Advances in Nanomaterials for Lithium-Ion/Post-Lithium-Ion Batteries and Supercapacitors

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

Deadline for manuscript submissions: closed (30 November 2021) | Viewed by 32466

Special Issue Editors

Helmholtz Institute Ulm & Institute for Applied Materials - Energy Storage Systems, Karlsruhe Institute of Technology, Karlsruhe, Germany
Interests: post-lithium battery materials, in operando studies, supercapacitors, hybrid systems
ZSW, Zentrum für Sonnenenergie und Wasserstoff-Forschung Baden-Württemberg, Helmholtzstraße 8, 89081 Ulm, Germany
Interests: lithium and post-lithium battery materials, electrolytes, electrochemical techniques

Special Issue Information

Dear Colleagues,

Environmentally friendly power generation technologies play an essential role in future energy supply due to the increased need for less dependence on fossil fuels for primary energy harvesting. The intermittent nature of many renewable energy sources, such as solar or wind power, makes the development and deployment of energy storage systems paramount. In this respect, Lithium-ion batteries dominate the market since their launch by Sony in 1991. However, the rareness and cost of Lithium quests for sustainable and abundant alternatives, like Sodium, Potassium, Magnesium etc. These new “post-lithium” technologies require the discovery and study of new electrode materials, electrolytes and cell components as well as a fundamental understanding of the phenomena occurring during the cell operation.

We invite authors to contribute with original research articles (short communications and full papers) or comprehensive review articles covering the most recent progress and new developments in the design, synthesis, study of materials for lithium and post-lithium systems, such as Sodium, Potassium, Magnesium, Zinc, Calcium, Aluminium etc. as well as those used for high power devices (e.g. in M-ion capacitors).

Potential topics include, but are not limited to, the following:

  • Synthesis of novel positive/negative electrode materials for lithium and post-lithium systems
  • Development of novel electrolytes
  • Metal anodes
  • Design/modeling
  • Hybrid Metal-ion capacitors
  • In operando studies
  • Electrodes engineering/design
  • New electrochemical techniques for battery cells analysis
  • Processes for electrode preparation

Dr. Sonia Dsoke
Dr. Mario Marinaro
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Nanomaterials is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2900 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Battery
  • Lithium-ion batteries
  • Post-lithium batteries
  • Beyond lithium systems
  • Supercapacitors
  • Hybrid systems
  • M-ion capacitors
  • Battery materials
  • Electrolytes
  • Interface
  • Electrochemistry

Published Papers (10 papers)

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Editorial

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3 pages, 193 KiB  
Editorial
Advances in Nanomaterials for Lithium-Ion/Post-Lithium-Ion Batteries and Supercapacitors
by Mario Marinaro and Sonia Dsoke
Nanomaterials 2022, 12(15), 2512; https://doi.org/10.3390/nano12152512 - 22 Jul 2022
Cited by 2 | Viewed by 1185
Abstract
Energy storage and conversion are key factors for enabling the transition from fossil fuels to intermittent renewables [...] Full article

Research

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15 pages, 6522 KiB  
Article
Crosslinked Chitosan Binder for Sustainable Aqueous Batteries
by Luca Bargnesi, Federica Gigli, Nicolò Albanelli, Christina Toigo and Catia Arbizzani
Nanomaterials 2022, 12(2), 254; https://doi.org/10.3390/nano12020254 - 14 Jan 2022
Cited by 10 | Viewed by 2513
Abstract
The increased percentage of renewable power sources involved in energy production highlights the importance of developing systems for stationary energy storage that satisfy the requirements of safety and low costs. Na ion batteries can be suitable candidates, specifically if their components are economic [...] Read more.
The increased percentage of renewable power sources involved in energy production highlights the importance of developing systems for stationary energy storage that satisfy the requirements of safety and low costs. Na ion batteries can be suitable candidates, specifically if their components are economic and safe. This study focuses on the development of aqueous processes and binders to prepare electrodes for sodium ion cells operating in aqueous solutions. We demonstrated the feasibility of a chitosan-based binder to produce freestanding electrodes for Na ion cells, without the use of organic solvents and current collectors in electrode processing. To our knowledge, it is the first time that water-processed, freestanding electrodes are used in aqueous Na ion cells, which could also be extended to other types of aqueous batteries. This is a real breakthrough in terms of sustainability, taking into account low risks for health and environment and low costs. Full article
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11 pages, 12984 KiB  
Article
Investigating the Cycling Stability of Fe2WO6 Pseudocapacitive Electrode Materials
by Julio César Espinosa-Angeles, Nicolas Goubard-Bretesché, Eric Quarez, Christophe Payen, Moulay-Tahar Sougrati, Olivier Crosnier and Thierry Brousse
Nanomaterials 2021, 11(6), 1405; https://doi.org/10.3390/nano11061405 - 26 May 2021
Cited by 9 | Viewed by 2701
Abstract
The stability upon cycling of Fe2WO6 used as a negative electrode material for electrochemical capacitors was investigated. The material was synthesized using low temperature conditions for the first time (220 °C). The electrochemical study of Fe2WO6 in [...] Read more.
The stability upon cycling of Fe2WO6 used as a negative electrode material for electrochemical capacitors was investigated. The material was synthesized using low temperature conditions for the first time (220 °C). The electrochemical study of Fe2WO6 in a 5 M LiNO3 aqueous electrolyte led to a specific and volumetric capacitance of 38 F g−1 and 240 F cm−3 when cycled at 2 mV·s−1, respectively, associated with a minor capacitance loss after 10,000 cycles. In order to investigate this very good cycling stability, both surface and bulk characterization techniques (such as Transmission Electron Microscopy, Mössbauer spectroscopy, and magnetization measurements) were used. Only a slight disordering of the Fe3+ cations was observed in the structure, explaining the good stability of the Fe2WO6 upon cycling. This study adds another pseudocapacitive material to the short list of compounds that exhibit such a behavior up to now. Full article
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11 pages, 3225 KiB  
Article
New Insights on the Conversion Reaction Mechanism in Metal Oxide Electrodes for Sodium-Ion Batteries
by Jadra Mosa, Francisco José García-García, Agustín R. González-Elipe and Mario Aparicio
Nanomaterials 2021, 11(4), 966; https://doi.org/10.3390/nano11040966 - 09 Apr 2021
Cited by 7 | Viewed by 2253
Abstract
Due to the abundance and low cost of exchanged metal, sodium-ion batteries have attracted increasing research attention for the massive energy storage associated with renewable energy sources. Nickel oxide (NiO) thin films have been prepared by magnetron sputtering (MS) deposition under an oblique [...] Read more.
Due to the abundance and low cost of exchanged metal, sodium-ion batteries have attracted increasing research attention for the massive energy storage associated with renewable energy sources. Nickel oxide (NiO) thin films have been prepared by magnetron sputtering (MS) deposition under an oblique angle configuration (OAD) and used as electrodes for Na-ion batteries. A systematic chemical, structural and electrochemical analysis of this electrode has been carried out. The electrochemical characterization by galvanostatic charge–discharge cycling and cyclic voltammetry has revealed a certain loss of performance after the initial cycling of the battery. The conversion reaction of NiO with sodium ions during the discharge process to generate sodium oxide and Ni metal has been confirmed by X-ray photoelectron spectra (XPS) and micro-Raman analysis. Likewise, it has been determined that the charging process is not totally reversible, causing a reduction in battery capacity. Full article
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10 pages, 2541 KiB  
Article
Li2(BH4)(NH2) Nanoconfined in SBA-15 as Solid-State Electrolyte for Lithium Batteries
by Qianyi Yang, Fuqiang Lu, Yulin Liu, Yijie Zhang, Xiujuan Wang, Yuepeng Pang and Shiyou Zheng
Nanomaterials 2021, 11(4), 946; https://doi.org/10.3390/nano11040946 - 08 Apr 2021
Cited by 6 | Viewed by 2433
Abstract
Solid electrolytes with high Li-ion conductivity and electrochemical stability are very important for developing high-performance all-solid-state batteries. In this work, Li2(BH4)(NH2) is nanoconfined in the mesoporous silica molecule sieve (SBA-15) using a melting–infiltration approach. This electrolyte exhibits [...] Read more.
Solid electrolytes with high Li-ion conductivity and electrochemical stability are very important for developing high-performance all-solid-state batteries. In this work, Li2(BH4)(NH2) is nanoconfined in the mesoporous silica molecule sieve (SBA-15) using a melting–infiltration approach. This electrolyte exhibits excellent Li-ion conduction properties, achieving a Li-ion conductivity of 5.0 × 10−3 S cm−1 at 55 °C, an electrochemical stability window of 0 to 3.2 V and a Li-ion transference number of 0.97. In addition, this electrolyte can enable the stable cycling of Li|Li2(BH4)(NH2)@SBA-15|TiS2 cells, which exhibit a reversible specific capacity of 150 mAh g−1 with a Coulombic efficiency of 96% after 55 cycles. Full article
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18 pages, 12700 KiB  
Article
Effect of the Anionic Counterpart: Molybdate vs. Tungstate in Energy Storage for Pseudo-Capacitor Applications
by Pratigya Sharma, Manickam Minakshi, Jonathan Whale, Annelise Jean-Fulcrand and Georg Garnweitner
Nanomaterials 2021, 11(3), 580; https://doi.org/10.3390/nano11030580 - 26 Feb 2021
Cited by 45 | Viewed by 2873
Abstract
Nickel-based bimetallic oxides (BMOs) have shown significant potential in battery-type electrodes for pseudo-capacitors given their ability to facilitate redox reactions. In this work, two bimetallic oxides, NiMoO4 and NiWO4, were synthesized using a wet chemical route. The structure and electrochemical [...] Read more.
Nickel-based bimetallic oxides (BMOs) have shown significant potential in battery-type electrodes for pseudo-capacitors given their ability to facilitate redox reactions. In this work, two bimetallic oxides, NiMoO4 and NiWO4, were synthesized using a wet chemical route. The structure and electrochemical properties of the pseudo-capacitor cathode materials were characterized. NiMoO4 showed superior charge storage performance in comparison to NiWO4, exhibiting a discharge capacitance of 124 and 77 F·g−1, respectively. NiMoO4, moreover, demonstrates better capacity retention after 1000 cycles with 87.14% compared to 82.22% for NiWO4. The lower electrochemical performance of the latter was identified to result from the redox behavior during cycling. NiWO4 reacts in the alkaline solution and forms a passivation layer composed of WO3 on the electrode, while in contrast, the redox behavior of NiMoO4 is fully reversible. Full article
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19 pages, 7321 KiB  
Article
Effects of SiC and Resorcinol–Formaldehyde (RF) Carbon Coatings on Silicon-Flake-Based Anode of Lithium Ion Battery
by Yonhua Tzeng, Jia-Lin He, Cheng-Ying Jhan and Yi-Hsuan Wu
Nanomaterials 2021, 11(2), 302; https://doi.org/10.3390/nano11020302 - 25 Jan 2021
Cited by 9 | Viewed by 3437
Abstract
Silicon flakes of about 100 × 1000 × 1000 nm in sizes recycled from wastes of silicon wafer manufacturing processes were coated with combined silicon carbide (SiC) and graphitic (Resorcinol–Formaldehyde (RF)) carbon coatings to serve as active materials of the anode of lithium [...] Read more.
Silicon flakes of about 100 × 1000 × 1000 nm in sizes recycled from wastes of silicon wafer manufacturing processes were coated with combined silicon carbide (SiC) and graphitic (Resorcinol–Formaldehyde (RF)) carbon coatings to serve as active materials of the anode of lithium ion battery (LIB). Thermal carbonization of silicon at 1000 °C for 5 h forms 5-nm SiC encapsulating silicon flakes. SiC provides physical strength to help silicon flakes maintain physical integrity and isolating silicon from irreversible reactions with the electrolyte. Lithium diffuses through SiC before alloying with silicon. The SiC buffer layer results in uniform alloying reactions between lithium and silicon on the surface around a silicon flake. RF carbon coatings provide enhanced electrical conductivity of SiC encapsulated silicon flakes. We characterized the coatings and anode by SEM, TEM, FTIR, XRD, cyclic voltammetry (CV), electrochemical impedance spectra (EIS), and electrical resistance measurements. Coin half-cells with combined SiC and RF carbon coatings exhibit an initial Coulombic efficiency (ICE) of 76% and retains a specific capacity of 955 mAh/g at 100th cycle and 850 mAh/g at 150th cycle of repetitive discharge and charge operation. Pre-lithiation of the anode increases the ICE to 97%. The SiC buffer layer reduces local stresses caused by non-uniform volume changes and improves the capacity retention and the cycling life. Full article
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12 pages, 3522 KiB  
Article
Binder-Free Electrode Based on ZnO Nanorods Directly Grown on Aluminum Substrate for High Performance Supercapacitors
by Faheem Ahmed, Ghzzai Almutairi, Bandar AlOtaibi, Shalendra Kumar, Nishat Arshi, Syed Ghazanfar Hussain, Ahmad Umar, Naushad Ahmad and Abdullah Aljaafari
Nanomaterials 2020, 10(10), 1979; https://doi.org/10.3390/nano10101979 - 07 Oct 2020
Cited by 23 | Viewed by 3057
Abstract
Herein, for the first time, the growth of ZnO nanorods directly on aluminum (Al) substrate via a low temperature (80 °C) wet chemical method, and used as binder-free electrode for supercapacitors were reported. XRD pattern and HRTEM images showed that high crystalline nanorods [...] Read more.
Herein, for the first time, the growth of ZnO nanorods directly on aluminum (Al) substrate via a low temperature (80 °C) wet chemical method, and used as binder-free electrode for supercapacitors were reported. XRD pattern and HRTEM images showed that high crystalline nanorods grown on Al substrate with c-axis orientation. Morphological studies revealed that the nanorods possessed well defined hexagon phase with length and diameter of ~2 µm and 100–180 nm, respectively. Raman spectrum of ZnO nanorods showed that the characteristic E2H mode corresponds to the vibration associated with the oxygen atoms of ZnO. The optical properties of ZnO nanorods studied using Room-temperature PL spectra revealed a near-band-edge (NBE) peak at ~388 nm emission and deep level (DLE) at ~507 nm. Electrochemical measurements showed that ZnO nanorods on Al substrate exhibited remarkably enhanced performance as electrode for supercapacitors with a value of specific capacitance of 394 F g−1 measured with scan rate of 20 mV s−1. This unique nanorods structures also exhibited excellent stability of >98% capacitance retention for 1000 cycles that were measured at 1A g−1. The presented easy and cost-effective method might open up the possibility for the mass production of binder-free electrodes for efficient electrochemical energy storage devices. Full article
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13 pages, 2253 KiB  
Article
Efficient Flexible All-Solid Supercapacitors with Direct Sputter-Grown Needle-Like Mn/MnOx@Graphite-Foil Electrodes and PPC-Embedded Ionic Electrolytes
by Apurba Ray, Delale Korkut and Bilge Saruhan
Nanomaterials 2020, 10(9), 1768; https://doi.org/10.3390/nano10091768 - 07 Sep 2020
Cited by 22 | Viewed by 3178
Abstract
Recent critical issues regarding next-generation energy storage systems concern the cost-effective production of lightweight, safe and flexible supercapacitors yielding high performances, such as high energy and power densities as well as a long cycle life. Thus, current research efforts are concentrated on the [...] Read more.
Recent critical issues regarding next-generation energy storage systems concern the cost-effective production of lightweight, safe and flexible supercapacitors yielding high performances, such as high energy and power densities as well as a long cycle life. Thus, current research efforts are concentrated on the development of high-performance advance electrode materials with high capacitance and excellent stability and solid electrolytes that confer flexibility and safety features. In this work, emphasis is placed on the binder-free, needle-like nanostructured Mn/MnOx layers grown onto graphite-foil deposited by reactive sputtering technique and to the polymer gel embedded ionic electrolytes, which are to be employed as new flexible pseudocapacitive supercapacitor components. Microstructural, morphological and compositional analysis of the layers has been investigated by X-ray diffractometer (XRD), Field Emission Scanning Electron Microscope (FE–SEM) and X-ray photoelectron spectroscopy (XPS). A flexible lightweight symmetric pouch-cell solid-state supercapacitor device is fabricated by sandwiching a PPC-embedded ionic liquid ethyl-methylimidazolium bis (trifluoromethylsulfonyl) imide (EMIM)(TFSI) polymer gel electrolyte (PGE) between two Mn/MnOx@Graphite-foil electrodes and tested to exhibit promising supercapacitive behaviour with a wide stable electrochemical potential window (up to 2.2 V) and long-cycle stability. This pouch-cell supercapacitor device offers a maximum areal capacitance of 11.71 mF/cm2@ 0.03 mA/cm2 with maximum areal energy density (Ea) of 7.87 mWh/cm2 and areal power density (Pa) of 1099.64 mW/cm2, as well as low resistance, flexibility and good cycling stability. This supercapacitor device is also environmentally safe and could be operated under a relatively wide potential window without significant degradation of capacitance performance compared to other reported values. Overall, these rationally designed flexible symmetric all-solid-state supercapacitors signify a new promising and emerging candidate for component integrated storage of renewable energy harvested current. Full article
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Review

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29 pages, 6585 KiB  
Review
An Overview on Anodes for Magnesium Batteries: Challenges towards a Promising Storage Solution for Renewables
by Federico Bella, Stefano De Luca, Lucia Fagiolari, Daniele Versaci, Julia Amici, Carlotta Francia and Silvia Bodoardo
Nanomaterials 2021, 11(3), 810; https://doi.org/10.3390/nano11030810 - 22 Mar 2021
Cited by 91 | Viewed by 7451
Abstract
Magnesium-based batteries represent one of the successfully emerging electrochemical energy storage chemistries, mainly due to the high theoretical volumetric capacity of metallic magnesium (i.e., 3833 mAh cm−3 vs. 2046 mAh cm−3 for lithium), its low reduction potential (−2.37 V vs. SHE), [...] Read more.
Magnesium-based batteries represent one of the successfully emerging electrochemical energy storage chemistries, mainly due to the high theoretical volumetric capacity of metallic magnesium (i.e., 3833 mAh cm−3 vs. 2046 mAh cm−3 for lithium), its low reduction potential (−2.37 V vs. SHE), abundance in the Earth’s crust (104 times higher than that of lithium) and dendrite-free behaviour when used as an anode during cycling. However, Mg deposition and dissolution processes in polar organic electrolytes lead to the formation of a passivation film bearing an insulating effect towards Mg2+ ions. Several strategies to overcome this drawback have been recently proposed, keeping as a main goal that of reducing the formation of such passivation layers and improving the magnesium-related kinetics. This manuscript offers a literature analysis on this topic, starting with a rapid overview on magnesium batteries as a feasible strategy for storing electricity coming from renewables, and then addressing the most relevant outcomes in the field of anodic materials (i.e., metallic magnesium, bismuth-, titanium- and tin-based electrodes, biphasic alloys, nanostructured metal oxides, boron clusters, graphene-based electrodes, etc.). Full article
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