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Advances in Hydrogen Storage Materials for Energy Utilization

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

Deadline for manuscript submissions: closed (31 December 2020) | Viewed by 47032

Special Issue Editor


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Guest Editor
Pacific Northwest National Laboratory, Richland, WA 99352, USA
Interests: metal hydrides; hydrogen storage materials and technologies; materials discovery; materials synthesis and characterization; reaction mechanisms; materials for metal hydride batteries; complex metal hydrides; metal borohydrides; metal hydride thermal energy storage; design of energy storage devices; scale-up of prototypes; hydrogen storage performance characterization; hydrogen permeation barriers; hydrogen getters; hydrogen effects; hydrogen embrittlement; hydride reorientation; isotope studies; phase transitions; crystal structure determination; solid state NMR; X-ray diffraction; neutron diffraction; synchrotron X-ray diffraction
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Special Issue Information

Dear Colleagues,

Hydrogen is the most abundant and light-weight element in the universe with the unique ability to form compounds with most elements. Hydrogen storage will be a cornerstone technology for energy utilization in the 21st century once all aspects of a hydrogen economy come together. During the past 20 years, several new classes of materials, both solid and liquid, have emerged as potential candidates for various energy applications based on hydrogen, including hydrogen storage, batteries, thermal energy storage, heating/cooling devices, thin films for smart solar collectors, smart windows, getters, and sensors. Immense advances have been made in the discovery, synthesis, and characterization of functional materials that can be used in sustainable infrastructure, including hydrogen production, storage, and delivery. Many applications require reversible reactions for hydrogen absorption/desorption at certain pressures and temperatures along with high hydrogen content, and it can be challenging to identify a material that can meet all performance requirements for a specific application, but several new strategies for materials engineering have emerged. Experimentalists and theorists have teamed up to facilitate the selection of promising materials candidates that can meet performance requirments.
Several physical phenomena have been observed with the introduction of hydrogen into a metal or metal alloy, e.g., electric, magnetic, optical, and mechanical transitions. Phase transitions occur reversibly from normal conductance to superconductivity, from metals to semiconductors or insulators, or from ferromagnetic to paramagnetic under certain pressures and temperatures. There are thus many other applications for metal hydrides, not only for hydrogen storage.
This Special Issue aims to cover recent progress and trends in the utilization of hydrogen in materials for various energy applications. Types of contributions to this Special Issue can be full research articles, short communications, and reviews focusing on recent advances in utilizing materials for hydrogen-based energy applications.

  • Hydrogen storage materials: their synthesis and characterization
    • Metal hydrides
    • Complex metal hydrides
    • Metal borohydrides, amides, and imides
    • Materials performance engineering; nanostructured materials, dopants, synthesis routes, etc.
    • Liquid organic hydrogen carriers
    • Metal organic frameworks
    • New materials
    • New reaction pathways
    • Computational advances
  • Metal hydride batteries
  • Hydride materials for thermal energy storage
  • Hydrides for smart solar collectors
  • Hydrides for sensors
  • Hydrogen getters

Dr. Ewa C.E. Rönnebro
Guest Editor

Manuscript Submission Information

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Published Papers (11 papers)

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Research

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12 pages, 1375 KiB  
Article
Effects of LiBF4 Addition on the Lithium-Ion Conductivity of LiBH4
by Laura M. de Kort, Valerio Gulino, Didier Blanchard and Peter Ngene
Molecules 2022, 27(7), 2187; https://doi.org/10.3390/molecules27072187 - 28 Mar 2022
Cited by 6 | Viewed by 2418
Abstract
Complex hydrides, such as LiBH4, are a promising class of ion conductors for all-solid-state batteries, but their application is constrained by low ion mobility at room temperature. Mixing with halides or complex hydride anions, i.e., other complex hydrides, is an effective [...] Read more.
Complex hydrides, such as LiBH4, are a promising class of ion conductors for all-solid-state batteries, but their application is constrained by low ion mobility at room temperature. Mixing with halides or complex hydride anions, i.e., other complex hydrides, is an effective approach to improving the ionic conductivity. In the present study, we report on the reaction of LiBH4 with LiBF4, resulting in the formation of conductive composites consisting of LiBH4, LiF and lithium closo-borates. It is believed that the in-situ formation of closo-borate related species gives rise to highly conductive interfaces in the decomposed LiBH4 matrix. As a result, the ionic conductivity is improved by orders of magnitude with respect to the Li-ion conductivity of the LiBH4, up to 0.9 × 10−5 S cm−1 at 30 °C. The insights gained in this work show that the incorporation of a second compound is a versatile method to improve the ionic conductivity of complex metal hydrides, opening novel synthesis pathways not limited to conventional substituents. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials for Energy Utilization)
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41 pages, 13242 KiB  
Article
Engineering Challenges of Solution and Slurry-Phase Chemical Hydrogen Storage Materials for Automotive Fuel Cell Applications
by Troy Semelsberger, Jason Graetz, Andrew Sutton and Ewa C. E. Rönnebro
Molecules 2021, 26(6), 1722; https://doi.org/10.3390/molecules26061722 - 19 Mar 2021
Cited by 5 | Viewed by 2508
Abstract
We present the research findings of the DOE-funded Hydrogen Storage Engineering Center of Excellence (HSECoE) related to liquid-phase and slurry-phase chemical hydrogen storage media and their potential as future hydrogen storage media for automotive applications. Chemical hydrogen storage media other than neat liquid [...] Read more.
We present the research findings of the DOE-funded Hydrogen Storage Engineering Center of Excellence (HSECoE) related to liquid-phase and slurry-phase chemical hydrogen storage media and their potential as future hydrogen storage media for automotive applications. Chemical hydrogen storage media other than neat liquid compositions will prove difficult to meet the DOE system level targets. Solid- and slurry-phase chemical hydrogen storage media requiring off-board regeneration are impractical and highly unlikely to be implemented for automotive applications because of the formidable task of developing solid- or slurry-phase transport systems that are commercially reliable and economical throughout the entire life cycle of the fuel. Additionally, the regeneration cost and efficiency of chemical hydrogen storage media is currently the single most prohibitive barrier to implementing chemical hydrogen storage media. Ideally, neat liquid-phase chemical hydrogen storage media with net-usable gravimetric hydrogen capacities of greater than 7.8 wt% are projected to meet the 2017 DOE system level gravimetric and volumetric targets. The research presented herein is a collection of research findings that do not in and of themselves warrant a dedicated manuscript. However, the collection of results do, in fact, highlight the engineering challenges and short-comings in scaling up and demonstrating fluid-phase ammonia borane and alane compositions that all future materials researchers working in hydrogen storage should be aware of. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials for Energy Utilization)
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10 pages, 1413 KiB  
Article
Kinetics of the Lattice Response to Hydrogen Absorption in Thin Pd and CoPd Films
by Sudhansu Sekhar Das, Gregory Kopnov and Alexander Gerber
Molecules 2020, 25(16), 3597; https://doi.org/10.3390/molecules25163597 - 07 Aug 2020
Cited by 11 | Viewed by 2616
Abstract
Hydrogen can penetrate reversibly a number of metals, occupy the interstitial sites and cause large expansion of the crystal lattice. The question discussed here is whether the kinetics of the structural response matches hydrogen absorption. We show that thin Pd and CoPd films [...] Read more.
Hydrogen can penetrate reversibly a number of metals, occupy the interstitial sites and cause large expansion of the crystal lattice. The question discussed here is whether the kinetics of the structural response matches hydrogen absorption. We show that thin Pd and CoPd films exposed to a relatively rich hydrogen atmosphere (4% H2) inflate irreversibly, demonstrate the controllable shape memory, and duration of the process can be of orders of magnitude longer than hydrogen absorption. The dynamics of the out-of-equilibrium plastic creep are well described by the Avrami-type model of the nucleation and lateral domain wall expansion of the swelled sites. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials for Energy Utilization)
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15 pages, 7233 KiB  
Article
Upcycling of Spent NiMH Battery Material—Reconditioned Battery Alloys Show Faster Activation and Reaction Kinetics than Pristine Alloys
by Yang Shen, Erik Svensson Grape, Dag Noréus, Erika Widenkvist and Stina Starborg
Molecules 2020, 25(10), 2338; https://doi.org/10.3390/molecules25102338 - 17 May 2020
Cited by 3 | Viewed by 10467
Abstract
During formation and cycling of nickel–metal hydride (NiMH cells), surface corrosion on the metal hydride particles forms a porous outer layer of needle-shaped rare-earth hydroxide crystals. Under this layer, a denser but thinner oxidized layer protects the inner metallic part of the MH [...] Read more.
During formation and cycling of nickel–metal hydride (NiMH cells), surface corrosion on the metal hydride particles forms a porous outer layer of needle-shaped rare-earth hydroxide crystals. Under this layer, a denser but thinner oxidized layer protects the inner metallic part of the MH electrode powder particles. Nano-sized nickel-containing clusters that are assumed to promote the charge and discharge reaction kinetics are also formed here. In this study, mechanical treatments are tested to recycle hydrogen storage alloys from spent NiMH batteries. This removes the outer corroded surface of the alloy particles, while maintaining the catalytic properties of the surface. Scanning electron microscopy images and powder X-ray diffraction measurements show that the corrosion layer can be partly removed by ball milling or sonication, combined with a simple washing procedure. The reconditioned alloy powders exhibit improved high rate properties and activate more quickly than the pristine alloy. This indicates that the protective interphase layer created on the alloy particle during their earlier cycling is rather stable. The larger active surface that is created by the mechanical impact on the surface by the treatments also improves the kinetic properties. Similarly, the mechanical strain during cycling cracks the alloy particles into finer fragments. However, some of these particles form agglomerates, reducing the accessibility for the electrolyte and rendering them inactive. The mechanical treatment also separates the agglomerates and thus further promotes reaction kinetics in the upcycled material. Altogether, this suggests that the MH electrode material can perform better in its second life in a new battery. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials for Energy Utilization)
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21 pages, 975 KiB  
Article
Destabilization of NaBH4 by Transition Metal Fluorides
by Isabel Llamas Jansa, Georgios N. Kalantzopoulos, Kari Nordholm and Bjørn C. Hauback
Molecules 2020, 25(4), 780; https://doi.org/10.3390/molecules25040780 - 12 Feb 2020
Cited by 14 | Viewed by 2702
Abstract
With the goal of improving performance of a hydrogen-rich storage medium, the influence of a collection of first and second period transition metal fluorides on the destabilization of NaBH4 is studied on samples produced by ball milling NaBH4 with 2 mol% [...] Read more.
With the goal of improving performance of a hydrogen-rich storage medium, the influence of a collection of first and second period transition metal fluorides on the destabilization of NaBH4 is studied on samples produced by ball milling NaBH4 with 2 mol% of a metal fluoride additive. The effects obtained by increasing additive amount and changing oxidation state are also evaluated for NbF5, CeF3, and CeF4. The as-milled products are characterized by in-house power X-ray diffraction, while the hydrogen release and decomposition are monitored by temperature programmed desorption with residual gas analysis, differential scanning calorimetry, and thermogravimetry. The screening of samples containing 2 mol% of additive shows that distinctive groups of transition metal fluorides affect the ball milling process differently depending on their enthalpy of formation, melting point, or their ability to react at the temperatures achieved during ball milling. This leads to the formation of NaBF4 in the case of TiF4, MnF3, VF4, CdF2, NbF5, AgF, and CeF3 and the presence of the metal in CrF3, CuF2, and AgF. There is no linear correlation between the position of the transition metal in the periodic table and the observed behavior. The thermal behavior of the products after milling is given by the remaining NaBH4, fluoride, and the formation of intermediate metastable compounds. A noticeable decrease of the decomposition temperature is seen for the majority of the products, with the exceptions of the samples containing YF3, AgF, and CeF3. The largest decrease of the decomposition temperature is observed for NbF5. When comparing increasing amounts of the same additive, the largest decrease of the decomposition temperature is observed for 10 mol% of NbF5. Higher amounts of additive result in the loss of the NaBH4 thermal signal and ultimately the loss of the crystalline borohydride. When comparing additives with the same transition metal and different oxidation states, the most efficient additive is found to be the one with a higher oxidation state. Furthermore, among all the samples studied, higher oxidation state metal fluorides are found to be the most destabilizing agents for NaBH4. Overall, the present study shows that there is no single parameter affecting the destabilization of NaBH4 by transition metal fluorides. Instead, parameters such as the transition metal electronegativity and oxidation state or the enthalpy of formation of the fluoride and its melting point are competing to influence the destabilization. In particular, it is found that the combination of a high metal oxidation state and a low fluoride melting point will enhance destabilization. This is observed for MnF3, NbF5, NiF2, and CuF2, which lead to high gas releases from the decomposition of NaBH4 at the lowest decomposition temperatures. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials for Energy Utilization)
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14 pages, 3326 KiB  
Article
Portable Power Generation for Remote Areas Using Hydrogen Generated via Maleic Acid-Promoted Hydrolysis of Ammonia Borane
by Taylor B. Groom, Jason R. Gabl and Timothée L. Pourpoint
Molecules 2019, 24(22), 4045; https://doi.org/10.3390/molecules24224045 - 08 Nov 2019
Cited by 3 | Viewed by 2697
Abstract
A significant drawback to ammonia borane as a hydrogen storage material is the production of ammonia gas during hydrolysis. As a possible solution, maleic acid is shown to be capable of fully promoting hydrolysis of ammonia borane while also preventing ammonia release in [...] Read more.
A significant drawback to ammonia borane as a hydrogen storage material is the production of ammonia gas during hydrolysis. As a possible solution, maleic acid is shown to be capable of fully promoting hydrolysis of ammonia borane while also preventing ammonia release in excess of single digit parts per million. The reaction is shown to be relatively insensitive towards common water contaminants, with seawater, puddle water, and synthetic urine resulting in hydrogen evolution comparable to that observed when using highly pure deionized water. A common cola beverage was also investigated as a potential water source, with results deviating from those observed when using the other water sources. The ability to use low quality water sources presents the option of acquiring water at the point of use, greatly increasing the energy density of the system during transportation. For each of the water sources being used, concentrations of ammonia in the gas products of maleic acid-promoted hydrolysis were found to be less than the lower detection limits of the employed analysis methods. Based on this reaction, a portable hydrogen reactor is reported and shown to be capable of on-demand hydrogen generation sufficient to power a proton exchange membrane fuel cell at varying loads without significant changes in system pressure. The overall power production system has substantial value in scenarios where electrical power is required but there is no access to an established electrical utility, with prime examples including disaster relief and expeditionary military operations. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials for Energy Utilization)
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14 pages, 1900 KiB  
Article
TiVZrNb Multi-Principal-Element Alloy: Synthesis Optimization, Structural, and Hydrogen Sorption Properties
by Jorge Montero, Claudia Zlotea, Gustav Ek, Jean-Claude Crivello, Lætitia Laversenne and Martin Sahlberg
Molecules 2019, 24(15), 2799; https://doi.org/10.3390/molecules24152799 - 31 Jul 2019
Cited by 63 | Viewed by 4847
Abstract
While the overwhelming number of papers on multi-principal-element alloys (MPEAs) focus on the mechanical and microstructural properties, there has been growing interest in these alloys as solid-state hydrogen stores. We report here the synthesis optimization, the physicochemical and the hydrogen sorption properties of [...] Read more.
While the overwhelming number of papers on multi-principal-element alloys (MPEAs) focus on the mechanical and microstructural properties, there has been growing interest in these alloys as solid-state hydrogen stores. We report here the synthesis optimization, the physicochemical and the hydrogen sorption properties of Ti0.325V0.275Zr0.125Nb0.275. This alloy was prepared by two methods, high temperature arc melting and ball milling under Ar, and crystallizes into a single-phase bcc structure. This MPEA shows a single transition from the initial bcc phase to a final bct dihydride and a maximum uptake of 1.7 H/M (2.5 wt%). Interestingly, the bct dihydride phase can be directly obtained by reactive ball milling under hydrogen pressure. The hydrogen desorption properties of the hydrides obtained by hydrogenation of the alloy prepared by arc melting or ball milling and by reactive ball milling have been compared. The best hydrogen sorption properties are shown by the material prepared by reactive ball milling. Despite a fading of the capacity for the first cycles, the reversible capacity of the latter material stabilizes around 2 wt%. To complement the experimental approach, a theoretical investigation combining a random distribution technique and first principle calculation was done to estimate the stability of the hydride. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials for Energy Utilization)
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Review

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11 pages, 2340 KiB  
Review
Overview of the Structure–Dynamics–Function Relationships in Borohydrides for Use as Solid-State Electrolytes in Battery Applications
by Tabbetha A. Dobbins
Molecules 2021, 26(11), 3239; https://doi.org/10.3390/molecules26113239 - 28 May 2021
Cited by 6 | Viewed by 3544
Abstract
The goal of this article is to highlight crucial breakthroughs in solid-state ionic conduction in borohydrides for battery applications. Borohydrides, Mz+BxHy, form in various molecular structures, for example, nido-M+BH4; closo-M2+B10 [...] Read more.
The goal of this article is to highlight crucial breakthroughs in solid-state ionic conduction in borohydrides for battery applications. Borohydrides, Mz+BxHy, form in various molecular structures, for example, nido-M+BH4; closo-M2+B10H10; closo-M2+B12H12; and planar-M6+B6H6 with M = cations such as Li+, K+, Na+, Ca2+, and Mg2+, which can participate in ionic conduction. This overview article will fully explore the phase space of boron–hydrogen chemistry in order to discuss parameters that optimize these materials as solid electrolytes for battery applications. Key properties for effective solid-state electrolytes, including ionic conduction, electrochemical window, high energy density, and resistance to dendrite formation, are also discussed. Because of their open structures (for closo-boranes) leading to rapid ionic conduction, and their ability to undergo phase transition between low conductivity and high conductivity phases, borohydrides deserve a focused discussion and further experimental efforts. One challenge that remains is the low electrochemical stability of borohydrides. This overview article highlights current knowledge and additionally recommends a path towards further computational and experimental research efforts. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials for Energy Utilization)
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22 pages, 1947 KiB  
Review
Anion and Cation Dynamics in Polyhydroborate Salts: NMR Studies
by Alexander V. Skripov, Alexei V. Soloninin, Olga A. Babanova and Roman V. Skoryunov
Molecules 2020, 25(12), 2940; https://doi.org/10.3390/molecules25122940 - 26 Jun 2020
Cited by 23 | Viewed by 4540
Abstract
Polyhydroborate salts represent the important class of energy materials attracting significant recent attention. Some of these salts exhibit promising hydrogen storage properties and/or high ionic conductivities favorable for applications as solid electrolytes in batteries. Two basic types of thermally activated atomic jump motion [...] Read more.
Polyhydroborate salts represent the important class of energy materials attracting significant recent attention. Some of these salts exhibit promising hydrogen storage properties and/or high ionic conductivities favorable for applications as solid electrolytes in batteries. Two basic types of thermally activated atomic jump motion are known to exist in these materials: the reorientational (rotational) motion of complex anions and the translational diffusion of cations or complex anions. The present paper reviews recent progress in nuclear magnetic resonance (NMR) studies of both reorientational and diffusive jump motion in polyhydroborate salts. The emphasis is put on sodium and lithium closo-borates exhibiting high ionic conductivity and on borohydride-based systems showing extremely fast reorientational motion down to low temperatures. For these systems, we discuss the effects of order–disorder phase transitions on the parameters of reorientations and diffusive jumps, as well as the mechanism of low-temperature rotational tunneling. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials for Energy Utilization)
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25 pages, 4605 KiB  
Review
Beyond Typical Electrolytes for Energy Dense Batteries
by Rana Mohtadi
Molecules 2020, 25(8), 1791; https://doi.org/10.3390/molecules25081791 - 14 Apr 2020
Cited by 22 | Viewed by 4553
Abstract
The ever-rising demands for energy dense electrochemical storage systems have been driving interests in beyond Li-ion batteries such as those based on lithium and magnesium metals. These high energy density batteries suffer from several challenges, several of which stem from the flammability/volatility of [...] Read more.
The ever-rising demands for energy dense electrochemical storage systems have been driving interests in beyond Li-ion batteries such as those based on lithium and magnesium metals. These high energy density batteries suffer from several challenges, several of which stem from the flammability/volatility of the electrolytes and/or instability of the electrolytes with either the negative, positive electrode or both. Recently, hydride-based electrolytes have been paving the way towards overcoming these issues. Namely, highly performing solid-state electrolytes have been reported and several key challenges in multivalent batteries were overcome. In this review, the classes of hydride-based electrolytes reported for energy dense batteries are discussed. Future perspectives are presented to guide research directions in this field. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials for Energy Utilization)
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39 pages, 6200 KiB  
Review
Tuning LiBH4 for Hydrogen Storage: Destabilization, Additive, and Nanoconfinement Approaches
by Julián Puszkiel, Aurelien Gasnier, Guillermina Amica and Fabiana Gennari
Molecules 2020, 25(1), 163; https://doi.org/10.3390/molecules25010163 - 31 Dec 2019
Cited by 46 | Viewed by 5156
Abstract
Hydrogen technology has become essential to fulfill our mobile and stationary energy needs in a global low–carbon energy system. The non-renewability of fossil fuels and the increasing environmental problems caused by our fossil fuel–running economy have led to our efforts towards the application [...] Read more.
Hydrogen technology has become essential to fulfill our mobile and stationary energy needs in a global low–carbon energy system. The non-renewability of fossil fuels and the increasing environmental problems caused by our fossil fuel–running economy have led to our efforts towards the application of hydrogen as an energy vector. However, the development of volumetric and gravimetric efficient hydrogen storage media is still to be addressed. LiBH4 is one of the most interesting media to store hydrogen as a compound due to its large gravimetric (18.5 wt.%) and volumetric (121 kgH2/m3) hydrogen densities. In this review, we focus on some of the main explored approaches to tune the thermodynamics and kinetics of LiBH4: (I) LiBH4 + MgH2 destabilized system, (II) metal and metal hydride added LiBH4, (III) destabilization of LiBH4 by rare-earth metal hydrides, and (IV) the nanoconfinement of LiBH4 and destabilized LiBH4 hydride systems. Thorough discussions about the reaction pathways, destabilizing and catalytic effects of metals and metal hydrides, novel synthesis processes of rare earth destabilizing agents, and all the essential aspects of nanoconfinement are led. Full article
(This article belongs to the Special Issue Advances in Hydrogen Storage Materials for Energy Utilization)
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