DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Isotopic Signatures of Lithium Carbonate and Lithium Hydroxide Monohydrate Measured Using Raman Spectroscopy

Journal Article · · Applied Spectroscopy

Lithium isotopic ratios have wide ranging applications as chemical signatures, including improved understanding of geochemical processes and battery development. Measurement of isotope ratios using optical spectroscopies would provide an alternative to traditional mass spectrometric methods, which are expensive and often limited to a chemical laboratory. In this work, Raman spectra of 7Li2CO3, 6Li2CO3, 7LiOH*H2O and 6LiOH*H2O have been measured to determine the effect of lithium isotope substitution on the Raman molecular vibrations. Thirteen peaks were observed in the spectrum of lithium carbonate, with discernable isotopic shifts occurring in eleven of the thirteen vibrations, two of which have not been previously reported in the literature. The spectrum of lithium hydroxide monohydrate contained nine peaks, with discernable isotopic shifts occurring in eight of the nine vibrations, four of which have not been previously reported in the literature. The Raman spectral data reported here for lithium carbonate and lithium hydroxide monohydrate are in agreement with the previously reported works in the literature, in which the Raman active modes of these molecules were first identified and assigned. However, due to the stability and resolution of the detection system used in this work, isotopic shifts with a magnitude less than one wavenumber have been identified. Principal Component Regression was used to evaluate the sensitivity to isotopic content of small Raman peak shifts in Li2CO3 and indicates differences greater than 2 atom-% could be reliably determined. These measurements add to the body of work on lithium isotope Raman spectroscopy for these two compounds and increases the number of Raman bands which could be used for lithium isotope content analysis.

Research Organization:
Savannah River National Lab (SRNL), Aiken, SC (United States); Savannah River Site (SRS), Aiken, SC (United States)
Sponsoring Organization:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Environmental Management (EM)
Grant/Contract Number:
89303321CEM000080
OSTI ID:
1898098
Report Number(s):
SRNL-STI--2021-00667
Journal Information:
Applied Spectroscopy, Journal Name: Applied Spectroscopy Journal Issue: 2 Vol. 77; ISSN 0003-7028
Publisher:
Society for Applied SpectroscopyCopyright Statement
Country of Publication:
United States
Language:
English

References (21)

Lithium hydroxide monohydrate single crystals: infrared reflectivity and Raman study journal January 2000
Raman spectroscopic study of four isotopically substituted lithium hydroxide monohydrates journal January 1981
The Raman active vibrational modes and isotopic effects of four isotopically substituted lithium hydroxides journal August 1979
Variation of lithium isotope composition in the marine environment: A preliminary report journal June 1988
Low frequency bands of Li2CO3 crystal journal January 1979
Raman and infrared studies of lithium and cesium carbonates journal July 1992
Multi-isotopic (Li, B, Sr, Nd) approach for geothermal reservoir characterization in the Limagne Basin (Massif Central, France) journal November 2007
Lithium isotope fractionation during incongruent melting: Constraints from post-collisional leucogranite and residual enclaves from Bengbu Uplift, China journal November 2016
Lithium and potassium isotope fractionation during silicate rock dissolution: An experimental approach journal May 2021
Lithium Isotope Effects upon Electrochemical Release from Lithium Manganese Oxide journal May 2015
Equilibrium lithium isotope fractionation in Li-bearing minerals journal August 2018
Unnatural Isotopic Composition of Lithium Reagents journal October 1997
Hyperfiltration-induced fractionation of lithium isotopes: Ramifications relating to representativeness of aquifer sampling journal February 1994
Raman and Infrared Spectral Studies of Anhydrous Li 2 CO 3 and Na 2 CO 3 journal June 1971
Raman spectra of lithium compounds journal November 2017
Raman scattering, defect luminescence, and phonon spectra of Li 7 H, Li 6 H, and Li 7 D crystals journal September 1983
Temperature Dependence of the Raman Spectrum in Lithium Oxide Single Crystal journal September 1991
Monitoring Uranium, Hydrogen, and Lithium and Their Isotopes Using a Compact Laser-Induced Breakdown Spectroscopy (LIBS) Probe and High-Resolution Spectrometer journal March 2012
Lithium Isotope Effect Accompanying Electrochemical Intercalation of Lithium into Graphite journal June 2003
Predicting olivine composition using Raman spectroscopy through band shift and multivariate analyses journal November 2018
Observation of Lithium Isotope Effects Accompanying Electrochemical Release from Lithium Cobalt Oxide journal February 2013