Intrinsic Conductivity in Magnesium–Oxygen Battery Discharge Products: MgO and MgO<sub>2</sub>

Smith, Jenna; Naruse, Junichi; Hiramatsu, Hidehiko; Siegel, Donald J.

doi:10.1021/acs.chemmater.7b00217

Cited by 53 publications

(34 citation statements)

References 100 publications

(281 reference statements)

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“…For instance, the nanocomposite of graphene/Mn‐based oxides/organic complex sustainably operates as a functional catalyst for highly reversible charge/discharge at a high current density. 2.In nonaqueous electrolyte, solubility and ionic transportation of O 2 in organic solvent (such as THF) are critical for the overall capacity and high–rate retention of secondary Mg–air cells . To better accommodate the active catalysts, a novel electrolyte system with better solubility and fast diffusivity will be helpful.…”

Section: Discussionmentioning

confidence: 99%

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Current Progress on Rechargeable Magnesium–Air Battery

Sun

Gebert

et al. 2017

Advanced Energy Materials

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in reversible oxidation/reduction reaction to achieve a high energy density. (ii) Fast charge transport and high exchanging current density of materials dramatically reduce the polarization and further provide a high power density. (iii) Uniform micro/nanostructures are associated with increased specific surfaces areas and decreased ionic diffusion over distance and time, resulting in a long lifetime and a good cycling stability.Among various energy sources in history, rechargeable cells are lead (Pb)-acid, nickel-chromium (Ni-Cr), nickel-metal hydride (Ni-MH), redox flow, lithiumion, fuel cells and metal-air batteries. [2] In particular, rechargeable metal-air batteries have received great interest due to a huge theoretical specific energy density, deriving from a unique cell structure. In this system, only the metal (Li, Na, Mg, Al, Zn, Si, Fe, Sn, etc.) anode is assembled in the cell, while the active cathode material is oxygen (O 2 ), directly obtained from the atmosphere. [12][13][14][15][16][17] Figure 1a presents a summary of basic theoretical properties and electrochemical reactions in typical metal-air batteries. For instance, rechargeable Li-air batteries can provide a theoretical cell voltage of 2.96 V and a theoretical specific energy density of 3.4 kW h kg −1 . In this particular battery, the decomposition of lithium peroxide (Li 2 O 2 ), despite being an explosive and poisonous compound, plays a vital role in the improved charge transport because it demonstrates a highly reversible reaction between the discharge and charge process. [18,19] The maximum specific capacity of secondary Li-air batteries reaches an initial discharge capacity of 14000 mA h g −1 at a current density of 140 mA g −1 , using Co 3 O 4 /reduced graphene oxide nanocomposites as electrocatalysts. [20] Unfortunately, although they are the focus of numerous investigations, lithium-air batteries are still accompanied by the major drawbacks of the high price of metallic lithium (The USD $160000-180000/ton as of May 2017) and safety issues in an organic electrolyte.Magnesium provides a number of improvements compared to metallic Li, including its abundance in the earth's crust (2.08% for Mg vs 0.0065% for Li) and environmental friendliness. Moreover, rechargeable Mg-O 2 battery allows a theoretical volumetric density and a specific energy density of 14 kW h L −1 and 3.9 kW h kg −1 , respectively, assuming MgO is formed as the discharge product. [21,22] These values are much larger than those of Li-O 2 cells on the basis of Li 2 O 2 (8.0 kW h L −1 and 3.4 kW h kg −1 ). Though a great number of efforts have focused on the widespread studies of Li-air Rechargeable Mg-air batteries are a promising alternative to Li-air cells owing to the safety, low price originating from the abundant resource on the earth, and high theoretical volumetric density (3832 A h L −1 for Mg anode vs 2062 A h L −1 for Li). Only a few works are related to the highly reversible Mg-air batteries. The fundamental scientific difficulties hindering the rapid developmen...

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Section: Discussionmentioning

confidence: 99%

“…The simulation results are in exact agreement with the above experimental data. Therefore, research should aim to reveal the superoxide–controlled discharging mechanism for secondary Mg–O 2 cells, encouraging extensive efforts to design novel high–efficient stable catalysts.…”

Section: The Rapid Development Of Rechargeable Mg–air Batteriesmentioning

confidence: 99%

Current Progress on Rechargeable Magnesium–Air Battery

Sun

Gebert

et al. 2017

Advanced Energy Materials

164

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“…However, during the charging process, a reverse reaction takes place, which requires breaking of the chemical bonds and corresponding decomposition of the discharge products. The chemical‐bonding energies in these Mg‐containing compounds (MgO, MgS, MgSe, and MgF 2 ) are considerably higher than their Li‐based counterparts (Li 2 O, Li 2 S, Li 2 Se, and LiF), indicating that higher activation energy is necessary to achieve comparable reversibility . Experimental data demonstrate that Mg cells using conversion‐type cathodes exhibit much lower rate capability (very difficult to be cycled at a reasonable current density such as 200 mA cm −2 ) and worse irreversibility (capacity of second cycle drops to only half of the first cycle capacity) compared with their Li analogs.…”

Section: High‐capacity Conversion‐type Cathodes For Rechargeable Mg Bmentioning

confidence: 99%

Rechargeable Magnesium Batteries using Conversion‐Type Cathodes: A Perspective and Minireview

et al. 2018

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would impose restrictions on the penetration of LIBs into these large-volume markets. [3,4] In addition, after 25 years of continuous improvements, the mature LIBs technology is approaching a fundamental limit in terms of energy density (slightly above 300 W h kg −1 ) and costs at the materials level. [4][5][6] With the aforementioned concerns, alternative battery concepts have significantly stimulated research interests to further drive battery technologies to increase both the gravimetric and volumetric energy densities, reduce the cost, and expand the cycling life. [3,6,7] The "beyond Li-ion" technologies such as lithium-air, lithium-sulfur (Li-S), multivalent batteries, and solid-state batteries show the unique feature of using metal anodes that can store more energy via a reversible metal plating/stripping process. Unfortunately, these emerging or reviving technologies involving lithium metal inevitably meet the critical challenges of resource shortage. Furthermore, the high reactivity of lithium metal leads to electrolyte consumption and nonuniform lithium distribution (even dendritic growth) during cycling. These issues still hamper the mainstream commercialization of the lithium-metal-based batteries. [8,9] Rechargeable magnesium (Mg) batteries may offer considerable advantages (see Table 1) over Li-metal batteries because the metallic Mg anode shows double the volumetric capacity, safer and easier processing features, more uniform and nondendritic electroplating during cell charging, and cheaper costs due to its greater abundance in the earth crust. [4,[10][11][12][13] Based on these advantages, intensive attention has been garnered toward the development of new electrolytes, cathodes, and their corresponding mechanistic understandings for the rechargeable Mg batteries. Additionally, several industries including Pellion Technologies (a spin-off company from Massachusetts Institute of Technology), the Toyota Research Institute of North America, and recently Sony Corporation have initiated R&D projects for the rechargeable Mg batteries and tried to find practical application pathways. Nonetheless, developing a high-energy-density Mg battery with long cycle life and high rate capability is still a huge challenge due to the lack of high-performance cathodes and suitable Mg-ion electrolytes. [9,12] It is fair to state that the Chevrel phases, reported by Aurbach et al. in 2000, are still the most attractive Mg-ion Rechargeable magnesium (Mg) batteries are one of the potential contenders to replace current Li-ion batteries to power future electric vehicles with lower cost, higher safety, and extended mileage. To achieve this goal, both high-voltage intercalation-type cathodes and high-capacity conversion-type cathodes are considered. However, there are still no reports to compare rechargeable Mg batteries with the state-of-the art Li-ion batteries in terms of their overall performance. Also, potential cathode materials to deliver higher energy density in rechargeable Mg batteries are rarely summarized. Here, t...

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“…The concept and electrochemistry of batteries based on divalent alkaline earth metal (e.g. Ca and Mg) superoxides have also evolved and been evaluated lately . Superoxide batteries, the essential features of which surpass those of current lithium‐ion technology, have become highly competitive candidates for storing renewable energy on a large scale.…”

Section: Figurementioning

confidence: 99%

Simultaneous Stabilization of Potassium Metal and Superoxide in K–O₂ Batteries on the Basis of Electrolyte Reactivity

Xiao

Gourdin

2018

Angewandte Chemie

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In superoxideb atteries based on O 2 /O 2 À redox chemistry,identifying an electrolyte to stabilizeboth the alkali metal and its superoxider emains challenging owing to their reactivity towards the electrolyte components.Bis(fluorosulfonyl)imide (FSI À )h as been recognized as a" magic anion" for passivating alkali metals.The KFSI-dimethoxyethane electrolyte passivates the potassium metal anode by cleavage of S À F bonds and the formation of aK F-richs olid-electrolyte interphase (SEI). However,t he KFSI salt is chemically unstable owingt on ucleophilic attackb ys uperoxide and/or hydroxide species.Onthe other hand, potassium bis(trifluorosulfonyl)imide (KTFSI) is stable to KO 2 ,b ut results in mossy potassium deposits and irreversible plating and stripping. To circumvent this dilemma, we developed an artificial SEI for the metal anode and thus long-cycle-life K-O 2 batteries.This study will guide the development of stable electrolytes and artificial SEIs for metal-O 2 batteries.Superoxide batteries based on reversible single-electron O 2 / MO 2 (M = Li, Na, and K) redox couples have promised high theoretical energy density,g ood energy efficiency,a nd low material cost. [1][2][3][4] These batteries provide an elegant solution to the challenges of two-electron oxygen reduction/evolution reactions in traditional Li-O 2 batteries without the use of any catalysts or redox mediators.T he concept and electrochemistry of batteries based on divalent alkaline earth metal (e.g. Ca and Mg) superoxides have also evolved and been evaluated lately. [5,6] Superoxide batteries,t he essential features of which surpass those of current lithium-ion technology, have become highly competitive candidates for storing renewable energy on al arge scale.S ince our research group invented K-O 2 batteries in 2013, much effort has been devoted to exploring KO 2 chemistry as well as electrode and electrolyte materials. [7][8][9][10][11][12] Unlike the Li and Na counterparts, KO 2 is both thermodynamically and kinetically stable,which ensures its long-term stability as ad ischarge product and provides unique advantages,a lthough an energy-density trade-off is expected (935 Wh kg À1 based on the mass of KO 2 ). [7,13] Kang and co-workers also demonstrated aN a-K alloy anode in K-O 2 batteries. [14] Lu and co-workers recently reported aD MSO-based K-O 2 battery with improved electrode kinetics. [15] Thus far,b ased on knowledge of reversible cathode chemistry,t he highly reductive and less stable potassium metal anode is deemed the major challenge to realizing afully reversible K-O 2 battery.An ideal solid-electrolyte interphase (SEI) is desired to enable the use of alkali-metal anodes.T he KPF 6 -dimethoxyethane (DME) electrolyte leads to ashort cycle life owing to the unstable SEI on Kmetal, which is vulnerable to both ether solvent and oxygen from crossover. [1,8] Although the KTFSI-DME electrolyte builds an impermeable layer that blocks solvent and oxygen, it causes low ionic conductivity for K + cations,which sacrifices the advantageous e...

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Intrinsic Conductivity in Magnesium–Oxygen Battery Discharge Products: MgO and MgO₂

Cited by 53 publications

References 100 publications

Current Progress on Rechargeable Magnesium–Air Battery

Current Progress on Rechargeable Magnesium–Air Battery

Rechargeable Magnesium Batteries using Conversion‐Type Cathodes: A Perspective and Minireview

Simultaneous Stabilization of Potassium Metal and Superoxide in K–O₂ Batteries on the Basis of Electrolyte Reactivity

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Intrinsic Conductivity in Magnesium–Oxygen Battery Discharge Products: MgO and MgO2

Cited by 53 publications

References 100 publications

Current Progress on Rechargeable Magnesium–Air Battery

Current Progress on Rechargeable Magnesium–Air Battery

Rechargeable Magnesium Batteries using Conversion‐Type Cathodes: A Perspective and Minireview

Simultaneous Stabilization of Potassium Metal and Superoxide in K–O2 Batteries on the Basis of Electrolyte Reactivity

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Product

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Intrinsic Conductivity in Magnesium–Oxygen Battery Discharge Products: MgO and MgO₂

Simultaneous Stabilization of Potassium Metal and Superoxide in K–O₂ Batteries on the Basis of Electrolyte Reactivity