The beneficial effect of increased cathode water content on Mg/MnO2 battery performance

Jarvis, L.P.

doi:10.1016/0378-7753(90)87020-r

Cited by 15 publications

(6 citation statements)

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“…As with other oxides, ionic diffusion is expected to be impeded by the combination of the highly ionic nature of the oxide host lattice and the large charge density of the MV ion. Electrochemical Li intercalation in MnO 2 was initially investigated as early as 1974, − while chemical insertion of Mg into a variety of MnO 2 phases was explored by Bruce et al Motivated by the abundant availability, environmental compatibility, low cost, the aforementioned large theoretical capacity, and structural versatility of a number of known MnO 2 polymorphs, electrochemical intercalation of Mg ,,− and Zn ,− in MnO 2 has received much attention recently. Researchers have suggested that the presence of large structural voids characteristic of some MnO 2 polymorphs, such as Hollandite (α-MnO 2 ), OMS-5 (a 4 × 2 tunnel structure under the Ramsdellite family), and the layered Birnessite (δ-MnO 2 ), as seen in Figure , could facilitate the diffusion of Mg 2+ (MV) ions. ,,, However, there is potential for conversion reactions that lead to the irreversible formation of MgO. , The presence of water in the cathode or electrolyte is reported to significantly affect the electrochemical performance of the MnO 2 system, with experiments claiming notable improvement in Mg-cycling in the layered-δ and the spinel-λ polymorphs ,, and a possible impact of water on the phase stability of the MnO 2 polymorphs upon Mg insertion. , Nevertheless, the presence of water can lead to parasitic side reactions, such as Mn 2+ dissolution − or proton intercalation (as discussed in previous sections), which can contribute to the electrochemical data observed.…”

Section: Oxidesmentioning

confidence: 99%

Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges

et al. 2017

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The rapidly expanding field of nonaqueous multivalent intercalation batteries offers a promising way to overcome safety, cost, and energy density limitations of state-of-the-art Li-ion battery technology. We present a critical and rigorous analysis of the increasing volume 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 analysis 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 experiments and theory, ranging from charting the design metrics useful for developing the next generation of MV-cathodes to targeted in-depth studies rationalizing complex experimental results. On the basis of our critical review of the literature, we provide suggestions for future multivalent cathode studies, including a strong emphasis on the unambiguous characterization of the intercalation mechanisms.

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Section: Oxidesmentioning

confidence: 99%

Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges

et al. 2017

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“…In the quest for an MVIB with an energy density greater than that of the Chevrel phase, MnO 2 polymorphs have been proposed as a promising candidate. − Offering a high theoretical voltage and capacity reaching up to 2.8 V and 308 mA h/g, respectively (for MgMnO 2 ), these materials make for an excellent cathode material when intercalated with multivalent ions. , In addition to a favorable energy density, the large number of MnO 2 polymorphs offer structural versatility, and many of the phases are abundant and consequently inexpensive …”

Section: Introductionmentioning

confidence: 99%

“…It is hopeful that utilizing metallic Ca and Al anodes with MnO 2 -based cathodes will provide batteries with a higher energy density than MgMnO 2 batteries, which is similar to the impact of intercalating the Chevrel phase with Ca and Al. ,, Ca-based batteries are often neglected because of the difficulty in plating the Ca anode and in finding appropriate cathodes and electrolytes. Yet, if these points are addressed, Ca-ion batteries are expected to yield a higher energy density than Mg-ion batteries because Ca produces a higher voltage and could potentially be made out of materials that are abundant in Earth’s crust. ,, While LiMnO 2 batteries have been investigated for decades, − more recently, MnO 2 polymorph cathodes combined with Mg and Zn anodes have generated significant interest. − ,, To the best of our knowledge, a comprehensive ab initio study has not yet been reported on the pairing of MnO 2 polymorphs with anodes including M = Li, Mg, Ca, Zn, and Al metals.…”

Section: Introductionmentioning

confidence: 99%

“…While MnO 2 polymorphs have been studied with several anode pairings, − ,− MnO 2 polymorphs intercalated with Ca and Al have not received much attention. It is hopeful that utilizing metallic Ca and Al anodes with MnO 2 -based cathodes will provide batteries with a higher energy density than MgMnO 2 batteries, which is similar to the impact of intercalating the Chevrel phase with Ca and Al. ,, Ca-based batteries are often neglected because of the difficulty in plating the Ca anode and in finding appropriate cathodes and electrolytes.…”

Section: Introductionmentioning

confidence: 99%

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Density Functional Theory Modeling of MnO₂ Polymorphs as Cathodes for Multivalent Ion Batteries

2018

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Multivalent ion batteries (MVIBs) provide an inexpensive and energy-dense alternative to Li-ion batteries when portability of the battery is not of primary concern. However, it is difficult to find cathode materials that provide optimal battery characteristics such as energy density, adequate charge/discharge rates, and cyclability when paired with a multivalent ion. To address this, we investigate six MnO 2 polymorphs as cathodes for MVIBs using density functional theory calculations. We find voltages as high as 3.7, 2.4, 2.7, 1.8, and 1.0 V for Li, Mg, Ca, Al, and Zn, respectively, and calculate the volume change due to intercalation. We then focus specifically on Ca and compute the energy barriers which are associated with the diffusion of the ion throughout the materials. Our findings show that the α-phase displays the most rapid diffusion kinetics for a Ca ion, with a diffusion barrier as low as 190 meV. We then investigate the potential for the five polymorphs exhibiting the highest voltage to intercalate additional atoms and demonstrate that it is energetically favorable for each to accept at least one additional Ca ion; furthermore, two of the phases can accept more than two Ca ions. However, in each case, there is also a corresponding drop in the voltage as further atoms are intercalated. We also utilize a crystal-chemistry approach to detail the structural evolution of each phase by computing the bond valence sum and effective coordination of the Mn 4+ ions upon intercalation of increasing numbers of Ca ions. Finally, by computing the electronic density of states, Bader charges, and real space charge density, we describe how the additional electrons from the Ca ions are distributed throughout the unit cell. These insights provide guidance in selecting a MnO 2 polymorph with the traits necessary for the realization of MVIBs.

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“…Magnesium batteries, both reserve and dry types, are attractive as power sources [1,2]. Investigations on magnesium anodes individually or in conjunction with several depolarizers have been described [3][4][5].…”

Section: Introductionmentioning

confidence: 99%

Performance of a magnesium?lithium alloy as an anode for magnesium batteries

Sivashanmugam

Kumar

Renganathan

et al. 2004

Journal of Applied Electrochemistry

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In this work, we describe an evaluation of an Mg-Li alloy (Li: 13 wt %) for possible use in magnesium primary reserve batteries. Higher OCP for the Mg-Li alloy have been observed in 2 M MgCl 2 and MgBr 2 electrolyte. The corrosion rate of the Mg-Li alloy is found to be in the order: MgCl 2 < Mg(COOCH 3 ) 2 < MgSO 4 < MgBr 2 < Mg(ClO 4 ) 2 . Mg-Li alloys exhibit higher (81%) anodic efficiencies even when the current density is increased to 8.6 mA cm )2 . It has been observed that Mg-Li/MgCl 2 /CuO cells offer higher operating voltage and capacity than those with the conventionally used Mg-Al alloy.

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The beneficial effect of increased cathode water content on Mg/MnO2 battery performance

Cited by 15 publications

References 1 publication

Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges

Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges

Density Functional Theory Modeling of MnO₂ Polymorphs as Cathodes for Multivalent Ion Batteries

Performance of a magnesium?lithium alloy as an anode for magnesium batteries

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The beneficial effect of increased cathode water content on Mg/MnO2 battery performance

Cited by 15 publications

References 1 publication

Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges

Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges

Density Functional Theory Modeling of MnO2 Polymorphs as Cathodes for Multivalent Ion Batteries

Performance of a magnesium?lithium alloy as an anode for magnesium batteries

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Density Functional Theory Modeling of MnO₂ Polymorphs as Cathodes for Multivalent Ion Batteries