Insights into Mg2+ Intercalation in a Zero-Strain Material: Thiospinel MgxZr2S4

Bonnick, Patrick; Blanc, Lauren; Vajargah, Shahrzad Hosseini; Lee, Chang-Wook; Sun, Xiaoqi; Balasubramanian, Mahalingam; Nazar, Linda F.

doi:10.1021/acs.chemmater.8b01345

Cited by 43 publications

(38 citation statements)

References 48 publications

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“…16,[44][45][46] Mn-cathode materials also suffer from low electronic conductivity, which can limit the diffusivity of divalent ions and diminish overall electrode performance. 47 Therefore, a wide variety of techniques (electrolyte additives, 20 structural modifications, [48][49][50] conductive composites, [51][52][53][54] and binder-free electrodes [55][56][57] ) have been developed to address these issues and enhance the electrochemical properties of Mn-cathode materials in ZIBs.…”

Section: Conversion Oxides: Manganese-and Cobalt-based Materialsmentioning

confidence: 99%

Scientific Challenges for the Implementation of Zn-Ion Batteries

Blanc

Kundu

Nazar

2020

Joule

Self Cite

1,483

950

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The safety, affordability, and impressive electrochemical performance of many Zn-ion batteries (ZIBs) has recently triggered an overwhelming literature surge. As is typical for a new area, initial enthusiasm and high expectations have now been replaced by a more measured period of research that reaches deep into the underlying factors controlling electrochemical properties. Rather than battery metrics, this review focuses on fundamental aspects of the chemistry of ZIBs that are the least understood and on which there has been progress over the last few years. We provide guidance for future research regarding (1) the significant challenge of proton/Zn 2+ co-intercalation in aqueous media, (2) limitations to conversion chemistry that often accompanies ZIB electrochemistry, (3) positive aspects of facile Zn 2+ (de)intercalation in nonaqueous electrolytes and organic cathode materials, (4) the desolvation penalty at electrode-electrolyte interfaces, (5) solutions for controlling Zn dendritic growth, and (6) suggested electrochemistry protocols for the field.

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Section: Conversion Oxides: Manganese-and Cobalt-based Materialsmentioning

confidence: 99%

Scientific Challenges for the Implementation of Zn-Ion Batteries

Blanc

Kundu

Nazar

2020

Joule

Self Cite

1,483

950

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“…The metal chalcogenides that have been experimentally tested as intercalation cathode for Mg batteries are Mo 6 S 8 , [5] Ti 2 S 4 , [38] TiS 2 , [31,36,39,40] MgTiS 2 , [41] MoS 2 , [42] TiSe 2 , [36,43,44] WSe 2 , [45] Cu 2 MoS 4 , [46] VS 2 , [47,48] VS 4 , [49,50] NbSe 2 , [51] Ni 3 Se 4 , [12] and Mg x ZrS 4. [52] On the other hand, metal chalcogenide compounds (M a X b, M = metal, X = S, Se, Te) which react with Mg 2+ to yield metallic nanoparticles embedded in the matrix of MgX (Figure 2b) are referred to as conversion-type cathodes. In these conversion cathodes, the redox couple is M/M n+ , which delivers higher capacity.…”

Section: Types and Structures Of Metal Chalcogenide Cathodesmentioning

confidence: 99%

Section: Types and Structures Of Metal Chalcogenide Cathodesmentioning

confidence: 99%

Designing Nanostructured Metal Chalcogenides as Cathode Materials for Rechargeable Magnesium Batteries

Regulacio

Nguyen

Horia

et al. 2021

Small

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Rechargeable magnesium batteries (RMBs) are regarded as promising candidates for beyond‐lithium‐ion batteries owing to their high energy density. Moreover, as Mg metal is earth‐abundant and has low propensity for dendritic growth, RMBs have the advantages of being more affordable and safer than the currently used lithium‐ion batteries. However, the commercial viability of RMBs has been negatively impacted by slow diffusion kinetics in most cathode materials due to the high charge density and strongly polarizing nature of the Mg2+ ion. Nanostructuring of potential cathode materials such as metal chalcogenides offers an effective means of addressing these challenges by providing larger surface area and shorter migration routes. In this article, a review of recent research on the design of metal chalcogenide nanostructures for RMBs’ cathode materials is provided. The different types and structures of metal chalcogenide cathodes are discussed, and the synthetic strategies through which nanostructuring of these materials can be achieved are described. An organized summary of their electrochemical performance is also presented, along with an analysis of the current challenges and future directions. Although particular focus is placed on RMBs, many of the nanostructuring concepts that are discussed here can be carried forward to other next‐generation energy storage systems.

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“…However, the facilitation of Mg 2+ diffusion within these electrode frameworks comes at the cost of average operating potentials (≈1 V vs Mg/Mg 2+ ) and gravimetric capacities, thus leading to low energy densities. [ 21,22 ] Noticeably, the low redox potential feature of these chalcogenide electrodes reveals that they are anodes virtually upon assembling to full MIBs, if cathodes with high operating potentials are applied. Switching to transition metal oxide electrodes can fundamentally elevate operating potentials and increase specific capacities.…”

Section: Figurementioning

confidence: 99%

Hydrated Mg_xV₅O₁₂ Cathode with Improved Mg²⁺ Storage Performance

Zhu

Huang

Yin

et al. 2020

Advanced Energy Materials

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Li + (0.76 Å) holds a great potential to deliver remarkable theoretical energy storage metrics. [10,11] Despite the straightforward concept of taking advantage of a divalent cation, developing rechargeable and stable MIBs has been plagued by various materials limitations, especially the lack of suitable intercalation electrode materials and stable electrolytes featuring wide electrochemical windows. [12-15] Indeed, the greatest of these limitations on simulating the working mechanism of LIBs using intercalation cathodes and anodes is primarily caused by the sluggish solid-state diffusion of divalent Mg ion. This is strongly related to the large polarization of anionic frameworks of electrodes and more intense repulsions among the intercalated divalent Mg ions due to a higher charge-to-radius ratio of Mg 2+ compared to Li +. [16-18] Because of heavy anionic frameworks and moderate polarity of anions, the classical Mo 6 S 8 Chevrel phases and transition metal dichalcogenides show an Mg 2+ screening effect, [19,20] mitigating the solid-state diffusion difficulty of Mg 2+ to some extent. However, the facilitation of Mg 2+ diffusion within these electrode frameworks comes at the cost of average operating potentials (≈1 V vs Mg/Mg 2+) and gravimetric capacities, thus leading to low energy densities. [21,22] Noticeably, the low redox potential feature of these chalcogenide electrodes reveals that they are anodes virtually upon assembling to full MIBs, if cathodes with high operating potentials are applied. Switching to transition metal oxide electrodes can fundamentally elevate operating potentials and increase specific capacities. [20,23-25] Nonetheless, the bivalency nature of Mg 2+ imposes a large energy penalty during the desolvation process at the electrode/electrolyte interface, resulting in insufficient power densities. To improve the rate capability, nanostructure engineering (e.g., increasing interlayer spacing of layered electrodes) and chemical composition control (e.g., structural H 2 O, cation doping) of oxide electrodes can be conducted to modify the kinetics and thermodynamics of Mg 2+ insertion. [26-28] Orthorhombic single-layered V 2 O 5 , consisting of alternating corner-and edge-sharing VO 5 square pyramids (Figure S1, Supporting Information), allows the diffusion of small, monovalent Li ions through the framework. However, the limited interlayer spacing of ≈4.5 Å is not sufficient for the intercalation of larger (e.g., Na +) or multivalent (e.g., Mg 2+) cations. [7,29,30] Employing single-layered V 2 O 5 to design bilayered vanadium bronzes through different chemical approaches enables the applicability Mg-ion batteries (MIBs) possess promising advantages over monovalent Li-ion battery technology. However, one of the myriad obstacles in realizing highly efficient MIBs is a limited selection of cathode materials that can enable reversible, stable Mg 2+ intercalation at a high operating voltage. Here, a scalable method is showcased to synthesize a hydrated Mg x V 5 O 12 cathode, which shows a high capa...

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Insights into Mg²⁺ Intercalation in a Zero-Strain Material: Thiospinel Mg_xZr₂S₄

Cited by 43 publications

References 48 publications

Scientific Challenges for the Implementation of Zn-Ion Batteries

Scientific Challenges for the Implementation of Zn-Ion Batteries

Designing Nanostructured Metal Chalcogenides as Cathode Materials for Rechargeable Magnesium Batteries

Hydrated Mg_xV₅O₁₂ Cathode with Improved Mg²⁺ Storage Performance

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Insights into Mg2+ Intercalation in a Zero-Strain Material: Thiospinel MgxZr2S4

Cited by 43 publications

References 48 publications

Scientific Challenges for the Implementation of Zn-Ion Batteries

Scientific Challenges for the Implementation of Zn-Ion Batteries

Designing Nanostructured Metal Chalcogenides as Cathode Materials for Rechargeable Magnesium Batteries

Hydrated MgxV5O12 Cathode with Improved Mg2+ Storage Performance

Contact Info

Product

Resources

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Insights into Mg²⁺ Intercalation in a Zero-Strain Material: Thiospinel Mg_xZr₂S₄

Hydrated Mg_xV₅O₁₂ Cathode with Improved Mg²⁺ Storage Performance