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1. Lithium Antiperovskite-Derived Glass Solid Electrolytes

   https://doi.org/10.1021/acsmaterialslett.4c02578  

   Milan, Emily; Rees, Gregory_J; Phillips, Aaron; Cano, Cristian; Wei, Yi; Guo, Hua; Feller, Steve; Pasta, Mauro (February 2025, ACS Materials Letters)
2. Evaluating the Potential of Rhyolitic Glass as a Lithium Source for Brine Deposits

   https://doi.org/10.5382/econgeo.4866  

   Ellis, B. S.; Szymanowski, D.; Harris, C.; Tollan, P.M.E.; Neukampf, J.; Guillong, M.; Cortes-Calderon, E. A.; Bachmann, O. (January 2022, Economic Geology)

   Abstract Lithium is an economically important element that is increasingly extracted from brines accumulated in continental basins. While a number of studies have identified silicic magmatic rocks as the ultimate source of dissolved brine lithium, the processes by which Li is mobilized remain poorly constrained. Here we focus on the potential of low-temperature, post-eruptive processes to remove Li from volcanic glass and generate Li-rich fluids. The rhyolitic glasses in this study (from the Yellowstone-Snake River Plain volcanic province in western North America) have interacted with meteoric water emplacement as revealed by textures and a variety of geochemical and isotopic signatures. Indices of glass hydration correlate with Li concentrations, suggesting Li is lost to the water during the water-rock interaction. We estimate the original Li content upon deposition and the magnitude of Li depletion both by direct in situ glass measurements and by applying a partition-coefficient approach to plagioclase Li contents. Across our whole sample set (19 eruptive units spanning ca. 10 m.y.), Li losses average 8.9 ppm, with a maximum loss of 37.5 ppm. This allows estimation of the dense rock equivalent of silicic volcanic lithologies required to potentially source a brine deposit. Our data indicate that surficial processes occurring post-eruption may provide sufficient Li to form economic deposits. We found no relationship between deposit age and Li loss, i.e., hydration does not appear to be an ongoing process. Rather, it occurs primarily while the deposit is cooling shortly after eruption, with δ18O and δD in our case study suggesting a temperature window of 40° to 70°C. 

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3. Liquid fragility maximum in lithium borate glass‐forming melts related to the local structure

   https://doi.org/10.1111/ijag.16611  

   Alderman, Oliver L. G.; Benmore, Chris J.; Reynolds, Bryce; Royle, Brock; Feller, Steve; Weber, Rick J. K. (September 2022, International Journal of Applied Glass Science)

   Abstract The structure of liquid lithium pyroborate, Li₄B₂O₅(J= Li/B = 2), has been measured over a wide temperature range by high‐energy X‐ray diffraction, and compared to that of its glass and borate liquids of other compositions. The results indicate a gradual increase in tetrahedral boron fraction from 3(1)% to 6(1)% during cooling fromT= 1271(15) to 721(8) K, consistent with the largerN₄ = 10(1)% found for the glass, and literature¹¹B nuclear magnetic resonance measurements. van't Hoff analysis based on a simple boron isomerization reaction BØ₃O^2–⇌ BØO₂^2–yields ΔH= 13(1) kJ mol^–1and ΔS= 40(1) J mol^–1 K^–1for the boron coordination change from 4 to 3, which are, respectively, smaller and larger than found for singly charged isomers forJ ≤ 1. With these, we extend our model forN₄(J,T), nonbridging oxygen fractionf_nbr(J,T), configurational heat capacity , and entropyS^conf(J,T) contributions up toJ= 3. A maximum is revealed in atJ= 1, and shown semi‐quantitatively to lead to a corresponding maximum in fragility contribution, akin to that observed in the total fragilities by temperature‐modulated differential scanning calorimetry. Lithium is bound to 4.6(2) oxygen in the pyroborate liquid, with 2.7(1) bonds centered around 1.946(8) Å and 1.9(1) around 2.42(1) Å. In the glass,n_LiO= 5.4(4), the increase being due to an increase in the number of short Li–O bonds. 

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4. Relationship between Ionic Conductivity, Glass Transition Temperature, and Dielectric Constant in Poly(vinyl ether) Lithium Electrolytes

   https://doi.org/10.1021/acsmacrolett.1c00305  

   Imbrogno, Jennifer; Maruyama, Kazuya; Rivers, Frederick; Baltzegar, Jacob R.; Zhang, Zidan; Meyer, Paul W.; Ganesan, Venkat; Aoshima, Sadahito; Lynd, Nathaniel A. (July 2021, ACS Macro Letters)

   null (Ed.)

   We report a partial elucidation of the relationship between polymer polarity and ionic conductivity in polymer electrolyte mixtures comprising a homologous series of nine poly(vinyl ether)s (PVEs) and lithium bis(trifluoromethylsulfonyl)imide. Recent simulation studies have suggested that low dielectric polymer hosts with glass transition temperatures far below ambient conditions are expected to have ionic conductivity limited by salt solubility and dissociation. In contrast, high dielectric hosts are expected to have the potential for high ion solubility but slow segmental dynamics due to strong polymer–polymer and polymer–ion interactions. We report results for PVEs in the low polarity regime with dielectric constants of about 1.3 to 9.0. Ionic conductivity measured for the PVE and salt mixtures ranged from about 10–10 to 10–3 S/cm. In agreement with the predictions from computer simulations, the ionic conductivity increased with dielectric constant and plateaued as the dielectric approached 9.0, comparable to the dielectric constant of the widely used poly(ethylene oxide). 

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5. The Relevance of Lithium Salt Solvate Crystals in Superconcentrated Electrolytes in Lithium Batteries

   https://doi.org/10.3390/en16093700  

   Klorman, Jake A.; Lau, Kah Chun (May 2023, Energies)

   Based on the unique ubiquity of similar solvate structures found in solvate crystals and superconcentrated electrolytes, we performed a systematic study of four reported solvate crystals which consist of different lithium salts (i.e., LiMPSA, LiTFSI, LiDFOB, and LiBOB) solvated by acetonitrile (MeCN) based on first principles calculations. Based on the calculations, these solvate crystals are predicted to be electronic insulators and are expected to be similar to their insulating liquid counterpart (e.g., 4 M superconcentrated LiTFSI-MeCN electrolyte), which has been confirmed to be a promising electrolyte in lithium batteries. Although the MeCN molecule is highly unstable during the reduction process, it is found that the salt-MeCN solvate molecules (e.g., LiTFSI-(MeCN)2, LiDFOB-(MeCN)2) and their charged counterparts (anions and cations) are both thermodynamically and electrochemically stable, which can be confirmed by Raman vibrational modes through the unique characteristic variation in C≡N bond stretching of MeCN molecules. Therefore, in addition to the development of new solvents or lithium salts, we suggest it is possible to utilize the formation of superconcentrated electrolytes with improved electrochemical stability based on existing known compounds to facilitate the development of novel electrolyte design in advanced lithium batteries. 

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