Electrodeposited Bi, Sb and Bi1-xSbx alloys as anodes for Mg-ion batteries

Arthur, Timothy S.; Singh, Nikhilendra; Matsui, Masaki

doi:10.1016/j.elecom.2011.12.010

Cited by 238 publications

(239 citation statements)

References 12 publications

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“…These systems provide a relatively facile delivery of Mg 2+ ions in a chloride-free electrolyte and an 28,30,48,49 in cells with a working Mg electrode. However, these electrolytes suffer from low (≤87%) CE, significant overpotential, destructive incompatibilities with Mg metal resulting in passivation of the anode surface, and parasitic loss of electrolyte due to the electrochemical decomposition of solvent (e.g., AN) mimicking Mg-plating/insertion.…”

Section: ■ Introductionmentioning

confidence: 99%

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)₂ in Diglyme: Implications for Multivalent Electrolytes

2016

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We reveal the general mechanisms of partial reduction of multivalent complex cations in conditions specific for the bulk solvent and in the vicinity of the electrified metal electrode surface and disclose the factors affecting the reductive stability of electrolytes for multivalent electrochemistry. Using a combination of ab initio techniques, we clarify the relation between the reductive stability of contact-ion pairs comprising a multivalent cation and a complex anion, their solvation structures, solvent dynamics, and the electrode overpotential. We found that for ion pairs with multiple configurations of the complex anion and the Mg cation whose available orbitals are partially delocalized over the molecular complex and have antibonding character, the primary factor of the reductive stability is the shape factor of the solvation sphere of the metal cation center and the degree of the convexity of a polyhedron formed by the metal cation and its coordinating atoms. We focused specifically on the details of Mg (II) bis(trifluoromethanesulfonyl)imide in diethylene glycol dimethyl ether (Mg(TFSI)2)/diglyme) and its singly charged ion pair, MgTFSI+. In particular, we found that both stable (MgTFSI)+ and (MgTFSI)0 ion pairs have the same TFSI configuration but drastically different solvation structures in the bulk solution. This implies that the MgTFSI/dyglyme reductive stability is ultimately determined by the relative time scale of the solvent dynamics and electron transfer at the Mg–anode interface. In the vicinity of the anode surface, steric factors and hindered solvent dynamics may increase the reductive stability of (MgTFSI)+ ion pairs at lower overpotential by reducing the metal cation coordination, in stark contrast to the reduction at high overpotential accompanied by TFSI decomposition. By examining other solute/solvent combinations, we conclude that the electrolytes with highly coordinated Mg cation centers are more prone to reductive instability due to the chemical decomposition of the anion or solvent molecules. The obtained findings disclose critical factors for stable electrolyte design and show the role of interfacial phenomena in reduction of multivalent ions.

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Section: ■ Introductionmentioning

confidence: 99%

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)₂ in Diglyme: Implications for Multivalent Electrolytes

2016

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“…15 Liu and coworkers reported ∼300 mAh/g capacities for chemically synthesized bismuth nanotubes in special electrolyte consisting of a Mg(BH 4 ) 2 /LiBH 4 mixture. 16 In addition, using 0.4 M Mg(TFSI) 2 in diglyme, ∼60 mAh/g was observed under repeated cycling in a cathode limited cell configuration.…”

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confidence: 99%

Composite Anodes for Secondary Magnesium Ion Batteries Prepared via Electrodeposition of Nanostructured Bismuth on Carbon Nanotube Substrates

DiLeo

Zhang

Marschilok

et al. 2014

ECS Electrochemistry Letters

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Magnesium-ion batteries are attractive in part due to the high environmental abundance and low cost of magnesium metal. Anode materials other than Mg metal can provide access to new electrochemistries in non-corrosive Mg 2+ electrolytes. A cyclic voltammetric method for the preparation of bismuth (Bi) based anodes was developed by systematically exploring electrodeposition using a quartz crystal microbalance. Controlled deposition of Bi on carbon nanotubes substrates could be achieved, enabling the first electrochemical investigation of bismuth-carbon nanotube (Bi-CNT) composite electrodes. Quasi-reversible Mg electrochemistry of Bi-CNT composite electrodes in non-corrosive magnesium-based electrolyte was demonstrated, with an initial delivered capacity exceeding 180 mAh/g. While the initial capacities were high, significant capacity decreases were observed with repeated cycling, indicating that additional development is warranted to further optimize this system. Interest in magnesium-ion batteries as possible replacements for lithium-ion batteries remains high, in part due to the low cost and high earth abundance of magnesium.1-5 Much of the research to date employs magnesium metal as the anode, given the high theoretical volumetric capacity of 3832 mAh/cm 3 and non-dendritic electrochemical behavior associated with magnesium metal.3,6 However, several challenges remain for full implementation of a magnesium anode battery technology. The surface of magnesium metal when exposed to conventional electrolytes based on carbonates does not generate a surface that is readily electrochemically stripped and plated, which has been attributed to the formation of a non-ion conducting layer on the metal surface. [6][7][8] In order to address the surface issues of the magnesium new classes of electrolytes have been investigated. [8][9][10] However, these electrolytes are typically corrosive and may display significant volatility.11-14 Thus, an alternative anode to magnesium metal that may enable use of less corrosive electrolytes is desirable.Recent reports have investigated the use of bismuth metal as an anode material in magnesium based batteries. 15,16 Assuming six electron equivalents of bismuth oxidation to form magnesium bismuthide, (3Mg 2+ + 2Bi + 6e − Mg 3 Bi 2 ) translates to a theoretical capacity of 385 mAh/g Bi, Figure 1. As bismuth is a dense material (9.8 g/cm 3 ), a significant volume expansion (25-40% increase in Bi-Bi bond length for Mg 3 Bi 2 ) is required to accommodate Mg 2+ insertion and thus loss of contact to the current collecting electrode substrate upon repeated cycling may occur.Matsui and coworkers demonstrated capacities of ∼240 mAh/g for electrodeposited bismuth in corrosive alkylmagnesium/ alkylaluminum chloride based electrolyte.15 Proof of concept quasi-reversible electrochemistry for electrodeposited bismuth in acetonitrile/Mg(TFSI) 2 based electrolyte was also provided, however, only one cycle was shown and the capacity under this condition was not reported. 15 Liu and coworkers reported ∼3...

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“…provide an opportunity to avoid the problems of the Mg metal anode. [127,128] This Mg ion cell concept might be able to lead to other approaches to overcome current issues, as in the case of Li ion cells.…”

Section: Future Challengesmentioning

confidence: 99%

Li‐Ion Batteries and Beyond: Future Design Challenges

Hwa

Cairns

2015

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Light metals have been widely used as electrode materials for batteries owing to their low standard redox potential, their low equivalent weight, large specific capacity, and great abundance. Both primary and secondary cells including light metals as electrode material have influenced all aspects of our lives, e.g., electrically operated toys, power tools, and portable electronics such as cell phones, smart pads, and laptop computers. Among all battery systems, rechargeable lithium (Li) ion cells have been used most widely in recent years owing to their high specific power, high energy density, and ambient temperature operation. However, Li‐ion cells are facing difficult challenges in satisfying the emerging market for advanced applications demanding high‐performance rechargeable batteries for applications such as electric vehicles, high‐performance portable electronics, and large‐scale electrical energy storage systems. Unfortunately, current Li‐ion cells cannot satisfy demands such as low cost, much improved safety, larger energy density, faster charge/discharge rates, and longer service life, so intensive effort is necessary to develop the next generation of cells. In this article, the limitations of current Li‐ion cells and various advanced materials for each component of the Li‐ion cell, in addition to other promising candidates for cells beyond Li ion, such as the Li/S cell and Na‐ and Mg‐based rechargeable cells, and metal/air cells are discussed.

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Electrodeposited Bi, Sb and Bi1-xSbx alloys as anodes for Mg-ion batteries

Cited by 238 publications

References 12 publications

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)₂ in Diglyme: Implications for Multivalent Electrolytes

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)₂ in Diglyme: Implications for Multivalent Electrolytes

Composite Anodes for Secondary Magnesium Ion Batteries Prepared via Electrodeposition of Nanostructured Bismuth on Carbon Nanotube Substrates

Li‐Ion Batteries and Beyond: Future Design Challenges

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Electrodeposited Bi, Sb and Bi1-xSbx alloys as anodes for Mg-ion batteries

Cited by 238 publications

References 12 publications

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)2 in Diglyme: Implications for Multivalent Electrolytes

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)2 in Diglyme: Implications for Multivalent Electrolytes

Composite Anodes for Secondary Magnesium Ion Batteries Prepared via Electrodeposition of Nanostructured Bismuth on Carbon Nanotube Substrates

Li‐Ion Batteries and Beyond: Future Design Challenges

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Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)₂ in Diglyme: Implications for Multivalent Electrolytes

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI)₂ in Diglyme: Implications for Multivalent Electrolytes