and improves the specific capacity. The nature of the ionic liquid had an important influence on the final electrochemical properties and the best performances were reached with the ionic liquid containing the longest alkyl chain. Full article

(This article belongs to the Special Issue Nanostructured Materials for Electrochemical Energy Storage)

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17 pages, 5777 KiB

Open AccessArticle

Studies of Nickel-Rich LiNi_0.85Co_0.10Mn_0.05O₂ Cathode Materials Doped with Molybdenum Ions for Lithium-Ion Batteries

by Francis Amalraj Susai, Daniela Kovacheva, Tatyana Kravchuk, Yaron Kauffmann, Sandipan Maiti, Arup Chakraborty, Sooraj Kunnikuruvan, Michael Talianker, Hadar Sclar, Yafit Fleger, Boris Markovsky and Doron Aurbach

Materials 2021, 14(8), 2070; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14082070 - 20 Apr 2021

Cited by 18 | Viewed by 4471

Abstract

In this work, we continued our systematic investigations on synthesis, structural studies, and electrochemical behavior of Ni-rich materials Li[Ni_xCo_yMn_z]O₂ (x + y + z = 1; x ≥ 0.8) for advanced lithium-ion batteries (LIBs). We focused, herein, on LiNi_0.85Co_0.10Mn_0.05O₂ (NCM85) and demonstrated that doping this material with high-charge cation Mo⁶⁺ (1 at. %, by a minor nickel substitution) results in substantially stable cycling performance, increased rate capability, lowering of the voltage hysteresis, and impedance in Li-cells with EC-EMC/LiPF₆ solutions. Incorporation of Mo-dopant into the NCM85 structure was carried out by in-situ approach, upon the synthesis using ammonium molybdate as the precursor. From X-ray diffraction studies and based on our previous investigation of Mo-doped NCM523 and Ni-rich NCM811 materials, it was revealed that Mo⁶⁺ preferably substitutes Ni residing either in 3a or 3b sites. We correlated the improved behavior of the doped NCM85 electrode materials in Li-cells with a partial Mo segregation at the surface and at the grain boundaries, a tendency established previously in our lab for the other members of the Li[Ni_xCo_yMn_z]O₂ family. Full article

(This article belongs to the Special Issue Nanostructured Materials for Electrochemical Energy Storage)

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22 pages, 5994 KiB

Open AccessArticle

Electrochemical Activation of Li₂MnO₃ Electrodes at 0 °C and Its Impact on the Subsequent Performance at Higher Temperatures

by Francis Amalraj Susai, Michael Talianker, Jing Liu, Rosy, Tanmoy Paul, Yehudit Grinblat, Evan Erickson, Malachi Noked, Larisa Burstein, Anatoly I. Frenkel, Yoed Tsur, Boris Markovsky and Doron Aurbach

Materials 2020, 13(19), 4388; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13194388 - 01 Oct 2020

Cited by 12 | Viewed by 3350

Abstract

This work continues our systematic study of Li- and Mn- rich cathodes for lithium-ion batteries. We chose Li₂MnO₃ as a model electrode material with the aim of correlating the improved electrochemical characteristics of these cathodes initially activated at 0 °C with the structural evolution of Li₂MnO₃, oxygen loss, formation of per-oxo like species (O₂²⁻) and the surface chemistry. It was established that performing a few initial charge/discharge (activation) cycles of Li₂MnO₃ at 0 °C resulted in increased discharge capacity and higher capacity retention, and decreased and substantially stabilized the voltage hysteresis upon subsequent cycling at 30 °C or at 45 °C. In contrast to the activation of Li₂MnO₃ at these higher temperatures, Li₂MnO₃ underwent step-by-step activation at 0 °C, providing a stepwise traversing of the voltage plateau at >4.5 V during initial cycling. Importantly, these findings agree well with our previous studies on the activation at 0 °C of 0.35Li₂MnO₃·0.65Li[Mn_0.45Ni_0.35Co_0.20]O₂ materials. The stability of the interface developed at 0 °C can be ascribed to the reduced interactions of the per-oxo-like species formed and the oxygen released from Li₂MnO₃ with solvents in ethylene carbonate–methyl-ethyl carbonate/LiPF₆ solutions. Our TEM studies revealed that typically, upon initial cycling both at 0 °C and 30 °C, Li₂MnO₃ underwent partial structural layered-to-spinel (Li₂Mn₂O₄) transition. Full article

(This article belongs to the Special Issue Nanostructured Materials for Electrochemical Energy Storage)

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17 pages, 2734 KiB

Open AccessArticle

Synthesis of High Surface Area α-K_yMnO₂ Nanoneedles Using Extract of Broccoli as Bioactive Reducing Agent and Application in Lithium Battery

by Ahmed M. Hashem, Hanaa M. Abuzeid, Martin Winter, Jie Li and Christian M. Julien

Materials 2020, 13(6), 1269; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13061269 - 11 Mar 2020

Cited by 5 | Viewed by 2653

Abstract

With the aim to reduce the entire cost of lithium-ion batteries and to diminish the environmental impact, the extract of broccoli is used as a strong benign reducing agent for potassium permanganate to synthesize α-K_yMnO₂ cathode material with pure nanostructured phase. Material purity is confirmed by X-ray powder diffraction and thermogravimetric analyses. Images of transmission electron microscopy show samples with a spider-net shape consisting of very fine interconnected nanoneedles. The nanostructure is characterized by crystallite of 4.4 nm in diameter and large surface area of 160.7 m² g⁻¹. The material delivers an initial capacity of 211 mAh g⁻¹ with high Coulombic efficiency of 99% and 82% capacity retention after 100 cycles. Thus, α-K_yMnO₂ synthesized via a green process exhibits very promising electrochemical performance in terms of initial capacity, cycling stability and rate capability. Full article

(This article belongs to the Special Issue Nanostructured Materials for Electrochemical Energy Storage)

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12 pages, 3545 KiB

Open AccessArticle

Electrochemical Performances Investigation of New Carbon-Coated Nickel Sulfides as Electrode Material for Supercapacitors

by Xinyu Lei, Mu Li, Min Lu and Xiaohui Guan

Materials 2019, 12(21), 3509; https://0-doi-org.brum.beds.ac.uk/10.3390/ma12213509 - 25 Oct 2019

Cited by 8 | Viewed by 2154

Abstract

A new carbon-coated nickel sulfides electrode material (NST/CNTs@C) has been synthesized through an easy-to-operate process: NiS₂/CNTs which was prepared by a hydrothermal method reacted with BTC (1,3,5-benzenetricarboxylic acid) under the condition of water bath heating to obtain the precursor, and then the precursor was calcined in 450 °C under a nitrogen atmosphere to obtain NST/CNTs@C. The electrochemical performance of NST/CNTs@C has been greatly improved because the formation of a carbon-coated layer effectively increased the specific surface area, reduced the charge transport resistance and inhibited the morphological change of nickel sulfides in the charge–discharge process. Compared with pure NiS₂ and NiS₂/CNTs, NST/CNTs@C presented great specific capacitance (620 F·g⁻¹ at a current density of 1 A·g⁻¹), better cycle stability (49.19% capacitance retention after 1000 cycles) and more superior rate capability (when the current density was raised to 10 A·g⁻¹ the specific capacitance remained 275 F·g⁻¹). Full article

(This article belongs to the Special Issue Nanostructured Materials for Electrochemical Energy Storage)

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