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A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Inorganic Chemistry".

Deadline for manuscript submissions: closed (30 April 2021) | Viewed by 58075

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

Special Issue Editors

Dr. Stephane Jobic

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Guest Editor
Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS, 2 rue de la Houssinière, BP 32229, 44322 Nantes, CEDEX 3, France
Interests: solid state chemistry (inorganic and organic-inorganic materials); optical materials (pigments, UV-absorbers, TCO, X-chromes, fluorescent and long lasting phosphorescent materials, p-type semiconductors, photovoltaics, etc.); structure-property relationship; impact of defects on properties
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Claude Delmas

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Guest Editor
CNRS Centre National de la Recherche Scientifique, Paris, France
Interests: layered oxides and hydroxides; positive electrodes for lithium and alkaline batteries
Prof. Dr. Myung-Hwan Whangbo

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Guest Editor
1. Department of Chemistry, North Carolina State University, Raleigh, NC 27695-8204, USA
2. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter (FJIRSM), Chinese Academy of Sciences (CAS), Fuzhou 350002, China
3. State key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China
Interests: solid state chemistry; materials chemistry; condensed matter physics; magnetic properties; optical properties; superconductivity; electronic band structure calculations; structure-property correlations
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Jean Étourneau

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Guest Editor
ICMCB - Institut de Chimie de la Matière Condensée de Bordeaux, University of Bordeaux, ICMCB – UMR5026, 87, Avenue du Docteur Schweitzer, 33608 PESSAC, CEDEX, France
Interests: chemical and physical properties of borides; intermetallics; high Tc superconductors; relations structure properties; prediction of new materials by first-principle investigations

Special Issue Information

Dear colleagues,

This Special Issue of Molecules is dedicated to Professor John B. Goodenough (born July 25, 1922, Jena, Germany), American physicist, who won the 2019 Nobel Prize for Chemistry for his work on developing lithium-ion batteries.

Goodenough received a bachelor’s degree in mathematics from Yale University (1943) while serving in the United States Army Air Forces as a meteorologist. After the end of World War II, he did his graduate studies in physics at the University of Chicago, where he earned a master’s degree in 1951 and a doctorate in 1952.

Goodenough joined Lincoln Laboratory at the Massachusetts Institute of Technology as a research scientist in 1952. In 1976, he became a professor and the head of the Inorganic Chemistry Laboratory at the University of Oxford (England). In 1986, he became a professor of the Departments of Mechanical Engineering and Electrical and Computer Engineering at the University of Texas at Austin. He has been honoured with a National Medal of Science (2011), a Charles Stark Draper Prize (2014), a Copley Medal (2019), and a Nobel Prize (2019).

Goodenough has made two seminal contributions in the area of solid-state materials. One is on superexchange interactions of magnetic materials, and the other on lithium-ion batteries based on transition metal oxides. His contribution to our understanding of superexchange interactions took place while working at Lincoln Laboratory. The magnetic moments of two magnetic cations joined to a common, nonmagnetic anion can couple either antiferromagnetically or ferromagnetically. This superexchange phenomenon was first noticed by Hendrik Kramers in 1934, and its theoretical description was given by Phillip Anderson in 1950. In the late 1950s, John Goodenough examined the structural factors governing the sign and strength of superexchange to develop a set of semi-empirical rules for superexchange, and so did Junjiro Kanamori. Ever since, these semi-empirical rules have been known as Goodenough–Kanamori rules and have greatly influenced our thinking about magnetic materials.

Goodenough made his contribution to lithium batteries while working at the University of Oxford. The intercalation and deintercalation of an alkali metal in transition metal chalcogenides had been actively investigated in several countries: at Bell Labs in the United States, by J. Rouxel in France, and by B. Steele in England. At that time, the main purpose of the studies was to examine electronic properties. Stanley Whittingham was the first to publish in 1976 the electrochemical intercalation of lithium in titanium disulfide. Then, several groups focused their studies on the intercalation of lithium and sodium in other chalcogenides and in oxides. In 1980, Goodenough and his collaborators made the very first Li-LiCoO2 battery, which attracted much attention toward practical applications. This seminal work opened the door to numerous practical applications of lithium-ion batteries, which have become indispensable in our everyday life. He also showed that the cell voltage could be increased by using the inductive effect of polyanions. Goodenough proposed the currently used positive electrode material, LiFePO4, in 1997.

We plan to organize a Special Issue honoring John Goodenough’s distinguished scientific career over the past 70 years. This Special Issue will consist of communications, original research articles, and review articles related to magnetic properties and alkali ion batteries as well as anecdotes on John Goodenough.

Dr. Stephane Jobic
Prof. Dr. Claude Delmas
Prof. Dr. Myung-Hwan Whangbo
Prof. Dr. Jean Étourneau 
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. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

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Editorial

Jump to: Research, Review, Other

5 pages, 469 KiB  
Editorial
In Honor of John Bannister Goodenough, an Outstanding Visionary
by Jean Etourneau, Claude Delmas, Stéphane Jobic and Myung-Hwan Whangbo
Molecules 2021, 26(21), 6624; https://doi.org/10.3390/molecules26216624 - 01 Nov 2021
Cited by 1 | Viewed by 2146
Abstract
John B [...] Full article
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
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Research

Jump to: Editorial, Review, Other

6 pages, 2879 KiB  
Article
High-Voltage Polyanion Positive Electrode Materials
by Atsuo Yamada
Molecules 2021, 26(17), 5143; https://doi.org/10.3390/molecules26175143 - 25 Aug 2021
Cited by 7 | Viewed by 2916
Abstract
High-voltage generation (over 4 V versus Li+/Li) of polyanion-positive electrode materials is usually achieved by Ni3+/Ni2+, Co3+/Co2+, or V4+/V3+ redox couples, all of which, however, encounter cost and toxicity issues. [...] Read more.
High-voltage generation (over 4 V versus Li+/Li) of polyanion-positive electrode materials is usually achieved by Ni3+/Ni2+, Co3+/Co2+, or V4+/V3+ redox couples, all of which, however, encounter cost and toxicity issues. In this short review, our recent efforts to utilize alternative abundant and less toxic Fe3+/Fe2+ and Cr4+/Cr3+ redox couples are summarized. Most successful examples are alluaudite Na2Fe2(SO4)3 (3.8 V versus sodium and hence 4.1 V versus lithium) and β1-Na3Al2(PO4)2F3-type Na3Cr2(PO4)2F3 (4.7 V versus sodium and hence 5.0 V versus lithium), where maximizing ΔG by edge-sharing Fe3+-Fe3+ Coulombic repulsion and the use of the 3d2/3d3 configuration of Cr4+/Cr3+ are essential for each case. Possible exploration of new high-voltage cathode materials is also discussed. Full article
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
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12 pages, 3682 KiB  
Article
Defect Engineering and Anisotropic Modulation of Ionic Transport in Perovskite Solid Electrolyte LixLa(1−x)/3NbO3
by Jinhua Hong, Shunsuke Kobayashi, Akihide Kuwabara, Yumi H. Ikuhara, Yasuyuki Fujiwara and Yuichi Ikuhara
Molecules 2021, 26(12), 3559; https://doi.org/10.3390/molecules26123559 - 10 Jun 2021
Cited by 7 | Viewed by 2827
Abstract
Solid electrolytes, such as perovskite Li3xLa2/1−xTiO3, LixLa(1−x)/3NbO3 and garnet Li7La3Zr2O12 ceramic oxides, have attracted extensive attention in lithium-ion battery research due to their good [...] Read more.
Solid electrolytes, such as perovskite Li3xLa2/1−xTiO3, LixLa(1−x)/3NbO3 and garnet Li7La3Zr2O12 ceramic oxides, have attracted extensive attention in lithium-ion battery research due to their good chemical stability and the improvability of their ionic conductivity with great potential in solid electrolyte battery applications. These solid oxides eliminate safety issues and cycling instability, which are common challenges in the current commercial lithium-ion batteries based on organic liquid electrolytes. However, in practical applications, structural disorders such as point defects and grain boundaries play a dominating role in the ionic transport of these solid electrolytes, where defect engineering to tailor or improve the ionic conductive property is still seldom reported. Here, we demonstrate a defect engineering approach to alter the ionic conductive channels in LixLa(1−x)/3NbO3 (x = 0.1~0.13) electrolytes based on the rearrangements of La sites through a quenching process. The changes in the occupancy and interstitial defects of La ions lead to anisotropic modulation of ionic conductivity with the increase in quenching temperatures. Our trial in this work on the defect engineering of quenched electrolytes will offer opportunities to optimize ionic conductivity and benefit the solid electrolyte battery applications. Full article
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
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14 pages, 4765 KiB  
Article
Electrochemical Assessment of Indigo Carmine Dye in Lithium Metal Polymer Technology
by Margaud Lécuyer, Marc Deschamps, Dominique Guyomard, Joël Gaubicher and Philippe Poizot
Molecules 2021, 26(11), 3079; https://doi.org/10.3390/molecules26113079 - 21 May 2021
Cited by 12 | Viewed by 2635
Abstract
Lithium metal batteries are inspiring renewed interest in the battery community because the most advanced designs of Li-ion batteries could be on the verge of reaching their theoretical specific energy density values. Among the investigated alternative technologies for electrochemical storage, the all-solid-state Li [...] Read more.
Lithium metal batteries are inspiring renewed interest in the battery community because the most advanced designs of Li-ion batteries could be on the verge of reaching their theoretical specific energy density values. Among the investigated alternative technologies for electrochemical storage, the all-solid-state Li battery concept based on the implementation of dry solid polymer electrolytes appears as a mature technology not only to power full electric vehicles but also to provide solutions for stationary storage applications. With an effective marketing started in 2011, BlueSolutions keeps developing further the so-called lithium metal polymer batteries based on this technology. The present study reports the electrochemical performance of such Li metal batteries involving indigo carmine, a cheap and renewable electroactive non-soluble organic salt, at the positive electrode. Our results demonstrate that this active material was able to reversibly insert two Li at an average potential of ≈2.4 V vs. Li+/Li with however, a relatively poor stability upon cycling. Post-mortem analyses revealed the poisoning of the Li electrode by Na upon ion exchange reaction between the Na countercations of indigo carmine and the conducting salt. The use of thinner positive electrodes led to much better capacity retention while enabling the identification of two successive one-electron plateaus. Full article
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
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18 pages, 2523 KiB  
Article
Fast Li-Ion Conduction in Spinel-Structured Solids
by Jan L. Allen, Bria A. Crear, Rishav Choudhury, Michael J. Wang, Dat T. Tran, Lin Ma, Philip M. Piccoli, Jeff Sakamoto and Jeff Wolfenstine
Molecules 2021, 26(9), 2625; https://doi.org/10.3390/molecules26092625 - 30 Apr 2021
Cited by 5 | Viewed by 3125
Abstract
Spinel-structured solids were studied to understand if fast Li+ ion conduction can be achieved with Li occupying multiple crystallographic sites of the structure to form a “Li-stuffed” spinel, and if the concept is applicable to prepare a high mixed electronic-ionic conductive, electrochemically [...] Read more.
Spinel-structured solids were studied to understand if fast Li+ ion conduction can be achieved with Li occupying multiple crystallographic sites of the structure to form a “Li-stuffed” spinel, and if the concept is applicable to prepare a high mixed electronic-ionic conductive, electrochemically active solid solution of the Li+ stuffed spinel with spinel-structured Li-ion battery electrodes. This could enable a single-phase fully solid electrode eliminating multi-phase interface incompatibility and impedance commonly observed in multi-phase solid electrolyte–cathode composites. Materials of composition Li1.25M(III)0.25TiO4, M(III) = Cr or Al were prepared through solid-state methods. The room-temperature bulk Li+-ion conductivity is 1.63 × 10−4 S cm−1 for the composition Li1.25Cr0.25Ti1.5O4. Addition of Li3BO3 (LBO) increases ionic and electronic conductivity reaching a bulk Li+ ion conductivity averaging 6.8 × 10−4 S cm−1, a total Li-ion conductivity averaging 4.2 × 10−4 S cm−1, and electronic conductivity averaging 3.8 × 10−4 S cm−1 for the composition Li1.25Cr0.25Ti1.5O4 with 1 wt. % LBO. An electrochemically active solid solution of Li1.25Cr0.25Mn1.5O4 and LiNi0.5Mn1.5O4 was prepared. This work proves that Li-stuffed spinels can achieve fast Li-ion conduction and that the concept is potentially useful to enable a single-phase fully solid electrode without interphase impedance. Full article
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
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18 pages, 3675 KiB  
Article
Unusual Spin Exchanges Mediated by the Molecular Anion P2S64−: Theoretical Analyses of the Magnetic Ground States, Magnetic Anisotropy and Spin Exchanges of MPS3 (M = Mn, Fe, Co, Ni)
by Hyun-Joo Koo, Reinhard Kremer and Myung-Hwan Whangbo
Molecules 2021, 26(5), 1410; https://doi.org/10.3390/molecules26051410 - 05 Mar 2021
Cited by 15 | Viewed by 2893
Abstract
We examined the magnetic ground states, the preferred spin orientations and the spin exchanges of four layered phases MPS3 (M = Mn, Fe, Co, Ni) by first principles density functional theory plus onsite repulsion (DFT + U) calculations. The magnetic ground states [...] Read more.
We examined the magnetic ground states, the preferred spin orientations and the spin exchanges of four layered phases MPS3 (M = Mn, Fe, Co, Ni) by first principles density functional theory plus onsite repulsion (DFT + U) calculations. The magnetic ground states predicted for MPS3 by DFT + U calculations using their optimized crystal structures are in agreement with experiment for M = Mn, Co and Ni, but not for FePS3. DFT + U calculations including spin-orbit coupling correctly predict the observed spin orientations for FePS3, CoPS3 and NiPS3, but not for MnPS3. Further analyses suggest that the ||z spin direction observed for the Mn2+ ions of MnPS3 is caused by the magnetic dipole–dipole interaction in its magnetic ground state. Noting that the spin exchanges are determined by the ligand p-orbital tails of magnetic orbitals, we formulated qualitative rules governing spin exchanges as the guidelines for discussing and estimating the spin exchanges of magnetic solids. Use of these rules allowed us to recognize several unusual exchanges of MPS3, which are mediated by the symmetry-adapted group orbitals of P2S64− and exhibit unusual features unknown from other types of spin exchanges. Full article
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
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13 pages, 4803 KiB  
Article
WO3 Nanowire/Carbon Nanotube Interlayer as a Chemical Adsorption Mediator for High-Performance Lithium-Sulfur Batteries
by Sang-Kyu Lee, Hun Kim, Sangin Bang, Seung-Taek Myung and Yang-Kook Sun
Molecules 2021, 26(2), 377; https://doi.org/10.3390/molecules26020377 - 13 Jan 2021
Cited by 12 | Viewed by 3816
Abstract
We developed a new nanowire for enhancing the performance of lithium-sulfur batteries. In this study, we synthesized WO3 nanowires (WNWs) via a simple hydrothermal method. WNWs and one-dimensional materials are easily mixed with carbon nanotubes (CNTs) to form interlayers. The WNW interacts [...] Read more.
We developed a new nanowire for enhancing the performance of lithium-sulfur batteries. In this study, we synthesized WO3 nanowires (WNWs) via a simple hydrothermal method. WNWs and one-dimensional materials are easily mixed with carbon nanotubes (CNTs) to form interlayers. The WNW interacts with lithium polysulfides through a thiosulfate mediator, retaining the lithium polysulfide near the cathode to increase the reaction kinetics. The lithium-sulfur cell achieves a very high initial discharge capacity of 1558 and 656 mAh g−1 at 0.1 and 3 C, respectively. Moreover, a cell with a high sulfur mass loading of 4.2 mg cm−2 still delivers a high capacity of 1136 mAh g−1 at a current density of 0.2 C and it showed a capacity of 939 mAh g−1 even after 100 cycles. The WNW/CNT interlayer maintains structural stability even after electrochemical testing. This excellent performance and structural stability are due to the chemical adsorption and catalytic effects of the thiosulfate mediator on WNW. Full article
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
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12 pages, 9265 KiB  
Article
Syntheses and Characterization of Novel Perovskite-Type LaScO3-Based Lithium Ionic Conductors
by Guowei Zhao, Kota Suzuki, Masaaki Hirayama and Ryoji Kanno
Molecules 2021, 26(2), 299; https://doi.org/10.3390/molecules26020299 - 08 Jan 2021
Cited by 12 | Viewed by 2724
Abstract
Perovskite-type lithium ionic conductors were explored in the (LixLa1−x/3)ScO3 system following their syntheses via a high-pressure solid-state reaction. Phase identification indicated that a solid solution with a perovskite-type structure was formed in the range 0 ≤ [...] Read more.
Perovskite-type lithium ionic conductors were explored in the (LixLa1−x/3)ScO3 system following their syntheses via a high-pressure solid-state reaction. Phase identification indicated that a solid solution with a perovskite-type structure was formed in the range 0 ≤ x < 0.6. When x = 0.45, (Li0.45La0.85)ScO3 exhibited the highest ionic conductivity and a low activation energy. Increasing the loading of lithium as an ionic diffusion carrier expanded the unit cell volume and contributed to the higher ionic conductivity and lower activation energy. Cations with higher oxidation numbers were introduced into the A/B sites to improve the ionic conductivity. Ce4+ and Zr4+ or Nb5+ dopants partially substituted the A-site (La/Li) and B-site Sc, respectively. Although B-site doping produced a lower ionic conductivity, A-site Ce4+ doping improved the conductive properties. A perovskite-type single phase was obtained for (Li0.45La0.78Ce0.05)ScO3 upon Ce4+ doping, providing a higher ionic conductivity than (Li0.45La0.85)ScO3. Compositional analysis and crystal-structure refinement of (Li0.45La0.85)ScO3 and (Li0.45La0.78Ce0.05)ScO3 revealed increased lithium contents and expansion of the unit cell upon Ce4+ co-doping. The highest ionic conductivity of 1.1 × 10−3 S cm−1 at 623 K was confirmed for (Li0.4Ce0.15La0.67)ScO3, which is more than one order of magnitude higher than that of the (LixLa1−x/3)ScO3 system. Full article
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
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10 pages, 2789 KiB  
Article
A Bifunctional Hybrid Electrocatalyst for Oxygen Reduction and Oxygen Evolution Reactions: Nano-Co3O4-Deposited La0.5Sr0.5MnO3 via Infiltration
by Seona Kim, Guntae Kim and Arumugam Manthiram
Molecules 2021, 26(2), 277; https://doi.org/10.3390/molecules26020277 - 08 Jan 2021
Cited by 5 | Viewed by 3219
Abstract
For rechargeable metal–air batteries, which are a promising energy storage device for renewable and sustainable energy technologies, the development of cost-effective electrocatalysts with effective bifunctional activity for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) has been a challenging task. To [...] Read more.
For rechargeable metal–air batteries, which are a promising energy storage device for renewable and sustainable energy technologies, the development of cost-effective electrocatalysts with effective bifunctional activity for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) has been a challenging task. To realize highly effective ORR and OER electrocatalysts, we present a hybrid catalyst, Co3O4-infiltrated La0.5Sr0.5MnO3-δ (LSM@Co3O4), synthesized using an electrospray and infiltration technique. This study expands the scope of the infiltration technique by depositing ~18 nm nanoparticles on unprecedented ~70 nm nano-scaffolds. The hybrid LSM@Co3O4 catalyst exhibits high catalytic activities for both ORR and OER (~7 times, ~1.5 times, and ~1.6 times higher than LSM, Co3O4, and IrO2, respectively) in terms of onset potential and limiting current density. Moreover, with the LSM@Co3O4, the number of electrons transferred reaches four, indicating that the catalyst is effective in the reduction reaction of O2 via a direct four-electron pathway. The study demonstrates that hybrid catalysts are a promising approach for oxygen electrocatalysts for renewable and sustainable energy devices. Full article
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
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14 pages, 4674 KiB  
Article
Electronic and Magnetic Structures of New Interstitial Boron Sub-Oxides B12O2:X (X = B, C, N, O)
by Samir F. Matar and Jean Etourneau
Molecules 2021, 26(1), 123; https://doi.org/10.3390/molecules26010123 - 29 Dec 2020
Cited by 3 | Viewed by 1746
Abstract
The boron-rich boron sub-oxide rhombohedral B6O considered in B12O2 full formulation has a large O-O spacing of ~3 Å and a central vacant position that can receive interstitial atoms X, forming a central O-X-O alignment in the dodecaboron [...] Read more.
The boron-rich boron sub-oxide rhombohedral B6O considered in B12O2 full formulation has a large O-O spacing of ~3 Å and a central vacant position that can receive interstitial atoms X, forming a central O-X-O alignment in the dodecaboron cage as observed in well-known triatomic B12 compounds as B12{C-C-C}, B12{N-B-N}, etc. Plane wave density functional theory (DFT) based calculations of unrestricted geometry relaxation of B12{O-X-O}, X = B, C, N, and O let one identify new ternary sub-oxides, all found cohesive while showing different d(X-O) distances ranging from d(B-O) = 1.95 Å down to d(O-O) = 1.73 Å with intermediate d(C-O) = 1.88 Å. The different magnitudes were assigned to the chemical affinities of X-inserts versus host oxygen with the increasing development of X-O bonding along the series with larger cohesive B12{O-O-O}. From the atom projected charge density, B presents none, while significant magnitudes are shown on C and N, the latter developing bonding with terminal oxygen atoms especially N. The presence of unpaired valence electrons leaves nonbonding charge density on X = C, N interstitial compounds, which, besides the relative isolation of the central C and N lead to the onset of magnetic moments: M(C) = 1.9 μB, and M(N) = 1 μB in a ferromagnetic ground state. Atom-resolved assessments are provided with the magnetic charge density and electron localization function electron localization function (ELF) projections on one hand and the site and spin projected density of states and the chemical bonding based on the overlap integral Sij within the COOP criterion, on the other hand. Full article
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
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Review

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12 pages, 2232 KiB  
Review
Insights into Layered Oxide Cathodes for Rechargeable Batteries
by Julia H. Yang, Haegyeom Kim and Gerbrand Ceder
Molecules 2021, 26(11), 3173; https://doi.org/10.3390/molecules26113173 - 26 May 2021
Cited by 16 | Viewed by 8050
Abstract
Layered intercalation compounds are the dominant cathode materials for rechargeable Li-ion batteries. In this article we summarize in a pedagogical way our work in understanding how the structure’s topology, electronic structure, and chemistry interact to determine its electrochemical performance. We discuss how alkali–alkali [...] Read more.
Layered intercalation compounds are the dominant cathode materials for rechargeable Li-ion batteries. In this article we summarize in a pedagogical way our work in understanding how the structure’s topology, electronic structure, and chemistry interact to determine its electrochemical performance. We discuss how alkali–alkali interactions within the Li layer influence the voltage profile, the role of the transition metal electronic structure in dictating O3-structural stability, and the mechanism for alkali diffusion. We then briefly delve into emerging, next-generation Li-ion cathodes that move beyond layered intercalation hosts by discussing disordered rocksalt Li-excess structures, a class of materials which may be essential in circumventing impending resource limitations in our era of clean energy technology. Full article
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
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27 pages, 21045 KiB  
Review
The Fascinating World of Low-Dimensional Quantum Spin Systems: Ab Initio Modeling
by Tanusri Saha-Dasgupta
Molecules 2021, 26(6), 1522; https://doi.org/10.3390/molecules26061522 - 10 Mar 2021
Cited by 4 | Viewed by 2381
Abstract
In recent times, ab initio density functional theory has emerged as a powerful tool for making the connection between models and materials. Insulating transition metal oxides with a small spin forms a fascinating class of strongly correlated systems that exhibit spin-gap states, spin–charge [...] Read more.
In recent times, ab initio density functional theory has emerged as a powerful tool for making the connection between models and materials. Insulating transition metal oxides with a small spin forms a fascinating class of strongly correlated systems that exhibit spin-gap states, spin–charge separation, quantum criticality, superconductivity, etc. The coupling between spin, charge, and orbital degrees of freedom makes the chemical insights equally important to the strong correlation effects. In this review, we establish the usefulness of ab initio tools within the framework of the N-th order muffin orbital (NMTO)-downfolding technique in the identification of a spin model of insulating oxides with small spins. The applicability of the method has been demonstrated by drawing on examples from a large number of cases from the cuprate, vanadate, and nickelate families. The method was found to be efficient in terms of the characterization of underlying spin models that account for the measured magnetic data and provide predictions for future experiments. Full article
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
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22 pages, 6314 KiB  
Review
Towards Reversible High-Voltage Multi-Electron Reactions in Alkali-Ion Batteries Using Vanadium Phosphate Positive Electrode Materials
by Edouard Boivin, Jean-Noël Chotard, Christian Masquelier and Laurence Croguennec
Molecules 2021, 26(5), 1428; https://doi.org/10.3390/molecules26051428 - 06 Mar 2021
Cited by 27 | Viewed by 4620
Abstract
Vanadium phosphate positive electrode materials attract great interest in the field of Alkali-ion (Li, Na and K-ion) batteries due to their ability to store several electrons per transition metal. These multi-electron reactions (from V2+ to V5+) combined with the high [...] Read more.
Vanadium phosphate positive electrode materials attract great interest in the field of Alkali-ion (Li, Na and K-ion) batteries due to their ability to store several electrons per transition metal. These multi-electron reactions (from V2+ to V5+) combined with the high voltage of corresponding redox couples (e.g., 4.0 V vs. for V3+/V4+ in Na3V2(PO4)2F3) could allow the achievement the 1 kWh/kg milestone at the positive electrode level in Alkali-ion batteries. However, a massive divergence in the voltage reported for the V3+/V4+ and V4+/V5+ redox couples as a function of crystal structure is noticed. Moreover, vanadium phosphates that operate at high V3+/V4+ voltages are usually unable to reversibly exchange several electrons in a narrow enough voltage range. Here, through the review of redox mechanisms and structural evolutions upon electrochemical operation of selected widely studied materials, we identify the crystallographic origin of this trend: the distribution of PO4 groups around vanadium octahedra, that allows or prevents the formation of the vanadyl distortion (O…V4+=O or O…V5+=O). While the vanadyl entity massively lowers the voltage of the V3+/V4+ and V4+/V5+ couples, it considerably improves the reversibility of these redox reactions. Therefore, anionic substitutions, mainly O2− by F−, have been identified as a strategy allowing for combining the beneficial effect of the vanadyl distortion on the reversibility with the high voltage of vanadium redox couples in fluorine rich environments. Full article
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
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26 pages, 2512 KiB  
Review
Spin Hamiltonians in Magnets: Theories and Computations
by Xueyang Li, Hongyu Yu, Feng Lou, Junsheng Feng, Myung-Hwan Whangbo and Hongjun Xiang
Molecules 2021, 26(4), 803; https://doi.org/10.3390/molecules26040803 - 04 Feb 2021
Cited by 33 | Viewed by 6078
Abstract
The effective spin Hamiltonian method has drawn considerable attention for its power to explain and predict magnetic properties in various intriguing materials. In this review, we summarize different types of interactions between spins (hereafter, spin interactions, for short) that may be used in [...] Read more.
The effective spin Hamiltonian method has drawn considerable attention for its power to explain and predict magnetic properties in various intriguing materials. In this review, we summarize different types of interactions between spins (hereafter, spin interactions, for short) that may be used in effective spin Hamiltonians as well as the various methods of computing the interaction parameters. A detailed discussion about the merits and possible pitfalls of each technique of computing interaction parameters is provided. Full article
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
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26 pages, 6763 KiB  
Review
Spin Exchanges between Transition Metal Ions Governed by the Ligand p-Orbitals in Their Magnetic Orbitals
by Myung-Hwan Whangbo, Hyun-Joo Koo and Reinhard K. Kremer
Molecules 2021, 26(3), 531; https://doi.org/10.3390/molecules26030531 - 20 Jan 2021
Cited by 21 | Viewed by 3019
Abstract
In this review on spin exchanges, written to provide guidelines useful for finding the spin lattice relevant for any given magnetic solid, we discuss how the values of spin exchanges in transition metal magnetic compounds are quantitatively determined from electronic structure calculations, which [...] Read more.
In this review on spin exchanges, written to provide guidelines useful for finding the spin lattice relevant for any given magnetic solid, we discuss how the values of spin exchanges in transition metal magnetic compounds are quantitatively determined from electronic structure calculations, which electronic factors control whether a spin exchange is antiferromagnetic or ferromagnetic, and how these factors are related to the geometrical parameters of the spin exchange path. In an extended solid containing transition metal magnetic ions, each metal ion M is surrounded with main-group ligands L to form an MLn polyhedron (typically, n = 3–6), and the unpaired spins of M are represented by the singly-occupied d-states (i.e., the magnetic orbitals) of MLn. Each magnetic orbital has the metal d-orbital combined out-of-phase with the ligand p-orbitals; therefore, the spin exchanges between adjacent metal ions M lead not only to the M–L–M-type exchanges, but also to the M–L…L–M-type exchanges in which the two metal ions do not share a common ligand. The latter can be further modified by d0 cations A such as V5+ and W6+ to bridge the L…L contact generating M–L…A…L–M-type exchanges. We describe several qualitative rules for predicting whether the M–L…L–M and M–L…A…L–M-type exchanges are antiferromagnetic or ferromagnetic by analyzing how the ligand p-orbitals in their magnetic orbitals (the ligand p-orbital tails, for short) are arranged in the exchange paths. Finally, we illustrate how these rules work by analyzing the crystal structures and magnetic properties of four cuprates of current interest: α-CuV2O6, LiCuVO4, (CuCl)LaNb2O7, and Cu3(CO3)2(OH)2. Full article
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
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10 pages, 888 KiB  
Commentary
John B. Goodenough’s Role in Solid State Chemistry Community: A Thrilling Scientific Tale Told by a French Chemist
by Michel Pouchard
Molecules 2020, 25(24), 6040; https://doi.org/10.3390/molecules25246040 - 21 Dec 2020
Cited by 5 | Viewed by 2988
Abstract
In this tribute to John B. Goodenough I will describe how John’s talk on the metal-to-nonmetal transition of vanadium oxide VO2, presented at the Bordeaux Conference (September 1964) attended by inorganic chemists, metallurgists, crystallographers, thermodynamicists and physicists, provided a pioneering vision [...] Read more.
In this tribute to John B. Goodenough I will describe how John’s talk on the metal-to-nonmetal transition of vanadium oxide VO2, presented at the Bordeaux Conference (September 1964) attended by inorganic chemists, metallurgists, crystallographers, thermodynamicists and physicists, provided a pioneering vision of interdisciplinary research to come. John gave a complete description of the paradigm on how the physical properties of a solid depend on its structure and bonding, by employing the chemical notions as local distortions and interatomic distances as well as the physics notions such as band width and the Hubbard on-site repulsion U. I will illustrate how inspiring John’s ideas were, by discussing the research examples of my own research group in the sixties-seventies. The fundamental approach of John B. Goodenough to Solid State Chemistry, leading particularly to lithium battery applications, is at the heart of the 2019 Nobel Prize awarded to John. Full article
(This article belongs to the Special Issue A Themed Issue Dedicated to Professor John B. Goodenough on the Occasion of His 100th Birthday Anniversary)
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