Presence of Li clusters in molten LiCl-Li
Abstract
Molten mixtures of lithium chloride and metallic lithium are of significant interest in various metal oxide reduction processes. These solutions have been reported to exhibit seemingly anomalous physical characteristics that lack a comprehensive explanation. ln the current work, the physical chemistry of molten solutions of lithium chloride and metallic lithium, with and without lithium oxide, was investigated using in situ Raman spectroscopy. The Raman spectra obtained from these solutions were in agreement with the previously reported spectrum of the lithium cluster, Li8. Furthermore, this observation is indicative of a nanofluid type colloidal suspension of Li8, in a molten salt matrix. It is suggested that the formation and suspension of lithium clusters in lithium chloride is the cause of various phenomena exhibited by these solutions that were previously unexplainable.
- Authors:
-
- Univ. of Nevada, Reno, NV (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- U.S. Nuclear Regulatory Commission (NRC); USDOE Office of Nuclear Energy (NE)
- OSTI Identifier:
- 1307568
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Scientific Reports
- Additional Journal Information:
- Journal Volume: 6; Journal ID: ISSN 2045-2322
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Merwin, Augustus, Phillips, William C., Williamson, Mark A., Willit, James L., Motsegood, Perry N., and Chidambaram, Dev. Presence of Li clusters in molten LiCl-Li. United States: N. p., 2016.
Web. doi:10.1038/srep25435.
Merwin, Augustus, Phillips, William C., Williamson, Mark A., Willit, James L., Motsegood, Perry N., & Chidambaram, Dev. Presence of Li clusters in molten LiCl-Li. United States. https://doi.org/10.1038/srep25435
Merwin, Augustus, Phillips, William C., Williamson, Mark A., Willit, James L., Motsegood, Perry N., and Chidambaram, Dev. Thu .
"Presence of Li clusters in molten LiCl-Li". United States. https://doi.org/10.1038/srep25435. https://www.osti.gov/servlets/purl/1307568.
@article{osti_1307568,
title = {Presence of Li clusters in molten LiCl-Li},
author = {Merwin, Augustus and Phillips, William C. and Williamson, Mark A. and Willit, James L. and Motsegood, Perry N. and Chidambaram, Dev},
abstractNote = {Molten mixtures of lithium chloride and metallic lithium are of significant interest in various metal oxide reduction processes. These solutions have been reported to exhibit seemingly anomalous physical characteristics that lack a comprehensive explanation. ln the current work, the physical chemistry of molten solutions of lithium chloride and metallic lithium, with and without lithium oxide, was investigated using in situ Raman spectroscopy. The Raman spectra obtained from these solutions were in agreement with the previously reported spectrum of the lithium cluster, Li8. Furthermore, this observation is indicative of a nanofluid type colloidal suspension of Li8, in a molten salt matrix. It is suggested that the formation and suspension of lithium clusters in lithium chloride is the cause of various phenomena exhibited by these solutions that were previously unexplainable.},
doi = {10.1038/srep25435},
journal = {Scientific Reports},
number = ,
volume = 6,
place = {United States},
year = {Thu May 05 00:00:00 EDT 2016},
month = {Thu May 05 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
Electrical Conductivities of Molten Bi–BiI 3 Solutions
journal, April 1963
- Grantham, L. F.; Yosim, S. J.
- The Journal of Chemical Physics, Vol. 38, Issue 7
Measurements of lithium cluster ionization potentials
journal, September 1992
- Dugourd, Ph.; Rayane, D.; Labastie, P.
- Chemical Physics Letters, Vol. 197, Issue 4-5
Electrochemical reduction of porous 17kg uranium oxide pellets by selection of an optimal cathode/anode surface area ratio
journal, November 2011
- Choi, Eun-Young; Hur, Jin-Mok; Choi, In-Kyu
- Journal of Nuclear Materials, Vol. 418, Issue 1-3
The physics of simple metal clusters: experimental aspects and simple models
journal, July 1993
- de Heer, Walt A.
- Reviews of Modern Physics, Vol. 65, Issue 3
The Dissolution of Lithium in Molten Lithium Chloride
journal, January 1974
- Watanabe, Nobuatsu; Nakanishi, Koichiro; Nakajima, Tsuyoshi
- NIPPON KAGAKU KAISHI, Issue 3
Thermal activated (“thermal”) battery technology
journal, March 2008
- Masset, Patrick J.; Guidotti, Ronald A.
- Journal of Power Sources, Vol. 178, Issue 1
Fluorodilithium(1+) and hydroxodilithium(1+) in molten alkali-metal nitrate
journal, September 1990
- Bengtsson, L.; Holmberg, Bertil; Ulvenlund, S.
- Inorganic Chemistry, Vol. 29, Issue 18
Silicon powder production by electrochemical reduction of SiO2 in molten LiCl–Li2O
journal, September 2008
- Lee, Su-Chul; Hur, Jin-Mok; Seo, Chung-Seok
- Journal of Industrial and Engineering Chemistry, Vol. 14, Issue 5
Miscibility of Lithium with Lithium Chloride and Lithium Chloride–Potassium Chloride Eutectic Mixture
journal, August 1974
- Nakajima, Tsuyoshi; Minami, Ryohei; Nakanishi, Koichiro
- Bulletin of the Chemical Society of Japan, Vol. 47, Issue 8
Equilibrium geometries of low-lying isomers of some Li clusters, within Hartree–Fock theory plus bond order or MP2 correlation corrections
journal, June 2004
- Grassi, A.; Lombardo, G. M.; Angilella, G. G. N.
- The Journal of Chemical Physics, Vol. 120, Issue 24
Vacuum ultraviolet absorption and ion track effects in LiF crystals irradiated with swift ions
journal, December 2002
- Davidson, A. T.; Schwartz, K.; Comins, J. D.
- Physical Review B, Vol. 66, Issue 21
Effect of aging on microstructure and mechanical properties of cobalt free 18%Ni (250 grade) maraging steel
journal, January 1998
- Sinha, P. P.; Tharian, K. T.; Sreekumar, K.
- Materials Science and Technology, Vol. 14, Issue 1
Thermal activated (thermal) battery technology
journal, January 2007
- Masset, Patrick; Guidotti, Ronald A.
- Journal of Power Sources, Vol. 164, Issue 1
Ab initio GW quasiparticle calculation of small alkali-metal clusters
journal, May 2002
- Ishii, Soh; Ohno, Kaoru; Kawazoe, Yoshiyuki
- Physical Review B, Vol. 65, Issue 24
Absolute Determination of the Wavelengths of the Sodium D 1 and D 2 Lines by Using a CW Tunable Dye Laser Stabilized on Iodine
journal, July 1981
- Juncar, P.; Pinard, J.; Hamon, J.
- Metrologia, Vol. 17, Issue 3
Nanocluster Formation in Electron-Irradiated L i 2 O Crystals Observed by Elastic Diffuse Neutron Scattering
journal, September 2003
- Krexner, G.; Prem, M.; Beuneu, F.
- Physical Review Letters, Vol. 91, Issue 13
The Electrical Conductivity of Solutions of Alkali Metals in their Molten Halides 1
journal, May 1958
- Bronstein, H. R.; Bredig, M. A.
- Journal of the American Chemical Society, Vol. 80, Issue 9
Influence of Some Factors upon Electrodeposition of Liquid Li and Mg
conference, January 2009
- Takenaka, Toshihide; Shigeta, Kouji; Masuhama, Hiroshi
- 214th ECS Meeting, ECS Transactions
[融解塩系におけるエマルジョンに関する研究 II 種々の融解塩への金属リチウムの分散]
journal, January 1975
- Nakajima, Tsuyoshi; Nakanishi, Koichiro; Watanabe, Nobuatsu
- NIPPON KAGAKU KAISHI, Issue 4
Ionization energies of hypervalent Li2F, Li2Cl and Na2Cl molecules obtained by surface ionization electron impact neutralization mass spectrometry
journal, January 2003
- Ne?kovi?, Olivera M.; Veljkovi?, Miomir V.; Veli?kovi?, Suzana R.
- Rapid Communications in Mass Spectrometry, Vol. 17, Issue 3
Electronic conductivity of salt-rich Li?LiCl melts
journal, November 1992
- Liu, J.; Poignet, J. -C.
- Journal of Applied Electrochemistry, Vol. 22, Issue 11
Study of Emulsions in Molten Salts. III. The Concentration, Stability and Particle-Size Distribution of Dispersed Lithium in Molten Lithium Chloride
journal, April 1976
- Nakajima, Tsuyoshi; Nakanishi, Koichiro; Watanabe, Nobuatsu
- Bulletin of the Chemical Society of Japan, Vol. 49, Issue 4
Recombination gamma-luminescence at the nanometal Li – dielectric LiF interfaces
journal, June 2015
- Ibragimova, E. M.; Mussaeva, M. A.; Buzrikov, Sh. N.
- Radiation Physics and Chemistry, Vol. 111
An experimental study for Li recycling in an electrolytic reduction process for UO2 with a Li2O–LiCl molten salt
journal, October 2013
- Park, Wooshin; Hur, Jin-Mok; Hong, Sun-Seok
- Journal of Nuclear Materials, Vol. 441, Issue 1-3
Determination of the Vapor Pressure of Sodium
journal, January 1955
- Makansi, M. M.; Muendel, C. H.; Selke, W. A.
- The Journal of Physical Chemistry, Vol. 59, Issue 1
Systematic ab initio configuration-interaction study of alkali-metal clusters: Relation between electronic structure and geometry of small Li clusters
journal, June 1987
- Boustani, I.; Pewestorf, W.; Fantucci, P.
- Physical Review B, Vol. 35, Issue 18
Raman spectroscopic investigation of small matrix-isolated lithium clusters
journal, April 2003
- Kornath, Andreas; Kaufmann, Alexander; Zoermer, Anja
- The Journal of Chemical Physics, Vol. 118, Issue 15
Thermal activated (“thermal”) battery technology
journal, March 2008
- Masset, Patrick J.; Guidotti, Ronald A.
- Journal of Power Sources, Vol. 177, Issue 2
Raman Measurements of Matrix-Isolated Small Metal Clusters
journal, March 1984
- Froben, F. W.; Schulze, W.
- Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 88, Issue 3
Ionization energies of LinX (n = 2, 3; X = Cl, Br, I) molecules
journal, January 2006
- Veličković, Suzana; Djordjević, Vesna; Cvetićanin, Jelena
- Rapid Communications in Mass Spectrometry, Vol. 20, Issue 20
Influence of Some Factors upon Electrodeposition of Liquid Li and Mg
journal, August 2008
- Takenaka, Toshihide; Shigeta, Kouji; Masuhama, Hiroshi
- ECS Meeting Abstracts, Vol. MA2008-02, Issue 49, p. 3058-3058
Electronic structure of metal-molten salt solutions: Electron localization and the metal-non-metal transition
journal, October 1996
- Beck, U.; Koslowski, Th.; Freyland, W.
- Journal of Non-Crystalline Solids, Vol. 205-207
Preparation of metallic niobium from niobium pentoxide by an indirect electrochemical reduction in a LiCl-Li2O molten salt
journal, March 2008
- Jeong, Sang Mun; Yoo, Hui Yong; Hur, Jin-Mok
- Journal of Alloys and Compounds, Vol. 452, Issue 1
Computational investigations of the liquid lithium/(LiCl-KCl eutectic melt) interface
journal, March 1998
- Hébant, Pascal; Picard, Gérard S.
- Journal of Molecular Structure: THEOCHEM, Vol. 426, Issue 1-3
Determination of the Vapor Pressure of Sodium
journal, January 1955
- Makansi, M. M.; Muendel, C. H.; Selke, W. A.
- The Journal of Physical Chemistry, Vol. 59, Issue 1
MISCIBILITY OF METALS WITH SALTS. VI. LITHIUM-LITHIUM HALIDE SYSTEMS 1
journal, March 1962
- Dworkin, A. S.; Bronstein, H. R.; Bredig, M. A.
- The Journal of Physical Chemistry, Vol. 66, Issue 3
Bulk and surface characteristics of metal-molten salt solutions
journal, February 1990
- Freyland, Werner
- Journal of Non-Crystalline Solids, Vol. 117-118
Formation and ionization energies of small chlorine-doped lithium clusters by thermal ionization mass spectrometry: TIMS study of small chlorine-doped lithium clusters
journal, January 2012
- Veličković, S. R.; Djustebek, J. B.; Veljković, F. M.
- Rapid Communications in Mass Spectrometry, Vol. 26, Issue 4
Electrochemical Reduction of TiO 2 in Molten LiCl–Li 2 O
journal, August 2007
- Hur, Jin-Mok; Lee, Su-Chul; Jeong, Sang-Mun
- Chemistry Letters, Vol. 36, Issue 8
Li colloids created by electron-irradiation of LiF: A great wealth of properties
journal, May 2002
- Beuneu, F.; Vajda, P.; Zogal, O. J.
- Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 191, Issue 1-4
Characteristics of an electrochemical reduction of Ta2O5 for the preparation of metallic tantalum in a LiCl–Li2O molten salt
journal, August 2007
- Jeong, Sang Mun; Jung, Jin-Young; Seo, Chung-Seok
- Journal of Alloys and Compounds, Vol. 440, Issue 1-2
Electrochemical reduction of UO2 in LiCl–Li2O molten salt using porous and nonporous anode shrouds
journal, January 2014
- Choi, Eun-Young; Won, Chan Yeon; Cha, Ju-Sun
- Journal of Nuclear Materials, Vol. 444, Issue 1-3
Assembly of metals and nanoparticles into novel nanocomposite superstructures
journal, April 2013
- Xu, Jiaquan; Chen, Lianyi; Choi, Hongseok
- Scientific Reports, Vol. 3, Issue 1
Electrolytic Reduction and Electrorefining of Uranium to Develop Pyrochemical Reprocessing of Oxide Fuels
journal, September 2010
- Sakamura, Yoshiharu; Omori, Takashi
- Nuclear Technology, Vol. 171, Issue 3
Vibrational frequencies and intensities of small molecules: All-electron, pseudopotential, and mixed-potential methodologies
journal, July 1998
- Briley, Arlin; Pederson, Mark R.; Jackson, Koblar A.
- Physical Review B, Vol. 58, Issue 4
Electrochemical investigations of the liquid lithium/(LiCl–KCl eutectic melt) interface. Chronopotentiometric and electrochemical impedance spectroscopy measurements
journal, May 1998
- Hébant, Pascal; Picard, Gérard S.
- Electrochimica Acta, Vol. 43, Issue 14-15
Influence of Some Factors upon Electrodeposition of Liquid Li and Mg
conference, January 2009
- Takenaka, Toshihide; Shigeta, Kouji; Masuhama, Hiroshi
- 214th ECS Meeting, ECS Transactions
Electrochemical reduction behavior of a highly porous SIMFUEL particle in a LiCl molten salt
journal, October 2012
- Choi, Eun-Young; Lee, Jae Won; Park, Jang Jin
- Chemical Engineering Journal, Vol. 207-208
Cathodic Phenomena in Li Electrolysis in LiCl-KCl Melt
book, May 2014
- Takenaka, T.; Morishige, T.; Umehara, M.
- Molten Salts Chemistry and Technology
Measurement of the activity of lithium in dilute solutions in molten lithium chloride between 650�C and 800�C
journal, September 1990
- Liu, J.; Poignet, J. -C.
- Journal of Applied Electrochemistry, Vol. 20, Issue 5
Electronic Properties of Metal/Molten Salt Solutions
book, January 2002
- Warren, William W.
- Molten Salts: From Fundamentals to Applications
Works referencing / citing this record:
Effect of Metallic Li on the Surface Chemistry of Inconel 625 Exposed to Molten LiCl-Li 2 O-Li
journal, January 2019
- Phillips, William; Chidambaram, Dev
- Journal of The Electrochemical Society, Vol. 166, Issue 11
Minimising oxygen contamination through a liquid copper-aided group IV metal production process
journal, November 2018
- Yoo, Bung Uk; Lee, Young Jun; Ri, Vladislav
- Scientific Reports, Vol. 8, Issue 1
Effect of Metallic Li on the Corrosion Behavior of Inconel 625 in Molten LiCl-Li 2 O-Li
journal, January 2019
- Phillips, William; Karmiol, Zachary; Chidambaram, Dev
- Journal of The Electrochemical Society, Vol. 166, Issue 6