Mg Intercalation in Layered and Spinel Host Crystal Structures for Mg Batteries

Emly, Alexandra; Ven, Anton Van der

doi:10.1021/acs.inorgchem.5b00188

Cited by 117 publications

(186 citation statements)

References 51 publications

Supporting

Mentioning

165

Contrasting

Order By: Relevance

“…Exfoliating bulk TiS 2 has been suggested as a possible method to superior performance, analogous to MoS 2 [27,161]. This intuition is supported by a theoretical study by Emly and Van der Ven [171], who looked at layered and spinel TiS 2 as a model system and compared some of the properties of Li x TiS 2 and Mg x TiS 2 . In the case of the layered polymorph, the diffusion barrier is reduced from 1.16 to 0.55 eV as the c-axis is augmented by 10% (Fig.…”

Section: Science China Materialsmentioning

confidence: 92%

Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries

2015

View full text Add to dashboard Cite

to develop and install renewable energy harvesting technologies [3]. However, their successful implementation will be dependent on reliable and robust storage devices since harvesting solar and wind energy is inherently intermittent and the majority of consumption targets cannot be readily tethered to the grid.As energy storage devices, batteries possess high portability, high energy density, high Coulombic efficiency, and long cycle life. They are ideal power sources for portable devices, automobiles, and backup power supplies; accordingly, batteries power nearly all of our mobile electronics and are used to improve the efficiency of hybrid electric vehicles [4,5]. Unfortunately, considerable improvements in performance are still required in order to meet the demands of advanced portable devices and achieve energy sustainability (e.g., through smart grid and electric vehicle technologies) [6]. These enduring needs have driven intensive research investments. While efforts have been successful, there is still significant room for improvement regarding the development and understanding of electrode materials [7]. The overall capacity and potential cycling window of many electrode materials are limited to prevent degradation over long term cycling. In addition to exploring new electrode materials, there have been strong efforts to improve those that are already utilized. Expense reduction is a priority as approximately 23% and 8% of the overall battery pack costs stem from the respective cathode and anode active materials alone [8].An alkali-ion battery consists of several electrochemical cells connected in parallel and/or in series to provide a designated current or voltage. Each electrochemical cell has two electrodes separated by an electrolyte that is electrically insulating but ionically conductive. During discharge, when the alkali-ion battery operates as a galvanic cell, alkali ions exit the negative electrode (typically carbon) and insert themselves into the positive electrode while electronsThe need for economical and sustainable energy storage drives battery research today. While Li-ion batteries are the most mature technology, scalable electrochemical energy storage applications benefit from reductions in cost and improved safety. Sodium-and magnesium-ion batteries are two technologies that may prove to be viable alternatives. Both metals are cheaper and more abundant than Li, and have better safety characteristics, while divalent magnesium has the added bonus of passing twice as much charge per atom. On the other hand, both are still emerging fields of research with challenges to overcome. For example, electrodes incorporating Na + are often pulverized under the repeated strain of shuttling the relatively large ion, while insertion and transport of Mg 2+ is often kinetically slow, which stems from larger electrostatic forces. This review provides an overview of cathode and anode materials for sodium-ion batteries, and a comprehensive summary of research on cathodes for magnesium-ion batteries. In additi...

show abstract

Section: Science China Materialsmentioning

confidence: 92%

Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries

2015

View full text Add to dashboard Cite

show abstract

“…Second, the honeycomb lattice of intercalant sites in P3 can result in complex sodium/vacancy ordering phenomena not seen in layered Li compounds. Bulk diffusion and interfacial ion-transfer kinetics appear to be much slower for magnesium, [277,287,288] and so some materials that are excellent for Li and Na batteries do not permit the electrochemical (de)intercalation of Mg. [8,282] The larger ionic radius of Na + (1.16 Å [283] ) compared to Li + (0.90 Å [283] ) also has other effects besides the stabilization of prismatic structures.…”

Section: Wwwadvancedsciencenewscommentioning

confidence: 99%

“…[8,282] The larger ionic radius of Na + (1.16 Å [283] ) compared to Li + (0.90 Å [283] ) also has other effects besides the stabilization of prismatic structures. [278,288] Relatively few studies have reported on the electrochemical (de)intercalation of elements beyond Li, Na, and Mg in layered materials. A second consequence of the larger size of Na + is that the greater discrepancy between the Na + radius and transition-metal radii results in a stronger tendency toward layering.…”

Section: Wwwadvancedsciencenewscommentioning

confidence: 99%

Narrowing the Gap between Theoretical and Practical Capacities in Li‐Ion Layered Oxide Cathode Materials

Radin

Sina

et al. 2017

Advanced Energy Materials

Self Cite

556

566

View full text Add to dashboard Cite

Although layered lithium oxides have become the cathode of choice for state‐of‐the‐art Li‐ion batteries, substantial gaps remain between the practical and theoretical energy densities. With the aim of supporting efforts to close this gap, this work reviews the fundamental operating mechanisms and challenges of Li intercalation in layered oxides, contrasts how these challenges play out differently for different materials (with emphasis on Ni–Co–Al (NCA) and Ni–Mn–Co (NMC) alloys), and summarizes the extensive corpus of modifications and extensions to the layered lithium oxides. Particular emphasis is given to the fundamental mechanisms behind the operation and degradation of layered intercalation electrode materials as well as novel modifications and extensions, including Na‐ion and cation‐disordered materials.

show abstract

“…As such, the Mg content of the outer shell of the active material is more likely x = 2 × 0.17 = 0.34, corresponding to the ordered composition Mg 1/3 TiS 2 where Mg occupies octahedral sites and whose existence was suggested by first-principles calculations. 31 These calculations also showed that as the unit cell increases in size with increasing Mg 2+ /e − content, the Mg 2+ preference for the octahedral site over the tetrahedral site is lessened, 31 suggesting an increased likelihood of tetrahedral occupation at high x values. Meanwhile, we note a possible parallel with lithium insertion in TiS 2 where a switchover in siting as a function of depth of intercalation occurs.…”

mentioning

confidence: 98%

“…Based on previous computational results, the octahedral site energy for Mg occupation is much lower than the tetrahedral site during the initial stages of intercalation. 31 This suggests preferred Mg insertion onto the octahedral sites during early discharge (A to C). In fact, at point C the Mg stoichiometry is likely larger than x = 0.17.…”

mentioning

confidence: 99%

Layered TiS₂ Positive Electrode for Mg Batteries

2016

View full text Add to dashboard Cite

Magnesium batteries are a good candidate for high energy storage systems, but the limited discovery of functional positive electrode materials beyond the seminal Chevrel phase (Mo 6 S 8 ) has slowed their development. Herein, we report on layered TiS 2 as a promising positive electrode intercalation material, providing 115 mAh g −1 stabilized capacity in a Mg full cell. Reversible Mg 2+ intercalation into the structure is proven by elemental analysis combined with X-ray diffraction studies that elucidate the phase behavior upon cycling. The voltage profiles reveal distinct Mg 2+ cation ordering, unlike the solid solution behavior exhibited by Li + . Our findings not only point to the important role of "soft" lattices to facilitate divalent solidstate cation mobility but also now provide an alternative sulfide to serve as a platform for the fundamental understanding of Mg 2+ intercalation in lattices.R echargeable Mg batteries are one of the candidate systems to possibly surpass Li-ion in volumetric energy density. 1−3 Their most significant advantage comes from the potential use of Mg metal as the negative electrode, which, in addition to its low-cost, also offers high volumetric capacity (3833 mAh cm −3 ) and dendrite free deposition during charging. Metals that alloy with Mg have also been explored as negative electrodes, such as Sn 4 and recently Pb, which has the lowest voltage and highest volumetric capacity of any Mg alloy yet reported. 5 However, available positive electrode materials have been limited to very few compounds, the first one to cycle well being the Chevrel phase (CP) Mo 6 S 8 reported by Aurbach et al. in 2000. 6 Recently our group also identified the titanium thiospinel as a Mg insertion host. 7 In contrast to the favorable Mg mobility in sulfide structures, sluggish Mg diffusion 8−13 or conversion reactions 14,15 are generally observed in oxide hosts. Hence, shifting to "softer" lattices (i.e., S, Se, etc. instead of O) is a promising means of discovering new Mg insertion structures that will contribute to the fundamental understanding of divalent ion diffusion in lattices, as well as Mg desolvation at the electrolyte/electrode interface. 16−21 For example, it has been shown that the low Mg desolvation barrier on the CP surface from the all-phenyl complex (APC) 22 electrolyte is a key factor for its good performance. 23 In our search for sulfide-based Mg positive electrode materials, here we re-examine the first Li insertion positive electrode material: layered TiS 2 . 24 Chemical Mg insertion into this structure was demonstrated long ago, but the Mg sites were not identified. 25,26 TiS 2 nanotubes, cycled in Mg(ClO 4 ) 2 / acetonitrile with a Mg negative electrode, were reported as a Mg positive electrode in 2004. 27 Mg deposition in such a system will be limited, 17 however, owing to the passivation of the Mg electrode, preventing further transport of Mg 2+ ions. 28,29 Another seminal report on TiS 2 showed low initial capacity in a Mg cell, followed by a significant capacity drop durin...

show abstract

Mg Intercalation in Layered and Spinel Host Crystal Structures for Mg Batteries

Cited by 117 publications

References 51 publications

Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries

Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries

Narrowing the Gap between Theoretical and Practical Capacities in Li‐Ion Layered Oxide Cathode Materials

Layered TiS₂ Positive Electrode for Mg Batteries

Contact Info

Product

Resources

About

Mg Intercalation in Layered and Spinel Host Crystal Structures for Mg Batteries

Cited by 117 publications

References 51 publications

Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries

Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries

Narrowing the Gap between Theoretical and Practical Capacities in Li‐Ion Layered Oxide Cathode Materials

Layered TiS2 Positive Electrode for Mg Batteries

Contact Info

Product

Resources

About

Layered TiS₂ Positive Electrode for Mg Batteries