Glyme Solvent Decomposition on Spinel Cathode Surface in Magnesium Battery

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This article references 29 other publications.

1. 1

   Kim, T.; Park, J.; Chang, S. K.; Choi, S.; Ryu, J. H.; Song, H. The Current Move of Lithium Ion Batteries towards the next Phase. Adv. Energy Mater. 2012, 2 (7), 860– 872,  DOI: 10.1002/aenm.201200028

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   The current move of lithium ion batteries towards the next phase

   Kim, Tae-Hee; Park, Jeong-Seok; Chang, Sung Kyun; Choi, Seungdon; Ryu, Ji Heon; Song, Hyun-Kon

   Advanced Energy Materials (2012), 2 (7), 860-872CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)

   A review. Application targets of lithium ion batteries (LIBs) are moving from small-sized mobile devices of information technol. to large-scale elec. vehicles (xEVs) and energy storage systems (ESSs). Environmental issues and abruptly increasing power demands are pushing high performance energy storage devices or systems onto markets. LIBs are one of the most potential candidates as the energy storage devices mainly due to their high energy densities with fairly good rate capabilities and a fairly long cycle life. As battery systems become larger in terms of stored energy as well as phys. size, the safety concerns should be more seriously cared. Each application target has its own specification so that electrode materials should be chosen to meet requirements of the corresponding application. This report diagnoses the current market trends of LIBs as a primary topic, followed by giving an overview of anode and cathode material candidates of LIBs for xEVs and ESSs based on their electrochem. properties.
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   Thackeray, M. M.; Wolverton, C.; Isaacs, E. D. Electrical Energy Storage for Transportation─Approaching the Limits of, and Going beyond, Lithium-Ion Batteries. Energy Environ. Sci. 2012, 5 (7), 7854– 7863,  DOI: 10.1039/c2ee21892e

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   Electrical energy storage for transportation-approaching the limits of, and going beyond, lithium-ion batteries

   Thackeray, Michael M.; Wolverton, Christopher; Isaacs, Eric D.

   Energy & Environmental Science (2012), 5 (7), 7854-7863CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)

   A review. The escalating and unpredictable cost of oil, the concn. of major oil resources in the hands of a few politically sensitive nations, and the long-term impact of CO2 emissions on global climate constitute a major challenge for the 21st century. They also constitute a major incentive to harness alternative sources of energy and means of vehicle propulsion. Today's lithium-ion batteries, although suitable for small-scale devices, do not yet have sufficient energy or life for use in vehicles that would match the performance of internal combustion vehicles. Energy densities 2 and 5 times greater are required to meet the performance goals of a future generation of plug-in hybrid-elec. vehicles (PHEVs) with a 40-80 mi all-elec. range, and all-elec. vehicles (EVs) with a 300-400 mi range, resp. Major advances have been made in lithium-battery technol. over the past two decades by the discovery of new materials and designs through intuitive approaches, exptl. and predictive reasoning, and meticulous control of surface structures and chem. reactions. Further improvements in energy d. of factors of two to three may yet be achievable for current day lithium-ion systems; factors of five or more may be possible for lithium-oxygen systems, ultimately leading to our ability to confine extremely high potential energy in a small vol. without compromising safety, but only if daunting technol. barriers can be overcome.
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   Aurbach, D.; Lu, Z.; Schechter, A.; Gofer, Y.; Gizbar, H.; Turgeman, R.; Cohen, Y.; Moshkovich, M.; Levi, E. Prototype Systems for Rechargeable Magnesium Batteries. Nature 2000, 407 (6805), 724– 727,  DOI: 10.1038/35037553

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   Prototype systems for rechargeable magnesium batteries

   Aurbach, D.; Lu, Z.; Schechter, A.; Gofer, Y.; Gizbar, H.; Turgeman, R.; Cohen, Y.; Moshkovich, M.; Levi, E.

   Nature (London) (2000), 407 (6805), 724-727CODEN: NATUAS; ISSN:0028-0836. (Nature Publishing Group)

   The thermodn. properties of magnesium make it a natural choice for use as an anode material in rechargeable batteries, because it may provide a considerably higher energy d. than the commonly used lead-acid and nickel-cadmium systems. Moreover, in contrast to lead and cadmium, magnesium is inexpensive, environmentally friendly and safe to handle. But the development of Mg batteries has been hindered by two problems. First, owing to the chem. activity of Mg, only solns. that neither donate nor accept protons are suitable as electrolytes; but most of these solns. allow the growth of passivating surface films, which inhibit any electrochem. reaction. Second, the choice of cathode materials has been limited by the difficulty of intercalating Mg ions in many hosts. Following previous studies of the electrochem. of Mg electrodes in various non-aq. solns., and of a variety of intercalation electrodes, we have now developed rechargeable Mg battery systems that show promise for applications. The systems comprise electrolyte solns. based on Mg organohaloaluminate salts, and MgxMo3S4 cathodes, into which Mg ions can be intercalated reversibly, and with relatively fast kinetics. We expect that further improvements in the energy d. will make these batteries a viable alternative to existing systems.
4. 4

   Taniguchi, K.; Gu, Y.; Katsura, Y.; Yoshino, T.; Takagi, H. Rechargeable Mg Battery Cathode TiS₃ with d-p Orbital Hybridized Electronic Structures. Appl. Phys. Express 2016, 9 (1), 011801,  DOI: 10.7567/APEX.9.011801

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   Rechargeable Mg battery cathode TiS3 with d-p orbital hybridized electronic structures

   Taniguchi, Kouji; Gu, Yunpeng; Katsura, Yukari; Yoshino, Takafumi; Takagi, Hidenori

   Applied Physics Express (2016), 9 (1), 011801/1-011801/4CODEN: APEPC4; ISSN:1882-0786. (IOP Publishing Ltd.)

   Rechargeable performance is realized in Mg batteries using a TiS3 cathode without the nanometer-scale downsizing of electrode particles. The specific capacity is about 80 mAh/g for the first 50 cycles at room temp. This obsd. specific capacity is comparable to that of the prototype cathode for Mg batteries. First-principles calcn. indicates that TiS3 is a semiconductor with d-p orbital hybridized electronic structures around the Fermi level. The reversible electrode performance is likely assisted by the delocalized electronic distribution over metal-ligand units through d-p orbital hybridization.
5. 5

   Wang, M.; Han, J.; Liu, W.; Kamiko, M.; Yagi, S. Energy Storage Mechanism of Monocrystalline Layered FePS₃ and FePSe₃ as Active Materials for Mg Batteries and Pseudocapacitors. J. Alloys Compd. 2021, 883, 160822,  DOI: 10.1016/j.jallcom.2021.160822

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   Energy storage mechanism of monocrystalline layered Iron phosphorus trichalcogenide and Iron Selenophosphate as active materials for magnesium batteries and pseudocapacitors

   Wang, Mengqiao; Han, Jonghyun; Liu, Wei; Kamiko, Masao; Yagi, Shunsuke

   Journal of Alloys and Compounds (2021), 883 (), 160822CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)

   We report the reversible intercalation of Mg2+ ions into monocryst. layered FePS3 in a THF electrolyte contg. 0.8 M PhMgCl and 0.4 M AlCl3. Mg2+ ions were not intercalated into FePSe3 because of the lower interlayer spacings (FePS3: 1.24 Å, FePSe3, 1.00 Å). The contribution of the non-Faradaic (double layer formation) and Faradaic (electrochem. intercalation/deintercalation, adsorption/desorption) processes toward the energy storage mechanism of FePS3 and FePSe3 were quantified. The max. specific capacity displayed by FePS3 was 232.7 mAh g-1 at a c.d. of 0.2 A g-1, which was higher than that of FePSe3 (153.1 mAh g-1). Even at high c.d. (2 A g-1), FePS3 exhibited a specific capacity of 100.7 mAh g-1 after 450 cycles; the specific capacity of the less robust FePSe3 was just 26.3 mAh g-1.
6. 6

   Orikasa, Y.; Masese, T.; Koyama, Y.; Mori, T.; Hattori, M.; Yamamoto, K.; Okado, T.; Huang, Z.-D.; Minato, T.; Tassel, C. High Energy Density Rechargeable Magnesium Battery Using Earth-Abundant and Non-Toxic Elements. Sci. Rep. 2014, 4 (1), 5622,  DOI: 10.1038/srep05622

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   High energy density rechargeable magnesium battery using earth-abundant and non-toxic elements

   Orikasa, Yuki; Masese, Titus; Koyama, Yukinori; Mori, Takuya; Hattori, Masashi; Yamamoto, Kentaro; Okado, Tetsuya; Huang, Zhen-Dong; Minato, Taketoshi; Tassel, Cedric; Kim, Jungeun; Kobayashi, Yoji; Abe, Takeshi; Kageyama, Hiroshi; Uchimoto, Yoshiharu

   Scientific Reports (2014), 4 (), 5622CODEN: SRCEC3; ISSN:2045-2322. (Nature Publishing Group)

   Rechargeable magnesium batteries are poised to be viable candidates for large-scale energy storage devices in smart grid communities and elec. vehicles. However, the energy d. of previously proposed rechargeable magnesium batteries is low, limited mainly by the cathode materials. Here, we present new design approaches for the cathode in order to realize a high-energy-d. rechargeable magnesium battery system. Ion-exchanged MgFeSiO4 demonstrates a high reversible capacity exceeding 300 mAh·g-1 at a voltage of approx. 2.4 V vs. Mg. Further, the electronic and crystal structure of ion-exchanged MgFeSiO4 changes during the charging and discharging processes, which demonstrates the (de)insertion of magnesium in the host structure. The combination of ion-exchanged MgFeSiO4 with a magnesium bis(trifluoromethylsulfonyl)imide-triglyme electrolyte system proposed in this work provides a low-cost and practical rechargeable magnesium battery with high energy d., free from corrosion and safety problems.
7. 7

   NuLi, Y.; Zheng, Y.; Wang, Y.; Yang, J.; Wang, J. Electrochemical Intercalation of Mg²⁺ in 3D Hierarchically Porous Magnesium Cobalt Silicate and Its Application as an Advanced Cathode Material in Rechargeable Magnesium Batteries. J. Mater. Chem. 2011, 21 (33), 12437– 12443,  DOI: 10.1039/c1jm10485c

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   Electrochemical intercalation of Mg2+ in 3D hierarchically porous magnesium cobalt silicate and its application as an advanced cathode material in rechargeable magnesium batteries

   NuLi, Yanna; Zheng, Yupei; Wang, Ying; Yang, Jun; Wang, Jiulin

   Journal of Materials Chemistry (2011), 21 (33), 12437-12443CODEN: JMACEP; ISSN:0959-9428. (Royal Society of Chemistry)

   We report the formation of three-dimensional hierarchically porous MgCoSiO4 and the electrochem. intercalation of the bivalent cation Mg2+ in MgCoSiO4 with regard to its use as a cathode material in rechargeable magnesium batteries. Reversible Mg2+ intercalation can be demonstrated and the process is enhanced by the use of a novel three-dimensional hierarchically porous architecture, consisting of a network of macropores with several nanometer wall and mesopores at the boundaries of grains or between grains. It is suggested that the interconnected wall structure, dual porosity and high surface area reduces the solid-state diffusion lengths for Mg diffusion, facilitates electrolyte penetration into particles and provides a large no. of active sites for charge-transfer reactions.
8. 8

   Hatakeyama, T.; Li, H.; Okamoto, N. L.; Shimokawa, K.; Kawaguchi, T.; Tanimura, H.; Imashuku, S.; Fichtner, M.; Ichitsubo, T. Accelerated Kinetics Revealing Metastable Pathways of Magnesiation-Induced Transformations in MnO₂ Polymorphs. Chem. Mater. 2021, 33 (17), 6983– 6996,  DOI: 10.1021/acs.chemmater.1c02011

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   Accelerated Kinetics Revealing Metastable Pathways of Magnesiation-Induced Transformations in MnO2 Polymorphs

   Hatakeyama, Takuya; Li, Hongyi; Okamoto, Norihiko L.; Shimokawa, Kohei; Kawaguchi, Tomoya; Tanimura, Hiroshi; Imashuku, Susumu; Fichtner, Maximilian; Ichitsubo, Tetsu

   Chemistry of Materials (2021), 33 (17), 6983-6996CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)

   The intrinsic potential of manganese dioxides, considered high-capacity cathodes of rechargeable magnesium batteries, was clearly exposed under conditions where the Mg migration kinetics are sufficiently enhanced. It has been reported to date that magnesium insertion into MnO2 is substantially confined to the surfaces of MnO2 particles due to its sluggish kinetics at room temp., which leads to local over-magnesiation conditions causing conversion reactions etc. To unveil its ergodic or metastable phase-transformation pathways of MnO2 polymorphs (α, β, γ, δ, and λ) during magnesiation, this study employed intermediate-temp. electrochem. expts. (at 150°C) using heat-tolerant ionic liq. electrolytes. Regardless of its original polymorphic structure, each MnO2 polymorph was found to transform into a Mg-including spinel and then to a rocksalt-like phase by magnesiation. Given this tendency of transformation, the defect spinel λ-MnO2 phase possessing the coherent framework of spinel/rocksalt structures is expected to follow a topotactic transformation pathway, but thermally unstable λ-MnO2 underwent spontaneous redn. into Mn3O4 before magnesiation in an electrolyte. Instead, α-MnO2 was found to be robust enough among MnO2 polymorphs to exhibit reversible magnesium intercalation at 150°C under limiting capacity conditions. This result highlights that reversible magnesium intercalation in oxide cathodes is feasible for structures that are kinetically resistant to irreversible transformation pathways to spinel and rocksalt structures.
9. 9

   Hatakeyama, T.; Okamoto, N. L.; Shimokawa, K.; Li, H.; Nakao, A.; Uchimoto, Y.; Tanimura, H.; Kawaguchi, T.; Ichitsubo, T. Electrochemical Phase Transformation Accompanied with Mg Extraction and Insertion in a Spinel MgMn₂O₄ Cathode Material. Phys. Chem. Chem. Phys. 2019, 21 (42), 23749– 23757,  DOI: 10.1039/C9CP04461B

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   Electrochemical phase transformation accompanied with Mg extraction and insertion in a spinel MgMn2O4 cathode material

   Hatakeyama, Takuya; Okamoto, Norihiko L.; Shimokawa, Kohei; Li, Hongyi; Nakao, Aiko; Uchimoto, Yoshiharu; Tanimura, Hiroshi; Kawaguchi, Tomoya; Ichitsubo, Tetsu

   Physical Chemistry Chemical Physics (2019), 21 (42), 23749-23757CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)

   One of the key challenges when developing magnesium rechargeable batteries (MRB) is to develop Mg-intercalation cathodes exhibiting higher redox potentials with larger specific capacities. Although Mg-transition-metal spinel oxides have been shown to be excellent candidates as MRB cathode materials by utilizing the valence change from trivalent to divalent of transition metals starting from Mg insertion, there is no clear evidence to date that Mg can be indeed extd. from the initial spinel hosts by utilizing the change from trivalent to quadrivalent. In this work, we clearly present various exptl. evidences of the electrochem. extn. of Mg from spinel MgMn2O4. The present electrochem. charge, i.e., extn. treatment of Mg, was performed in an ionic liq. at 150 °C to ensure Mg hopping in the spinel host. Our analyses show that Mg can be extd. from Mg1-xMn2O4 up to x = 0.4 and, afterwards, successively be inserted into the Mg-extd. (demagnesiated) host via a two-phase reaction between tetragonal and cubic spinels. Finally, we also discuss the difference in electrochem. features between LiMn2O4 and MgMn2O4.
10. 10

    Okamoto, S.; Ichitsubo, T.; Kawaguchi, T.; Kumagai, Y.; Oba, F.; Yagi, S.; Shimokawa, K.; Goto, N.; Doi, T.; Matsubara, E. Intercalation and Push-Out Process with Spinel-to-Rocksalt Transition on Mg Insertion into Spinel Oxides in Magnesium Batteries. Adv. Sci. 2015, 2 (8), 1500072,  DOI: 10.1002/advs.201500072

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    Intercalation and Push-Out Process with Spinel-to-Rocksalt Transition on Mg Insertion into Spinel Oxides in Magnesium Batteries

    Okamoto Shinya; Ichitsubo Tetsu; Kawaguchi Tomoya; Shimokawa Kohei; Goto Natsumi; Matsubara Eiichiro; Kumagai Yu; Oba Fumiyasu; Yagi Shunsuke; Doi Takayuki

    Advanced science (Weinheim, Baden-Wurttemberg, Germany) (2015), 2 (8), 1500072 ISSN:2198-3844.

    On the basis of the similarity between spinel and rocksalt structures, it is shown that some spinel oxides (e.g., MgCo2O4, etc) can be cathode materials for Mg rechargeable batteries around 150 °C. The Mg insertion into spinel lattices occurs via "intercalation and push-out" process to form a rocksalt phase in the spinel mother phase. For example, by utilizing the valence change from Co(III) to Co(II) in MgCo2O4, Mg insertion occurs at a considerably high potential of about 2.9 V vs. Mg(2+)/Mg, and similarly it occurs around 2.3 V vs. Mg(2+)/Mg with the valence change from Mn(III) to Mn(II) in MgMn2O4, being comparable to the ab initio calculation. The feasibility of Mg insertion would depend on the phase stability of the counterpart rocksalt XO of MgO in Mg2X2O4 or MgX3O4 (X = Co, Fe, Mn, and Cr). In addition, the normal spinel MgMn2O4 and MgCr2O4 can be demagnesiated to some extent owing to the robust host structure of Mg1-xX2O4, where the Mg extraction/insertion potentials for MgMn2O4 and MgCr2O4 are both about 3.4 V vs. Mg(2+)/Mg. Especially, the former "intercalation and push-out" process would provide a safe and stable design of cathode materials for polyvalent cations.
11. 11

    Shimokawa, K.; Atsumi, T.; Harada, M.; Ward, R. E.; Nakayama, M.; Kumagai, Y.; Oba, F.; Okamoto, N. L.; Kanamura, K.; Ichitsubo, T. Zinc-Based Spinel Cathode Materials for Magnesium Rechargeable Batteries: Toward the Reversible Spinel-Rocksalt Transition. J. Mater. Chem. A 2019, 7 (19), 12225– 12235,  DOI: 10.1039/C9TA02281C

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    Zinc-based spinel cathode materials for magnesium rechargeable batteries: toward the reversible spinel-rocksalt transition

    Shimokawa, Kohei; Atsumi, Taruto; Harada, Maho; Ward, Robyn E.; Nakayama, Masanobu; Kumagai, Yu; Oba, Fumiyasu; Okamoto, Norihiko L.; Kanamura, Kiyoshi; Ichitsubo, Tetsu

    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (19), 12225-12235CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)

    The spinel-to-rocksalt transition with Mg insertion into spinel oxides upon discharge can be utilized as a cathode reaction for magnesium rechargeable batteries. However, the formation of the resulting robust rocksalt phase can be harmful to the cyclability, in that it is sluggish to revert to the original spinel structure. In this work, we show that the inverse "rocksalt-to-spinel" transition can be facilitated upon charge by stabilizing the spinel structure with Zn preferring a tetrahedral environment. Our ab initio calcn. study substantiates that Zn-based spinel oxides (space group #227) favor a normal-spinel configuration owing to covalency of Zn-O in the tetrahedral 8a site and cation disordering or migration from 8a to 16c sites tends to be unfavorable in terms of thermodn. and kinetics. Based on this theor. prediction, we show exptl. that such a stabilized normal spinel structure (i.e., ZnCo2O4 and ZnFe2O4) consequently allows the reversible spinel-rocksalt transition upon charge and discharge. Furthermore, the vol. change of ZnFe2O4 in discharge/charge is much smaller than that of Co-based spinel oxides, which can provide a nearly zero-strain cathode material consisting of abundant elements.
12. 12

    Sun, X.; Bonnick, P.; Duffort, V.; Liu, M.; Rong, Z.; Persson, K. A.; Ceder, G.; Nazar, L. F. A High Capacity Thiospinel Cathode for Mg Batteries. Energy Environ. Sci. 2016, 9 (7), 2273– 2277,  DOI: 10.1039/C6EE00724D

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    A high capacity thiospinel cathode for Mg batteries

    Sun, Xiaoqi; Bonnick, Patrick; Duffort, Victor; Liu, Miao; Rong, Ziqin; Persson, Kristin A.; Ceder, Gerbrand; Nazar, Linda F.

    Energy & Environmental Science (2016), 9 (7), 2273-2277CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)

    Magnesium batteries are energy storage systems that potentially offer high energy d. owing to their ability to employ magnesium metal as a neg. electrode. Their development, however, has been thwarted by a paucity of functional pos. electrode materials after the seminal discovery of the Mo6S8 Chevrel phase over 15 years ago. Herein, we report the second such material - a thiospinel - and demonstrate fully reversible Mg2+ electrochem. cycling vs. a Mg anode, which is complemented by diffraction and first principles calcns. The capacity approaches 80% of the theor. value at a practical rate (C/5) at 60 °C, and yields a specific energy of 230 Wh kg-1, twice that of the Chevrel benchmark. Our results emphasize the advantage in employing "soft" anions to achieve practical divalent cation mobility.
13. 13

    Kolli, S. K.; Van der Ven, A. Elucidating the Factors That Cause Cation Diffusion Shutdown in Spinel-Based Electrodes. Chem. Mater. 2021, 33 (16), 6421– 6432,  DOI: 10.1021/acs.chemmater.1c01668

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    Elucidating the Factors That Cause Cation Diffusion Shutdown in Spinel-Based Electrodes

    Kolli, Sanjeev Krishna; Van der Ven, Anton

    Chemistry of Materials (2021), 33 (16), 6421-6432CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)

    We report on a systematic study of guest cation (i.e., Li, Na, or Mg) diffusion within spinel intercalation compds., a promising class of materials for Li-, Na-, and Mg-ion batteries. Using kinetic Monte Carlo simulations, we identify factors that are responsible for a strong concn. dependence of the cation diffusion coeff. We focus on spinels in which the guest cations prefer the octahedral sites and where diffusion is mediated by vacancy clusters. Starting with MgyTiS2, we predict an abrupt drop in the Mg diffusion coeff. that spans several orders of magnitude around y ≈ 0.5 due to the onset of highly correlated Mg diffusion. The prediction is consistent with previous exptl. studies that are only able to achieve half the theor. capacity of MgyTiS2. We next perform a parametric study of diffusion in spinels using kinetic Monte Carlo simulations applied to lattice model Hamiltonians and identify a crit. topol. weakness of the spinel crystal structure that makes it prone to highly correlated cation diffusion at intermediate-to-high guest cation concns. We find that the onset of this highly correlated diffusion becomes more pronounced as the nearest-neighbor repulsion between pairs of guest cations becomes stronger, since this increases the dependence of long-range cation diffusion on triple-vacancy clusters. The results of this study provide guidance with which the concn. dependence of cation diffusion coeffs. in spinel can be tailored to reduce the onset of sluggish diffusion at high cation concns. The conclusions drawn from this study also apply to other close-packed anion hosts such as disordered rocksalt electrodes and partially ordered spinels.
14. 14

    Johnson, I. D.; Mistry, A. N.; Yin, L.; Murphy, M.; Wolfman, M.; Fister, T. T.; Lapidus, S. H.; Cabana, J.; Srinivasan, V.; Ingram, B. J. Unconventional Charge Transport in MgCr₂O₄ and Implications for Battery Intercalation Hosts. J. Am. Chem. Soc. 2022, 144 (31), 14121– 14131,  DOI: 10.1021/jacs.2c03491

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    14

    Unconventional charge transport in MgCr2O4 and implications for battery intercalation hosts

    Johnson, Ian D.; Mistry, Aashutosh N.; Yin, Liang; Murphy, Megan; Wolfman, Mark; Fister, Timothy T.; Lapidus, Saul H.; Cabana, Jordi; Srinivasan, Venkat; Ingram, Brian J.

    Journal of the American Chemical Society (2022), 144 (31), 14121-14131CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)

    Ion transport in solid-state cathode materials prescribes a fundamental limit to the rates batteries can operate; therefore, an accurate understanding of ion transport is a crit. missing piece to enable new battery technologies, such as magnesium batteries. Based on our conventional understanding of lithium-ion materials, MgCr2O4 is a promising magnesium-ion cathode material given its high capacity, high voltage against an Mg anode, and acceptable computed diffusion barriers. Electrochem. examns. of MgCr2O4, however, reveal significant energetic limitations. Motivated by these disparate observations; herein, we examine long-range ion transport by elec. polarizing dense pellets of MgCr2O4. Our conventional understanding of ion transport in battery cathode materials, e.g., Nernst-Einstein conduction, cannot explain the measured response since it neglects frictional interactions between mobile species and their nonideal free energies. We propose an extended theory that incorporates these interactions and reduces to the Nernst-Einstein conduction under dil. conditions. This theory describes the measured response, and we report the first study of long-range ion transport behavior in MgCr2O4. We conclusively show that the Mg chem. diffusivity is comparable to lithium-ion electrode materials, whereas the total cond. is rate-limiting. Given these differences, energy storage in MgCr2O4 is limited by particle-scale voltage drops, unlike lithium-ion particles that are limited by concn. gradients. Future materials design efforts should consider the interspecies interactions described in this extended theory, particularly with respect to multivalent-ion systems and their resultant effects on continuum transport properties.
15. 15

    Bayliss, R. D.; Key, B.; Sai Gautam, G.; Canepa, P.; Kwon, B. J.; Lapidus, S. H.; Dogan, F.; Adil, A. A.; Lipton, A. S.; Baker, P. J. Probing Mg Migration in Spinel Oxides. Chem. Mater. 2020, 32 (2), 663– 670,  DOI: 10.1021/acs.chemmater.9b02450

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    15

    Probing Mg Migration in Spinel Oxides

    Bayliss, Ryan D.; Key, Baris; Sai Gautam, Gopalakrishnan; Canepa, Pieremanuele; Kwon, Bob Jin; Lapidus, Saul H.; Dogan, Fulya; Adil, Abdullah A.; Lipton, Andrew S.; Baker, Peter J.; Ceder, Gerbrand; Vaughey, John T.; Cabana, Jordi

    Chemistry of Materials (2020), 32 (2), 663-670CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)

    Mg batteries utilizing oxide cathodes can theor. surpass the energy d. of current Li-ion technologies. The absence of functional devices so far has been ascribed to impeded Mg2+ migration within oxides, which severely handicaps intercalation reactions at the cathode. Broadly, knowledge of divalent cation migration in solid frameworks is surprisingly deficient. Here, we present a combined exptl. and theor. study of Mg migration within three spinel oxides, which reveal crit. features that influence it. Exptl. activation energies for a Mg2+ hop to an adjacent vacancy, as low as ∼0.6 eV, are reported. These barriers are low enough to support functional electrodes based on the intercalation of Mg2+. Subsequent electrochem. expts. demonstrate that significant demagnesiation is indeed possible, but the challenges instead lie with the chem. stability of the oxidized states. Our findings enhance the understanding of cation transport in solid structures and renew the prospects of finding materials capable of high d. of energy storage.
16. 16

    Sai Gautam, G.; Canepa, P.; Urban, A.; Bo, S.-H.; Ceder, G. Influence of Inversion on Mg Mobility and Electrochemistry in Spinels. Chem. Mater. 2017, 29 (18), 7918– 7930,  DOI: 10.1021/acs.chemmater.7b02820

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    Influence of Inversion on Mg Mobility and Electrochemistry in Spinels

    Sai Gautam, Gopalakrishnan; Canepa, Pieremanuele; Urban, Alexander; Bo, Shou-Hang; Ceder, Gerbrand

    Chemistry of Materials (2017), 29 (18), 7918-7930CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)

    Magnesium oxide and sulfide spinels have recently attracted interest as cathode and electrolyte materials for energy-dense Mg batteries, but their obsd. electrochem. performance depends strongly on synthesis conditions. Using first-principles calcns. and percolation theory, we explore the extent to which spinel inversion influences Mg2+ ionic mobility in MgMn2O4 as a prototypical cathode, and MgIn2S4 as a potential solid electrolyte. We find that spinel inversion and the resulting changes of the local cation ordering give rise to both increased and decreased Mg2+ migration barriers, along specific migration pathways, in the oxide as well as the sulfide. To quantify the impact of spinel inversion on macroscopic Mg2+ transport, we det. the percolation thresholds in both MgMn2O4 and MgIn2S4. Furthermore, we analyze the impact of inversion on the electrochem. properties of the MgMn2O4 cathode via changes in the phase behavior, av. Mg insertion voltages and extractable capacities, at varying degrees of inversion. Our results confirm that inversion is a major performance limiting factor of Mg spinels and that synthesis techniques or compns. that stabilize the well-ordered spinel structure are crucial for the success of Mg spinels in multivalent batteries.
17. 17

    Kwon, B. J.; Yin, L.; Roy, I.; Leon, N. J.; Kumar, K.; Kim, J. J.; Han, J.; Gim, J.; Liao, C.; Lapidus, S. H. Facile Electrochemical Mg-Ion Transport in a Defect-Free Spinel Oxide. Chem. Mater. 2022, 34 (8), 3789– 3797,  DOI: 10.1021/acs.chemmater.2c00237

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    Facile Electrochemical Mg-Ion Transport in a Defect-Free Spinel Oxide

    Kwon, Bob Jin; Yin, Liang; Roy, Indrani; Leon, Noel J.; Kumar, Khagesh; Kim, Jae Jin; Han, Jinhyup; Gim, Jihyeon; Liao, Chen; Lapidus, Saul H.; Cabana, Jordi; Key, Baris

    Chemistry of Materials (2022), 34 (8), 3789-3797CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)

    Inversion, i.e., Mg/Mn antisite disorder, in a spinel oxide simultaneously causes blockage of favorable Mg2+ migration paths, raising activation barriers for diffusion, and it reduces the no. of redox-active metals, limiting the max. capacity in the spinel. An inversion-free spinel, MgCr1.5Mn0.5O4, was synthesized by exploiting the different intrinsic crystal field stabilization of redox-active Cr and Mn in the form of a solid soln. The capability of the tailored spinel to reversibly (de)intercalate Mg2+ at high redox potentials was investigated. The decrease in inversion dramatically lowered the electrochem. overpotential and hysteresis and enabled utilization of high potentials at ~ 2.9 V (vs Mg/Mg2+) upon re-intercalation of Mg2+. A combination of characterization techniques reveals that the structural, compositional, and redox changes within the spinel oxide were consistent with the obsd. electrochem. Mg2+ activity. Quantification of selection solely to lattice Mg2+ upon the electrochem. reaction was investigated by monitoring NMR signals in isotope 25Mg-enriched spinel oxides. Our findings enhance the understanding of Mg2+ transport within spinel oxide frameworks and provide conclusive evidence for bulk Mg migration in oxide lattices at high redox potentials with minimized electrochem. hysteresis.
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    Canepa, P.; Gautam, G. S.; Malik, R.; Jayaraman, S.; Rong, Z.; Zavadil, K. R.; Persson, K.; Ceder, G. Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Nonaqueous Electrolytes. Chem. Mater. 2015, 27 (9), 3317– 3325,  DOI: 10.1021/acs.chemmater.5b00389

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    Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Nonaqueous Electrolytes

    Canepa, Pieremanuele; Gautam, Gopalakrishnan Sai; Malik, Rahul; Jayaraman, Saivenkataraman; Rong, Ziqin; Zavadil, Kevin R.; Persson, Kristin; Ceder, Gerbrand

    Chemistry of Materials (2015), 27 (9), 3317-3325CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)

    Multivalent (MV) battery architectures based on pairing a Mg metal anode with a high-voltage (∼3 V) intercalation cathode offer a realistic design pathway toward significantly surpassing the energy storage performance of traditional Li-ion-based batteries, but there are currently only few electrolyte systems that support reversible Mg deposition. Using both static 1st-principles calcns. and ab initio mol. dynamics, the authors perform a comprehensive adsorption study of several salt and solvent species at the interface of Mg metal with an electrolyte of Mg2+ and Cl- dissolved in liq. THF. The authors' findings not only provide a picture of the stable species at the interface but also explain how this system can support reversible Mg deposition, and as such, the authors provide insights in how to design other electrolytes for Mg plating and stripping. The active depositing species are identified to be (MgCl)+ monomers coordinated by THF, which exhibit preferential adsorption on Mg compared to possible passivating species (such as THF solvent or neutral MgCl2 complexes). Upon deposition, the energy to desolvate these adsorbed complexes and facilitate charge transfer is small (∼61-46.2 kJ mol-1 to remove three THF from the strongest adsorbing complex), and the stable orientations of the adsorbed but desolvated (MgCl)+ complexes appear to be favorable for charge transfer. Finally, observations of Mg-Cl dissocn. at the Mg surface at very low THF coordinations (0 and 1) suggest that deleterious Cl incorporation in the anode may occur upon plating. In the stripping process, this is beneficial by further facilitating the Mg removal reaction.
19. 19

    Canepa, P.; Sai Gautam, G.; Hannah, D. C.; Malik, R.; Liu, M.; Gallagher, K. G.; Persson, K. A.; Ceder, G. Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges. Chem. Rev. 2017, 117 (5), 4287– 4341,  DOI: 10.1021/acs.chemrev.6b00614

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    19

    Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges

    Canepa, Pieremanuele; Sai Gautam, Gopalakrishnan; Hannah, Daniel C.; Malik, Rahul; Liu, Miao; Gallagher, Kevin G.; Persson, Kristin A.; Ceder, Gerbrand

    Chemical Reviews (Washington, DC, United States) (2017), 117 (5), 4287-4341CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)

    A review. The rapidly expanding field of nonaq. multivalent intercalation batteries offers a promising way to overcome safety, cost, and energy d. limitations of state-of-the-art Li-ion battery technol. The authors present a crit. and rigorous anal. of the increasing vol. of multivalent battery research, focusing on a wide range of intercalation cathode materials and the mechanisms of multivalent ion insertion and migration within those frameworks. The present anal. covers a wide variety of material chemistries, including chalcogenides, oxides, and polyanions, highlighting merits and challenges of each class of materials as multivalent cathodes. The review underscores the overlap of expts. and theory, ranging from charting the design metrics useful for developing the next generation of MV-cathodes to targeted in-depth studies rationalizing complex exptl. results. From the crit. review of the literature, the authors provide suggestions for future multivalent cathode studies, including a strong emphasis on the unambiguous characterization of the intercalation mechanisms.
20. 20

    Han, J.; Yagi, S.; Takeuchi, H.; Nakayama, M.; Ichitsubo, T. Catalytic Mechanism of Spinel Oxides for Oxidative Electrolyte Decomposition in Mg Rechargeable Batteries. J. Mater. Chem. A 2021, 9 (46), 26401– 26409,  DOI: 10.1039/D1TA08115B

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    Catalytic mechanism of spinel oxides for oxidative electrolyte decomposition in magnesium rechargeable batteries

    Han, Jonghyun; Yagi, Shunsuke; Takeuchi, Hirokazu; Nakayama, Masanobu; Ichitsubo, Tetsu

    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2021), 9 (46), 26401-26409CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)

    One of the primary drawbacks in the development of Mg rechargeable batteries is their low operating voltage. Although electrolytes with a wide potential window have been used for high-voltage Mg rechargeable batteries, these electrolytes undergo oxidative decompn. at the surface of the pos. electrode active materials at relatively low potentials. Moreover, the overpotential and kinetics of oxidative electrolyte decompn. significantly depend on the transition metal ion in spinel oxides (e.g., MgMn2O4, MgFe2O4, or MgCo2O4) used as pos. electrode active materials. Because the catalytic activities of spinel oxides for electrolyte decompn. are different, electrolyte decompn. can be effectively suppressed by using transition metal ions with high overpotential for electrolyte decompn. in target spinel oxides. However, the mechanism of the catalytic reaction has not yet been elucidated. Herein, we detd. that the direct electron transfer from the electrolyte to the electrode was slow, whereas the electron transfer via the oxidn. reaction of spinel oxides was fast. Furthermore, we used exptl. data and calcns. to demonstrate that the catalytic activity for oxidative electrolyte decompn. was correlated with the valence band max. (VBM) of spinel oxides; i.e., low VBMs were correlated with high overpotentials for oxidative electrolyte decompn.
21. 21

    Doe, R. E.; Han, R.; Hwang, J.; Gmitter, A. J.; Shterenberg, I.; Yoo, H. D.; Pour, N.; Aurbach, D. Novel, Electrolyte Solutions Comprising Fully Inorganic Salts with High Anodic Stability for Rechargeable Magnesium Batteries. Chem. Commun. 2014, 50 (2), 243– 245,  DOI: 10.1039/C3CC47896C

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    Novel, electrolyte solutions comprising fully inorganic salts with high anodic stability for rechargeable magnesium batteries

    Doe, Robert E.; Han, Ruoban; Hwang, Jaehee; Gmitter, Andrew J.; Shterenberg, Ivgeni; Yoo, Hyun Deog; Pour, Nir; Aurbach, Doron

    Chemical Communications (Cambridge, United Kingdom) (2014), 50 (2), 243-245CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)

    Herein the first inorg. magnesium salt soln. capable of highly reversible magnesium electrodeposition is presented. Synthesized by acid-base reaction of MgCl2 and Lewis acidic compds. such as AlCl3, this salt class demonstrates upwards of 99% Coulombic efficiency, deposition overpotential of <200 mV, and anodic stability of 3.1 V.
22. 22

    Okoshi, M.; Yamada, Y.; Yamada, A.; Nakai, H. Theoretical Analysis on De-Solvation of Lithium, Sodium, and Magnesium Cations to Organic Electrolyte Solvents. J. Electrochem. Soc. 2013, 160 (11), A2160,  DOI: 10.1149/2.074311jes

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    Theoretical analysis on de-solvation of lithium, sodium, and magnesium cations to organic electrolyte solvents

    Okoshi, Masaki; Yamada, Yuki; Yamada, Atsuo; Nakai, Hiromi

    Journal of the Electrochemical Society (2013), 160 (11), A2160-A2165CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)

    De-solvation of a Li ion at an electrode/electrolyte interface can be the rate-detg. step of the reaction in lithium-ion secondary batteries. The present study theor. evaluates the de-solvation energies of Li, Na, and Mg ions to org. electrolyte solvents. The Na-ion complexes revealed commonly smaller de-solvation energies compared to the Li-ion complexes due to the weaker Lewis acidity, while the solvation structures were similar to each other. The Mg-ion complexes showed remarkably larger de-solvation energies because of the double pos. charge. The increase of coordination no., which was assocd. with the change in the solvation structure, was obsd. for the Mg-ion complexes. Detailed anal. revealed good correlations between the de-solvation energies and the electrostatic potentials induced by the solvents, as well as the chem. hardness of the solvents.
23. 23

    Kaneko, T.; Fujihara, Y.; Kobayashi, H.; Sodeyama, K. First-Principles Study of the Reconstruction of MgM₂O₄ (M= Mn, Fe, Co) Spinel Surface. Appl. Surf. Sci. 2023, 613, 156065,  DOI: 10.1016/j.apsusc.2022.156065

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    First-principles study of the reconstruction of MgM2O4 (M = Mn, Fe, Co) spinel surface

    Kaneko, Tomoaki; Fujihara, Yui; Kobayashi, Hiroaki; Sodeyama, Keitaro

    Applied Surface Science (2023), 613 (), 156065CODEN: ASUSEE; ISSN:0169-4332. (Elsevier B.V.)

    MgM2O4 (M = Mn, Fe, Co) spinels, which transform into rock-salt phases on Mg incorporation, are attractive cathode materials for future Mg battery applications. In this study, we investigated the energetics and reconstruction of MgM2O4 (M = Mn, Fe, Co) spinel surfaces using first-principles calcns. We found that the MgM2O4 spinels stabilized when the Mg atoms in the topmost layer occupied the rock-salt-like sites. With an increase in the no. of Mg atoms, the rock salt phase preferentially grew on the spinel surface rather than in the bulk. These features agree well with the core-shell growth of the rock-salt phase obsd. by recent aberration-cor. scanning transmission electron microscopy measurements.
24. 24

    Han, J.; Yagi, S.; Takeuchi, H.; Nakayama, M.; Ichitsubo, T. Control of Electrolyte Decomposition by Mixing Transition Metal Ions in Spinel Oxides as Positive Electrode Active Materials for Mg Rechargeable Batteries. J. Phys. Chem. C 2022, 126 (45), 19074– 19083,  DOI: 10.1021/acs.jpcc.2c06443

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    Control of Electrolyte Decomposition by Mixing Transition Metal Ions in Spinel Oxides as Positive Electrode Active Materials for Mg Rechargeable Batteries

    Han, Jonghyun; Yagi, Shunsuke; Takeuchi, Hirokazu; Nakayama, Masanobu; Ichitsubo, Tetsu

    Journal of Physical Chemistry C (2022), 126 (45), 19074-19083CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)

    The development of Mg rechargeable batteries is hindered by both oxidative and reductive electrolyte decompn. on the pos. electrode, which results in poor cyclability. Although improving the stability of the electrolyte is one soln., we found that the oxidative decompn. of the electrolyte can be suppressed by introducing Fe ions to spinel oxides. Furthermore, the mechanism was clarified from the viewpoint of the electronic state of the spinel oxides, with MgFe2O4 exhibiting the lowest valence band max. in our previous study. Here, by developing an interpretation of this mechanism, we demonstrated that the type of transition metal ions in spinel oxides has an effect on the reductive decompn. of the electrolyte. Based on the above knowledge, we synthesized mixed Co-Fe spinel oxides that exhibited a suppressive effect on both oxidative and reductive electrolyte decompn. and successfully improved the cyclability. This study provides guidelines for developing pos. electrode active materials for Mg rechargeable batteries.
25. 25

    Kresse, G.; Joubert, D. From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method. Phys. Rev. B 1999, 59 (3), 1758– 1775,  DOI: 10.1103/PhysRevB.59.1758

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    From ultrasoft pseudopotentials to the projector augmented-wave method

    Kresse, G.; Joubert, D.

    Physical Review B: Condensed Matter and Materials Physics (1999), 59 (3), 1758-1775CODEN: PRBMDO; ISSN:0163-1829. (American Physical Society)

    The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Blochl's projector augmented wave (PAW) method is derived. The total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addn., crit. tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed-core all-electron methods. These tests include small mols. (H2, H2O, Li2, N2, F2, BF3, SiF4) and several bulk systems (diamond, Si, V, Li, Ca, CaF2, Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.
26. 26

    Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 3865– 3868,  DOI: 10.1103/PhysRevLett.77.3865

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    Generalized gradient approximation made simple

    Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias

    Physical Review Letters (1996), 77 (18), 3865-3868CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)

    Generalized gradient approxns. (GGA's) for the exchange-correlation energy improve upon the local spin d. (LSD) description of atoms, mols., and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental consts. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential.
27. 27

    Zhou, F.; Cococcioni, M.; Marianetti, C. A.; Morgan, D.; Ceder, G. First-Principles Prediction of Redox Potentials in Transition-Metal Compounds with LDA+ U. Phys. Rev. B 2004, 70 (23), 235121,  DOI: 10.1103/PhysRevB.70.235121

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    First-principles prediction of redox potentials in transition-metal compounds with LDA+U

    Zhou, F.; Cococcioni, M.; Marianetti, C. A.; Morgan, D.; Ceder, G.

    Physical Review B: Condensed Matter and Materials Physics (2004), 70 (23), 235121/1-235121/8CODEN: PRBMDO; ISSN:1098-0121. (American Physical Society)

    First-principles calcns. within the local d. approxn. (LDA) or generalized gradient approxn. (GGA), though very successful, are known to underestimate redox potentials, such as those at which lithium intercalates in transition metal compds. We argue that this inaccuracy is related to the lack of cancellation of electron self-interaction errors in LDA/GGA and can be improved by using the DFT + U method with a self-consistent evaluation of the U parameter. We show that, using this approach, the exptl. lithium intercalation voltages of a no. of transition metal compds., including the olivine LixMPO4 (M = Mn, Fe Co, Ni), layered LixMO2 (x = Co, Ni) and spinel-like LixM2O4 (M = Mn, Co), can be reproduced accurately.
28. 28

    Guo, H.; Durham, J. L.; Brady, A. B.; Marschilok, A. C.; Takeuchi, E. S.; Takeuchi, K. J.; Liu, P. Essential Role of Spinel MgFe₂O₄ Surfaces during Discharge. J. Electrochem. Soc. 2020, 167 (9), 090506,  DOI: 10.1149/1945-7111/ab7f89

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    Essential role of spinel MgFe2O4 surfaces during discharge

    Guo, Haoyue; Durham, Jessica L.; Brady, Alexander B.; Marschilok, Amy C.; Takeuchi, Esther S.; Takeuchi, Kenneth J.; Liu, Ping

    Journal of the Electrochemical Society (2020), 167 (9), 090506CODEN: JESOAN; ISSN:1945-7111. (IOP Publishing Ltd.)

    Spinel magnesium ferrite (MgFe2O4) is a prospective anode material in lithium ion battery (LIB) due to its large theor. capacity. Here, we employed D. Functional Theory (DFT) to study the contribution from diverse facets of three spinel systems of MgFe2O4, normal-spinel, mixed-spinel and inverse-spinel, to the initial discharge behaviors. The mixed-spinel (1 0 0) surface terminated by MgFeOx is found to be the most active among the diverse surfaces studied. It can provide the high capacity, the high voltage and facile Li+ transport during the initial discharge stage. The high performance is found to be assocd. with the high surface activity to capture Li+ ions, and the ability to accommodate a large amt. of Li+ ions and facilitate the sequential smooth transport to subsurface. The DFT-estd. discharge voltages based on the mixed-spinel (1 0 0) surface terminated by MgFeOx are much higher than those using the stoichiometric bulk models and fit well with the corresponding exptl. measurement at the initial stage. Our results develop new design strategies for optimization of particle morphologies, enabling the enhancement in stability and discharge performance of ferrite materials.
29. 29

    Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu. J. Chem. Phys. 2010, 132 (15), 154104,  DOI: 10.1063/1.3382344

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    A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu

    Grimme, Stefan; Antony, Jens; Ehrlich, Stephan; Krieg, Helge

    Journal of Chemical Physics (2010), 132 (15), 154104/1-154104/19CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)

    The method of dispersion correction as an add-on to std. Kohn-Sham d. functional theory (DFT-D) has been refined regarding higher accuracy, broader range of applicability, and less empiricism. The main new ingredients are atom-pairwise specific dispersion coeffs. and cutoff radii that are both computed from first principles. The coeffs. for new eighth-order dispersion terms are computed using established recursion relations. System (geometry) dependent information is used for the first time in a DFT-D type approach by employing the new concept of fractional coordination nos. (CN). They are used to interpolate between dispersion coeffs. of atoms in different chem. environments. The method only requires adjustment of two global parameters for each d. functional, is asymptotically exact for a gas of weakly interacting neutral atoms, and easily allows the computation of at. forces. Three-body nonadditivity terms are considered. The method has been assessed on std. benchmark sets for inter- and intramol. noncovalent interactions with a particular emphasis on a consistent description of light and heavy element systems. The mean abs. deviations for the S22 benchmark set of noncovalent interactions for 11 std. d. functionals decrease by 15%-40% compared to the previous (already accurate) DFT-D version. Spectacular improvements are found for a tripeptide-folding model and all tested metallic systems. The rectification of the long-range behavior and the use of more accurate C6 coeffs. also lead to a much better description of large (infinite) systems as shown for graphene sheets and the adsorption of benzene on an Ag(111) surface. For graphene it is found that the inclusion of three-body terms substantially (by about 10%) weakens the interlayer binding. We propose the revised DFT-D method as a general tool for the computation of the dispersion energy in mols. and solids of any kind with DFT and related (low-cost) electronic structure methods for large systems. (c) 2010 American Institute of Physics.