abstract
The commercially ubiquitous liquid electrolytes for lithium-ion batteries have several shortcomings in terms of safety. Therefore, development of solid electrolytes, especially those that are glass-based, has been gaining increasing interest in recent times. However, the fundamental understanding of the changes in the glass structure and the corresponding changes in the properties due to the addition of dopants is necessary for the development of glasses. Therefore, here, we report a study on the role of vanadium on the glass structure, ionic conduction, crystallization behavior, and other properties of lithium silicate-based glasses (23Li(2)O-2.64K(2)O-2.64Al(2)O(3)-71.72SiO(2)) as a solid electrolyte for high-temperature Li-ion battery applications. Furthermore, we proposed a mathematical model to describe/quantify the ion-conducting channels' connectivity in glasses. The experimental glass structures were assessed using Si-29, V-51, Al-27 nuclear magnetic resonance, Fourier transform infrared, and ultraviolet-visible spectroscopy techniques. The ionic conductivity was measured by impedance spectroscopy, and the crystallization behavior was studied by optical microscopy and X-ray diffraction. Furthermore, molecular dynamics simulations were also used to gain structural insights of the glasses. In the designed compositions, the addition of vanadium decreased the overall concentration of Li+ ions. However, the results revealed that the ionic conductivity improved with the addition of vanadium in spite of a decrease in the number of charge carriers. This suggests that vanadium makes the pathways easier for the conducting ions. Thus, we conclude that vanadium modifies the conduction channels to promote better hoping of the ions from one site to another.
keywords
ANISOTROPIC SHIELDING TENSORS; MAS NMR; RELATIVE ORIENTATION; CRYSTALLIZATION; AL; SPECTROSCOPY; SPECTRA; STATES; XPS; COORDINATION
subject category
Chemistry, Physical; Nanoscience & Nanotechnology; Materials Science, Multidisciplinary
authors
Gaddam, A; Allu, AR; Ganisetti, S; Fernandes, HR; Stan, GE; Negrila, CC; Jamale, AP; Mear, F; Montagne, L; Ferreira, JMF
our authors
Groups
G1 - Porous Materials and Nanosystems
G3 - Electrochemical Materials, Interfaces and Coatings
G5 - Biomimetic, Biological and Living Materials
Projects
CICECO - Aveiro Institute of Materials (UIDB/50011/2020)
acknowledgements
This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 and UIDP/50011/2020, financed by national funds through the FCT/MEC and when appropriate cofinanced by FEDER under the PT2020 Partnership Agreement. A.G. is grateful for the financial support from CICECO. A.P.J. is thankful for the support provided by national funds (OE), through FCT, IP, in the scope of the framework contract foreseen in the numbers 4, 5, and 6 of the article 23 of the Decree-Law 57/2016, of August 29, changed by Law 57/2017, of July 19. The NMR spectrometers from CICECO are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project No 022161 (cofinanced by FEDER through COMPETE 2020, and POCI, PORL, and FCT through PIDDAC). A.G. is thankful to Chevreul Institute (FR 2638) for providing access to the NMR measurements. Chevreul Institute (FR 2638), Ministe`re de l'Enseignement Superieur, de la Recherche et de l'Innovation, Hauts-de-France Region, and FEDER are acknowledged for supporting and partially funding this work. G.E.S. and C.C.N. acknowledge the support of PN-III-P1-1.1-TE-2019-0463 and PED-PN-III-P2-2.1-PED2019-4519 grants and Institutional Core Program 21 N. H.R.F. is grateful for the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 and UIDP/50011/2020, financed by national funds through the FCT/MEC and when appropriate cofinanced by FEDER under the PT2020 Partnership Agreement. Part of the work was developed under the frame of the project funded by DST-SERB (ECR/2 018/000292). A.R.A. acknowledges the financial support by DST-SERB (ECR/2 018/000292). S.G. would like to thank Dr. Julien Guenole and Dr. Yedukondalu Neelam for their support and encouragement.