Effect of Li 2 O–В 2 O 3 –SiO 2  glass on conductivity, microstructure, and stability of Li 2 ZrO 3  solid electrolyte

Anastasiya V. Kalashnova; Nailya S. Saetova; Konstantin V. Druzhinin

doi:10.15826/elmattech.2025.4.060

Effect of Li₂O–В₂O₃–SiO₂ glass on conductivity, microstructure, and stability of Li₂ZrO₃ solid electrolyte

Anastasiya V. Kalashnova, Nailya S. Saetova, Konstantin V. Druzhinin

Abstract

(100–x) Li₂ZrO₃–x 65Li₂O · 27B₂O₃ · 8SiO₂ (x = 1–8 wt. %) composites have been prepared. Relative density of the composites is shown to be higher than that of the sintered Li₂ZrO₃. According to the X-ray diffraction analysis, the formation of an impurity phase is observed at x of 8 wt. %, while other samples demonstrate peaks corresponding to monoclinic Li₂ZrO₃. Conductivity studies reveal that the application of the lithium borosilicate glass as sintering additives increases the total conductivity from ~ 10^–7 to ~ 10^–5 S · cm^–1. The Li | 94Li₂ZrO₃–6LBS|Li electrochemical cell has been tested for the stability against molten lithium at 250 °C for 336 h and superior stability of the composite has been proven. Based on the obtained results, the 94Li₂ZrO₃–6LBS composite can be recommended for application in lithium batteries.

Keywords

composites; solid electrolytes; glasses; lithium zirconates; ionic conductivity; impedance spectroscopy

Full Text:

PDF

References

Hellstrom EE, Van Gool W, Constraints for the selection of lithium solid electrolytes, Rev. Chim. Miner., 17 (1980) 263–282.

Dong Y, Zhao Y, Duan H, Huang J, Electrochemical performance and lithium-ion insertion/extraction mechanism studies on the novel Li2ZrO3 anode materials, Electrochimica Acta, 161 (2015) 219–225. https://doi.org/10.1016/j.electacta.2015.01.220

Miao X, Ni H, Zhang H, Wang C, et al., Li2ZrO3–coated 0.4Li2MnO3 · 0.6LiNi1/3Co1/3Mn1/3O2 for high performance cathode material in lithium-ion battery, J. Power Sources, 265 (2014) 147–154. https://doi.org/10.1016/j.jpowsour.2014.04.068

Yi H, Wang X, Ju B, Shu H, et al., Effective enhancement of electrochemical performance for spherical spinel LiMn2O4 via Li-ion conductive Li2ZrO3 coating, Electrochimica Acta, 134 (2014) 143–49. https://doi.org/10.1016/j.electacta.2014.04.148

Huang S, Wilson B, Wang Bo, Fang Y, et al., Y-doped Li8ZrO6: A Li-ion battery cathode material with high capacity, J. Amer. Chem. Soc., 137(34) (2015) 10992–11003. https://doi.org/10.1021/jacs.5b04690

Huang S, Wilson B, Smyrl WH, Truhlar DG, et al., Transition-metal-doped M-Li8ZrO6 (M = Mn, Fe, Co, Ni, Cu, Ce) as high-specific-capacity Li-ion battery cathode materials: Synthesis, electrochemistry, and quantum mechanical characterization, Chem. mater., 28(3) (2016) 746–755. https://doi.org/10.1021/acs.chemmater.5b03554

Hellstrom EE, Van Gool W, Lithium-ion conduction in Li2ZrO3, Li4ZrO4 and LiScO2, Solid State Ionics, 2(1) (1981) 59–64. https://doi.org/10.1016/0167-2738(81)90021-7

Sree Rama Murthy A, Gnanasekaran T, Jayaraman V, Preparation and characterization of some lithium-ion conductors, Solid State Ionics, 303 (2017) 138–143. https://doi.org/10.1016/j.ssi.2017.03.006

Andreev OL, Pantyukhina MI, Antonov BD, Batalov NN, Synthesis and electrical properties of lithium metazirconate, Russ. J. Electrochem., 36 (2000) 1335–1337. https://doi.org/10.1023/A:1026672202194

Pantyukhina MI, Andreev OL, Antonov BD, Batalov NN, Synthesis and electrical properties of lithium zirconates, Russ. J. Inorg. Chem., 47 (2002) 1778–1781.

Kalashnova AV, Plaksin SV, Vovkotrub EG, Shekhtman GS, Electric conductivity of lithium metazirconate, Russian Journal of Electrochemistry, 54 (2018) 709–713. https://doi.org/10.1134/S1023193518090033

Zhan X, Cheng YT, Shirpour M. Nonstoichiometry and Li‐ion transport in lithium zirconate: the role of oxygen vacancies, Journal of the American Ceramic Society, 101(9) (2018) 4053–4065. https://doi.org/10.1111/jace.15583

Liao Y, Singh P, Park KS, Li W, et al., Li6Zr2O7 interstitial lithium-ion solid electrolyte, Electrochimica acta, 102 (2013) 446–450. https://doi.org/10.1016/j.electacta.2013.04.029

Wang D, Zhong G, Li Y, Gong Z, et al., Enhanced ionic conductivity of Li3.5Si0.5P0.5O4 with addition of lithium borate, Solid State Ionics, 283 (2015) 109–114. https://doi.org/10.1016/j.ssi.2015.10.009

Gundale SS, Deshpande AV, Ionic conductivity of Li3.4V0.6Si0.4O4 ceramic containing LiBO2 glass as solid electrolyte, Journal of The Electrochemical Society, 165(11) (2018) A2563. https://doi.org/10.1149/2.0521811jes

Gundale SS, Deshpande AV, Improvement of ionic conductivity in Li3.6Si0.6V0.4O4 ceramic inorganic electrolyte by addition of LiBO2 glass for Li ion battery application, Electrochimica Acta, 265 (2018) 65–70. https://doi.org/10.1016/j.electacta.2018.01.122

Zhang L, Cheng L, Cabana J, Chen G, et al., Effect of lithium borate addition on the physical and electrochemical properties of the lithium ion conductor Li3.4Si0.4P0.6O4, Solid State Ionics, 231 (2013) 109–115. https://doi.org/10.1016/j.ssi.2012.09.002

Pershina SV, Il’ina EA, Reznitskikh OG, Phase composition, density, and ionic conductivity of the Li7La3Zr2O12-based composites with LiPO3 glass addition, Inorganic Chemistry, 56(16) (2017) 9880–9891. https://doi.org/10.1021/acs.inorgchem.7b01379

Il’ina EA, Raskovalov AA, Antonov BD, Pankratov AA, et al., Composite electrolytes ceramic Li7La3Zr2O12/glassy Li2O–Y2O3–SiO2, Materials Research Bulletin, 93 (2017) 157–161. https://doi.org/10.1016/j.materresbull.2017.04.050

Il'ina EA, Raskovalov AA, Saetova NS, Antonov BD, et al., Composite electrolytes Li7La3Zr2O12–glassy Li2O–B2O3–SiO2, Solid State Ionics, 296 (2016) 26–30. https://doi.org/10.1016/j.ssi.2016.09.003

Sherstobitova EA, Gubkin AF, Bobrikov AF, Kalashnova AV, et al., Bottle-necked ionic transport in Li2ZrO3: high temperature neutron diffraction and impedance spectroscopy, Electrochim. Acta, 209 (2016) 574–581. https://doi.org/10.1016/j.electacta.2016.05.113

Saetova NS, Raskovalov AA, Antonov BD, Yaroslavtseva TV, et al., The influence of lithium oxide concentration on the transport properties of glasses in the Li2O–B2O3–SiO2 system, Journal of Non-Crystalline Solids, 443 (2016) 75–81. https://doi.org/10.1016/j.jnoncrysol.2016.04.025

Il’ina EA, Druzhinin KV, Antonov BD, Stability of composite electrolytes based on Li7La3Zr2O12 to metallic lithium, Ionics, 26 (2020) 163–172. https://doi.org/10.1007/s11581-019-03177-0

Hodeau JL, Marezio M, Santoro A, Roth RS, et al., Neutron profile refinement of the structures of Li2SnO3 and Li2ZrO3, J. Solid State Chem., 45(2) (1982) 170–179. https://doi.org/10.1016/0022-4596(82)90273-0

Lin YY, Qu J, Gustafson WJ, Kung PC, et al., Coordination flexibility as a high-throughput descriptor for identifying solid electrolytes with Li+ sublattice disorder: A computational and experimental study, Journal of Power Sources, 553 (2023) 232251. https://doi.org/10.1016/j.jpowsour.2022.232251

DOI: https://doi.org/10.15826/elmattech.2025.4.060

Copyright (c) 2025 Anastasiya V. Kalashnova, Nailya S. Saetova, Konstantin V. Druzhinin

This work is licensed under a Creative Commons Attribution 4.0 International License.

Username
Password
Remember me