Rechargeable Batteries Studied Using Advanced Spectroscopic and Computational Techniques II

A special issue of Condensed Matter (ISSN 2410-3896). This special issue belongs to the section "Condensed Matter Theory".

Deadline for manuscript submissions: closed (15 December 2023) | Viewed by 20046

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Department of Low Temperature Physics, Faculty of Mathematics and Physics, Charles University, Prague, Czech Republic
Interests: condensed matter theory; computational physics; positron condensed matter physics; hyperfine interactions
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Department of Physics, University of Antwerp, Antwerp, Belgium
Interests: condensed matter theory; computational materials science; superconductivity; positron spectroscopy
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Special Issue Information

Dear Colleagues,

A complete understanding of the principles and mechanisms underlying the functioning of rechargeable batteries has not been reached, despite several decades of research. The present Special Issue, which will focus on modern spectroscopy techniques and first-principles computations applied to rechargeable batteries, will help to unravel the relationships between key battery characteristics and the nature of the electronic orbitals involved in intercalation reactions. The issue aims at providing fundamental insight into how batteries work, as well as validating standard diagnostics and characterization techniques, which mostly probe the average behavior of the battery as a whole. We expect that the findings presented in this Special Issue will facilitate better battery designs and better power management concepts toward alleviating battery aging, as well as a deeper understanding of the underlying physical principles. For example, one of the main challenges in the development of large-scale batteries is to monitor inhomogeneous positive ion distribution in electrodes. Improved uniformity lowers the damaging mechanical stress on the electrodes and improves battery cyclability. These and other important issues can be studied with spectroscopy, computational modeling, and simulations to invent the batteries of the future.

Dr. Jan Kuriplach
Dr. Rolando Saniz
Guest Editors

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Keywords

  • Li-ion battery
  • Na-ion battery
  • Li-air battery
  • spectroscopy techniques for batteries
  • first principles calculations
  • cathode materials
  • anode materials
  • electrolytes
  • Li diffusion and intercalation

Related Special Issue

Published Papers (7 papers)

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Research

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10 pages, 4219 KiB  
Article
Anodic Potential and Conversion Chemistry of Anhydrous Iron (II) Oxalate in Na-Ion Batteries
by Vasilii Gromov, Atlas Noubir, Fatemeh Keshavarz, Ekaterina Laakso, Bernardo Barbiellini and Arun Bansil
Condens. Matter 2023, 8(2), 38; https://doi.org/10.3390/condmat8020038 - 23 Apr 2023
Viewed by 1519
Abstract
Anhydrous ferrous (II) oxalate (AFO) outperforms its hydrated form when used as an anode material in Li-ion batteries (LIBs). With the increasing interest in Na-ion batteries (NIBs) in mind, we examine the potential of AFO as the anode in NIBs through first principles [...] Read more.
Anhydrous ferrous (II) oxalate (AFO) outperforms its hydrated form when used as an anode material in Li-ion batteries (LIBs). With the increasing interest in Na-ion batteries (NIBs) in mind, we examine the potential of AFO as the anode in NIBs through first principles calculations involving both periodic and non-periodic structures. Our analysis based on periodic (non-periodic) modeling scheme shows that the AFO anode generates a low reaction potential of 1.22 V (1.45 V) in the NIBs, and 1.34 V (1.24 V) in the LIBs, which is much lower than the potential of NIBs with mixed oxalates. The conversion mechanism in the underlying electrochemical process involves the reduction of Fe2+ with the addition of Na or Li. Such conversion electrodes can achieve high capacities through the Fe2+ valence states of iron. Full article
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9 pages, 820 KiB  
Article
First Principles Calculations of the Optical Response of LiNiO2
by Veenavee Nipunika Kothalawala, Assa Aravindh Sasikala Devi, Johannes Nokelainen, Matti Alatalo, Bernardo Barbiellini, Tao Hu, Ulla Lassi, Kosuke Suzuki, Hiroshi Sakurai and Arun Bansil
Condens. Matter 2022, 7(4), 54; https://doi.org/10.3390/condmat7040054 - 26 Sep 2022
Cited by 4 | Viewed by 2609
Abstract
We discuss optical properties of layered Lithium Nickel oxide (LiNiO2), which is an attractive cathode material for realizing cobalt-free lithium-ion batteries, within the first-principles density functional theory (DFT) framework. Exchange correlation effects are treated using the generalized gradient approximation (GGA) and [...] Read more.
We discuss optical properties of layered Lithium Nickel oxide (LiNiO2), which is an attractive cathode material for realizing cobalt-free lithium-ion batteries, within the first-principles density functional theory (DFT) framework. Exchange correlation effects are treated using the generalized gradient approximation (GGA) and the strongly-constrained-and-appropriately-normed (SCAN) meta-GGA schemes. A Hubbard parameter (U) is used to model Coulomb correlation effects on Ni 3d electrons. The GGA+U is shown to correctly predict an indirect (system wide) band gap of 0.46 eV in LiNiO2, while the GGA yields a bandgap of only 0.08 eV. The calculated refractive index and its energy dependence is found to be in good agreement with the corresponding experimental results. Finally, our computed optical energy loss function yields insight into the results of recent RIXS experiments on LiNiO2. Full article
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9 pages, 513 KiB  
Article
Anodic Activity of Hydrated and Anhydrous Iron (II) Oxalate in Li-Ion Batteries
by Fatemeh Keshavarz, Marius Kadek, Bernardo Barbiellini and Arun Bansil
Condens. Matter 2022, 7(1), 8; https://doi.org/10.3390/condmat7010008 - 12 Jan 2022
Cited by 4 | Viewed by 2846
Abstract
We discuss the applicability of the naturally occurring compound Ferrous Oxalate Dihydrate (FOD) (FeC2O4·2H2O) as an anode material in Li-ion batteries. Using first-principles modeling, we evaluate the electrochemical activity of FOD and demonstrate how its structural water [...] Read more.
We discuss the applicability of the naturally occurring compound Ferrous Oxalate Dihydrate (FOD) (FeC2O4·2H2O) as an anode material in Li-ion batteries. Using first-principles modeling, we evaluate the electrochemical activity of FOD and demonstrate how its structural water content affects the intercalation reaction and contributes to its performance. We show that both Li0 and Li+ intercalation in FOD yields similar results. Our analysis indicates that fully dehydrated ferrous oxalate is a more promising anodic material with higher electrochemical stability: it carries 20% higher theoretical Li storage capacity and a lower voltage (0.68 V at the PBE/cc-pVDZ level), compared to its hydrated (2.29 V) or partially hydrated (1.43 V) counterparts. Full article
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7 pages, 614 KiB  
Article
Magnetic Compton Scattering Study of Li-Rich Battery Materials
by Kosuke Suzuki, Yuji Otsuka, Kazushi Hoshi, Hiroshi Sakurai, Naruki Tsuji, Kentaro Yamamoto, Naoaki Yabuuchi, Hasnain Hafiz, Yuki Orikasa, Yoshiharu Uchimoto, Yoshiharu Sakurai, Venkatasubramanian Viswanathan, Arun Bansil and Bernardo Barbiellini
Condens. Matter 2022, 7(1), 4; https://doi.org/10.3390/condmat7010004 - 28 Dec 2021
Cited by 6 | Viewed by 3136
Abstract
The redox process in a lithium-ion battery occurs when a conduction electron from the lithium anode is transferred to the redox orbital of the cathode. Understanding the nature of orbitals involved in anionic as well as cationic redox reactions is important for improving [...] Read more.
The redox process in a lithium-ion battery occurs when a conduction electron from the lithium anode is transferred to the redox orbital of the cathode. Understanding the nature of orbitals involved in anionic as well as cationic redox reactions is important for improving the capacity and energy density of Li-ion batteries. In this connection, we have obtained magnetic Compton profiles (MCPs) from the Li-rich cation-disordered rock-salt compound LixTi0.4Mn0.4O2 (LTMO). The MCPs, which involved the scattering of circularly polarized hard X-rays, are given by the momentum density of all the unpaired spins in the material. The net magnetic moment in the ground state can be extracted from the area under the MCP, along with a SQUID measurement. Our analysis gives insight into the role of Mn 3d magnetic electrons and O 2p holes in the magnetic redox properties of LTMO. Full article
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11 pages, 1425 KiB  
Article
Positron Annihilation Spectroscopy as a Diagnostic Tool for the Study of LiCoO2 Cathode of Lithium-Ion Batteries
by Gioele Pagot, Valerio Toso, Bernardo Barbiellini, Rafael Ferragut and Vito Di Noto
Condens. Matter 2021, 6(3), 28; https://doi.org/10.3390/condmat6030028 - 29 Jul 2021
Cited by 5 | Viewed by 3260
Abstract
Positron annihilation spectroscopy using lifetime and Doppler broadening allows the characterization of the lithiation state in LiCoO2 thin film used in cathode of lithium-ion batteries. The lifetime results reflect positron spillover because of the presence of graphite in between the oxide grains [...] Read more.
Positron annihilation spectroscopy using lifetime and Doppler broadening allows the characterization of the lithiation state in LiCoO2 thin film used in cathode of lithium-ion batteries. The lifetime results reflect positron spillover because of the presence of graphite in between the oxide grains in real cathode Li-ion batteries. This spillover produces an effect in the measured positron parameters which are sensitive to delocalized electrons from lithium atoms as in Compton scattering results. The first component of the positron lifetime corresponds to a bulk-like state and can be used to characterize the state of charge of the cathode while the second component represents a surface state at the grain-graphite interface. Full article
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11 pages, 1526 KiB  
Article
Cross-Investigation on Copper Nitroprusside: Combining XRD and XAS for In-Depth Structural Insights
by Angelo Mullaliu, Giuliana Aquilanti, Jasper Rikkert Plaisier and Marco Giorgetti
Condens. Matter 2021, 6(3), 27; https://doi.org/10.3390/condmat6030027 - 25 Jul 2021
Cited by 5 | Viewed by 2715
Abstract
The emerging energy demand and need to develop sustainable energy storage systems have drawn extensive attention to fundamental and applied research. Anion redox processes were proposed in cathodic materials in addition to traditional transition metal redox to boost the specific capacity and the [...] Read more.
The emerging energy demand and need to develop sustainable energy storage systems have drawn extensive attention to fundamental and applied research. Anion redox processes were proposed in cathodic materials in addition to traditional transition metal redox to boost the specific capacity and the electrochemical performance. Alternatively, copper nitroprusside (CuNP) features an electroactive nitrosyl ligand alongside the two structural metals (Fe, Cu), representing an alternative to anion redox in layered oxides. Here, a deep structural investigation is carried out on CuNP by complementing the long-range order sensitivity of X-ray diffraction (XRD) and the local atomic probe of X-ray absorption (XAS). Two different CuNP materials are studied, the hydrated and dehydrated forms. A new phase for hydrated CuNP not reported in the literature is solved, and Rietveld refined. The XAS spectra of the two materials at the Cu and Fe K-edges show a similar yet different atomic environment. The extended XAS spectra (EXAFS) analysis is accomplished by considering three- and four-body terms due to the high collinearity of the atomic chains and gives accurate insight into the first-, second-, and third-shell interatomic distances. Both materials are mounted in Li-ion and Na-ion cells to explore the link between structure and electrochemical performance. As revealed by the charge/discharge cycles, the cyclability in Na-ion cells is negatively affected by interstitial water. The similarity in the local environment and the electrochemical differences suggest a long-range structural dependence on the electrochemical performance. Full article
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Review

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18 pages, 3428 KiB  
Review
Identifying Redox Orbitals and Defects in Lithium-Ion Cathodes with Compton Scattering and Positron Annihilation Spectroscopies: A Review
by Johannes Nokelainen, Bernardo Barbiellini, Jan Kuriplach, Stephan Eijt, Rafael Ferragut, Xin Li, Veenavee Kothalawala, Kosuke Suzuki, Hiroshi Sakurai, Hasnain Hafiz, Katariina Pussi, Fatemeh Keshavarz and Arun Bansil
Condens. Matter 2022, 7(3), 47; https://doi.org/10.3390/condmat7030047 - 26 Jul 2022
Cited by 4 | Viewed by 2531
Abstract
Reduction-oxidation (redox) reactions that transfer conduction electrons from the anode to the cathode are the fundamental processes responsible for generating power in Li-ion batteries. Electronic and microstructural features of the cathode material are controlled by the nature of the redox orbitals and how [...] Read more.
Reduction-oxidation (redox) reactions that transfer conduction electrons from the anode to the cathode are the fundamental processes responsible for generating power in Li-ion batteries. Electronic and microstructural features of the cathode material are controlled by the nature of the redox orbitals and how they respond to Li intercalation. Thus, redox orbitals play a key role in performance of the battery and its degradation with cycling. We unravel spectroscopic descriptors that can be used to gain an atomic-scale handle on the redox mechanisms underlying Li-ion batteries. Our focus is on X-ray Compton Scattering and Positron Annihilation spectroscopies and the related computational approaches for the purpose of identifying orbitals involved in electrochemical transformations in the cathode. This review provides insight into the workings of lithium-ion batteries and opens a pathway for rational design of next-generation battery materials. Full article
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