Many-body effects in x-ray photoemission from magnesium

Ley, L.; McFeely, F. R.; Kowalczyk, S. P.; Jenkin, J.G.; Shirley, D. A.

doi:10.1103/physrevb.11.600

Cited by 155 publications

(33 citation statements)

References 33 publications

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“…It has been reported that metallic Mg is highly reactive to O 2 even under a very high vacuum (∼10 −8 Torr) and therefore thin films prepared under different background pressures must exhibit the surface characteristics of the oxides in their respective XPS results. 45 Ley et al 46 have studied the XPS of pure Mg films in the pressure range 3 × 10 −10 -6 × 10 −11 Torr and the positions of the peaks in the core electron spectra were 49.4 eV and 88.55 eV for the Mg 2p and Mg 2s levels, respectively. Herein, the peak shifts for Mg on oxidation are 1.2 eV and 1.05 eV for the Mg 2p and Mg 2s levels, respectively.…”

Section: Resultsmentioning

confidence: 99%

Magnesium Borohydride-Based Electrolytes Containing 1-butyl-1-methylpiperidinium bis(trifluoromethyl sulfonyl)imide Ionic Liquid for Rechargeable Magnesium Batteries

Nuli

Wang

et al. 2016

J. Electrochem. Soc.

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The electrolytes containing halide-free inorganic magnesium salt Mg(BH 4 ) 2 dissolved in ether solvents have shown reversible Mg deposition-dissolution performance. Herein, we improved the anodic stability of the electrolytes on non-inert stainless-steel electrode by mixing PP 14 TFSI ionic liquid with tetraglyme (TG) and dimethoxyethane (DME) ether solvents. The effect of mixing ratios and salt concentrations on the electrochemical behavior of the electrolyte were investigated. High anodic stability, good ionic conductivity, excellent cycling efficiency, feasibility of the preparation and good compatibility toward Mo 6 S 8 and TiO 2 insertion cathode make the electrolytes promising for the potential application in rechargeable magnesium batteries. 3-5 The development of magnesium electrolytes is considered as the most important challenge for the commercial application of rechargeable magnesium batteries because electrolyte properties govern battery performance and determine the class of cathodes to be utilized. 6 The significant progress is the reports of 0.25 mol L −1 Mg(AlCl 2 BuEt) 2 /THF (Bu=butyl, Et=ethyl) electrolyte 7,8 and 0.4 mol L −1 (PhMgCl) 2 -AlCl 3 /THF electrolyte, 9,10 which have high anodic stability (2.5 V and 3.3 V vs. Mg RE on inert Pt electrode, respectively) and reversibility of Mg deposition-dissolution. Recently, a family of novel boron based electrolytes with high ionic conductivity, excellent Mg deposition reversibility as well as high anodic potential were proposed.11,12 On the other hand, phenolate-based 13 and alkoxide-based 14 electrolytes exhibit air insensitive character and excellent magnesium depositiondissolution performance. Meanwhile, inorganic magnesium salt solutions synthesized by the acid-base reaction of MgCl 2 and Lewis acidic compounds such as AlCl 3 show high coulombic efficiency, low overpotential for magnesium deposition-dissolution and good anodic stability. [15][16][17][18] However, these electrolytes may corrode non-inert current collectors at lower anodic potentials duo to the presence of halides in the cation and anion components of the electrolytes, although some of these electrolytes have shown impressive stability against electrochemical oxidation.19 Hence, it is still necessary to find electrolytes with high stabilities on non-inert current collectors for a practical rechargeable Mg battery system. Nelson et al. showed that decreasing the chloride content in Mg electrolytes by switching the Lewis acid from AlCl 3 to Al(OPh) 3 greatly improves the anodic stability up to 5 V on both Pt and stainless steel electrodes.20 Ha et al. proposed a new class of electrolytes based on magnesium (II) bis(trifluoromethane sulfonyl)imide (Mg[N-(SO 2 CF 3 ) 2 ] 2 , Mg(TFSI) 2 ) dissolved in glymebased solvents with unique characteristics such as highly reduced corrosive nature toward the current collector, low volatility, high solvating power, and the ability to form an appropriate solvation sheath structure for Mg deposition-dissolution. 21 Recently, a whole new promisi...

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Section: Resultsmentioning

confidence: 99%

Magnesium Borohydride-Based Electrolytes Containing 1-butyl-1-methylpiperidinium bis(trifluoromethyl sulfonyl)imide Ionic Liquid for Rechargeable Magnesium Batteries

Nuli

Wang

et al. 2016

J. Electrochem. Soc.

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“…A concept that makes independent use of the energies of the photoelectrons and the Auger electrons, as well as the Auger parameter, is the two-dimensional chemical state plot (6). In this, for each element, the kinetic energies of pho- toelectrons for various chemical states are plotted on the abscissa, and those of corresponding Auger electrons on the ordinate.…”

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confidence: 99%

Two-dimensional chemical state plots: a standardized data set for use in identifying chemical states by x-ray photoelectron spectroscopy

Wagner¹,

Gale²,

Raymond³

1979

Anal. Chem.

673

253

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The comblned use of both photoelectron and X-ray excited Auger llnes increases the utility of ESCA for identifying chemical states. A useful format for displaying reference data is the two-dimenslonal plot where the kinetic energy of the sharpest Auger llne is plotted vs. the binding energy of the most Intense photoelectron line. A compilation of data for 24 elements is presented, including critically evaluated data from the literature which have been referenced to a uniform calibration line. The format of the plots is applicable to data obtained with Ionizing photons of any energy. The data included for silicon, bromine, and tungsten were obtained with higher energy X-rays from a Au X-ray source.The ESCA (Electron Spectroscopy for Chemical Analysis) or XPS (X-Ray Photoelectron Spectroscopy) technique has a special value among methods for analysis of surfaces because it furnishes information on the nature of chemical states. This is possible because the X-radiation used ordinarily does not produce chemical changes in the surface layers.In the original concept (I), chemical shifts in photoelectron energies were stressed as the means by which chemical states can be identified. This feature is limited, however, since ranges in chemical shifts for some elements are small, and because there are difficulties in defining accurately the spectral line energies from insulating samples due to static charging.There are other spectral features that can be useful in identifying chemical states. I t has been found that chemical shifts in X-ray excited Auger lines are usually larger and very different from those in photoelectron lines ( 2 ) . Those Auger lines that originate from Auger transitions resulting in vacancies in core levels have at least one sharp, intense component (3). Chemical shifts in this component can be measured as accurately as those in photoelectron lines, and this extra information is of significant value.Since the chemical shifts of photoelectrons and Auger electrons are different, the differences between their kinetic energies constitute a special spectral property. This difference has been called the Auger parameter ( 4 ) and its numerical value is unique to each chemical state. It is more accurately determinable than either the photoelectron or Auger electron energy alone, because the static charge corrections in these lines then cancel. The chemical shift in the Auger parameter between two chemical states is related to the difference in extra-atomic relaxation energy between the two chemical states ( 5 ) .The Auger parameter is still a one-dimensional quantity, like the photoelectron energy or the Auger electron energy alone. A concept that makes independent use of the energies of the photoelectrons and the Auger electrons, as well as the Auger parameter, is the two-dimensional chemical state plot (6). In this, for each element, the kinetic energies of phoPresent address: 29 Starview Drive, Oakland, California 94618. 0003-2700/79/0351-0466$0 1 .OO/Otoelectrons for various chemical states are plotted...

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“…Access to broad energy ranges is extremely important because the plasmons are quantized in energy, permitting a series of energy loss peaks at x, 2x, 3x, etc., to be identified as the signature of the volume plasmon loss; the lower intensity surface plasmon loss is generally seen as a shoulder at $0.7x, while the subsequent quantizations, at 1.4x, 2.1x, etc., are hidden in the larger volume plasmon loss peaks. Shirley and coworkers have been major contributors to the use of XPS to study plasmon losses [11][12][13][14]. Several examples of their results are found in Table 2.…”

Section: Experimental Observationsmentioning

confidence: 88%