Dual Intercalating Molten Electrolyte Batteries

Carlin, Richard T.; Long, Hugh C. De; Fuller, Joan; Trulove, Paul C.

doi:10.1149/1.2055041

Cited by 348 publications

(238 citation statements)

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“…31 With the addition of water, the prominent absorption feature around ∼3078 cm -1 spossibly the symmetric and antisymmetric stretch vibrational modes of HC (4) Figure 4c, the IR absorption spectra in this range are almost identical for both samples, suggesting the imidazolium cation separated from the anion and was surrounded by water molecules. The change in the 2800-3000 cm -1 range with increasing water content is relatively minor for both samples; the blue shift of ν SS CH 3 and ν FR CH 3 of the butyl chain was ∼10 cm -1 with increasing water content based on multipeak Gaussian fitting. 31 4 ] it is nearly intact even 48 h after the mixture was made (Figure 5b).…”

Section: Resultsmentioning

confidence: 88%

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Structures of Ionic Liquids with Different Anions Studied by Infrared Vibration Spectroscopy

et al. 2008

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We investigated the structures of ionic liquids (1-butyl-3-methylimidazolium iodide [BMIM][I] and 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF 4 ]) and their aqueous mixtures using attenuated total reflection (ATR) infrared absorption and Raman spectroscopy. The ATR spectrum in the CH x (x ) 1, 2, 3) vibration region from 2800 to 3200 cm [BF 4 ]. These differences are considered to come from the variation in the position of the anion, where I -is expected to be closer to the C(2) hydrogen of the imidazolium cation and interacting more specifically as compared to BF 4 -.

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Section: Resultsmentioning

confidence: 88%

“…[1][2][3] Thus molecular design, synthesis, and characterization of RILs have been the focus of many recent scientific investigations. [4][5][6] However, one of the barriers in the application of RILs is the general lack of physical property data for these compounds toward fundamental understanding of the system.…”

Section: Introductionmentioning

confidence: 99%

Structures of Ionic Liquids with Different Anions Studied by Infrared Vibration Spectroscopy

et al. 2008

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“…This would be due to the electrochemical organic cation intercalation into the graphite layers [1,2] before the formation of a solid electrolyte interface (SEI) film on the graphite particles during the 1st charging. Recently, it has been reported that the graphite electrode indicated good charge-discharge characteristics by adding an additive such as vinylene carbonate [3] to the RTILs or using the RTILs such as…”

Section: Introductionmentioning

confidence: 99%

Influence of the binder types on the electrochemical characteristics of natural graphite electrode in room-temperature ionic liquid

Ui¹,

Towada²,

Agatsuma³

et al. 2011

Journal of Power Sources

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“…The reversible fluorination of graphite using the principle of dual ͑de͒intercalation of Li + at the anode and F − at the cathode opens the door to an interesting and potentially high-energy density variant on the Li-ion battery cell design. Other groups [6][7][8][9] have considered the advantages of a dual-ion intercalating battery, such as high cell voltage, using for example lithium cations and large polyatomic anions PF 6 − or ClO 4 − . These studies demonstrated successful cell operation, albeit with modest capacity and cycle life presumably due to the ͑de͒-intercalation of large polyatomic anions and poor anodic stability of the electrolyte solvent.…”

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confidence: 99%

Reversible Intercalation of Fluoride-Anion Receptor Complexes in Graphite

West

Whitacre

Leifer

et al. 2007

J. Electrochem. Soc.

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We have demonstrated a route to reversibly intercalate fluoride-anion receptor complexes in graphite via a nonaqueous electrochemical process. This approach may find application for a rechargeable lithium-fluoride dual-ion intercalating battery with high specific energy. The cell chemistry presented here uses graphite cathodes with LiF dissolved in a nonaqueous solvent through the aid of anion receptors. Cells have been demonstrated with reversible cathode specific capacity of approximately 80 mAh/g at discharge plateaus of upward of 4.8 V, with graphite staging of the intercalant observed via in situ synchrotron X-ray diffraction during charging. Electrochemical impedance spectroscopy and 11 B nuclear magnetic resonance studies suggest that cointercalation of the anion receptor with the fluoride occurs during charging, which likely limits the cathode specific capacity. The anion receptor type dictates the extent of graphite fluorination, and must be further optimized to realize high theoretical fluorination levels. To find these optimal anion receptors, we have designed an ab initio calculations-based scheme aimed at identifying receptors with favorable fluoride binding and release properties. As cathodes in lithium batteries, carbon-fluoride ͑C-F͒ compounds offer very high theoretical specific capacity, on the scale of 1785 mAh/g for C 1.25 F, though to date, all C-F compounds regardless of preparation conditions are strictly non-rechargeable. A rechargeable C-F cathode would be very desirable in terms of specific energy relative to conventional lithium-ion transition metal oxide cathodes, though there are numerous difficulties associated with reversible fluorination of carbon which relate to a large extent to the nature of the C-F bond.The reaction of carbon and fluorine is well known to yield a wide range of useful compounds with varying properties, depending on preparation conditions and synthesis route. Many of these compounds, despite their relatively poor electronic conductivity, are useful as cathodes for primary Li batteries. Direct reaction of fluorine gas with graphite at temperatures greater than 350°C results in covalent bonding of C x -F with the transition of the planar sp 2 graphene sheets to buckled sp 3 carbon, and concomitant drop in electrical conductivity with decreasing x. Room temperature chemical fluorination of graphite in the presence of various fluorides such as HF, WF 6 , SbF 5 , and IF 5 has been demonstrated by others up to C 1.0 F 0.89 ͑I 0.02 H 0.06 ͒. 1 Under these preparation conditions, the sp 2 carbon hybridization is maintained, and the C-F bonding is ionic. Electrochemical fluorination of graphite in aqueous or anhydrous HF media is also possible, resulting in ionic or semi-covalent C x -F depending on the degree of fluorination, though this process is not significantly reversible and has poor Coulombic efficiency. 2-4 A candidate rechargeable C-F cathode must retain good electronic conductivity and thus the practical lower bound on C x F is likely near the C-F delocalizati...

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Dual Intercalating Molten Electrolyte Batteries

Cited by 348 publications

References 1 publication

Structures of Ionic Liquids with Different Anions Studied by Infrared Vibration Spectroscopy

Structures of Ionic Liquids with Different Anions Studied by Infrared Vibration Spectroscopy

Influence of the binder types on the electrochemical characteristics of natural graphite electrode in room-temperature ionic liquid

Reversible Intercalation of Fluoride-Anion Receptor Complexes in Graphite

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