Magnetic properties and vanadium oxidation state in α-Li3V2(PO4)3/C composite: Magnetization and ESR measurements

Гаврилова, Т. П.; Khantimerov, S. M.; Fatykhov, Ranis; Yatsyk, I. V.; Черосов, М.А.; Lee, H.S.; Vishwanathan, R.; Kuppan, Saravanan; Suleimanov, N. M.

doi:10.1016/j.ssc.2020.114108

Cited by 10 publications

(10 citation statements)

References 19 publications

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“…The unit cell contains Z = 4 formula units. The obtained lattice parameters are very close to those that were previously reported and can slightly differ depending on the synthesis process and monoclinic axis selection [ 13 , 32 , 33 , 37 , 38 , 39 , 40 , 41 , 42 ]. The structure of LVPO consists of a three-dimensional framework of slightly distorted VO 6 octahedra and PO 4 tetrahedra.…”

Section: Resultssupporting

confidence: 87%

“…The LVPO crystal structure visualization is well represented in the literature, for example, as shown in Figure 1 of Ref. [ 32 ].…”

Section: Resultsmentioning

confidence: 99%

“…The second condition for ESR detection from the exited (S = 1) state in the conventional perpendicular state is that the energy of the microwave field should be sufficient for the transition between these sublevels. Based on a set of experimental data given in the literature [ 31 , 45 , 46 ] and our previous works [ 13 , 32 , 33 ], no signal is expected from trivalent vanadium in perpendicular mode for the above reasons, which may exist separately or together. The direct probe of V 3+ via the ESR test was presented in [ 31 ].…”

Section: Resultsmentioning

confidence: 99%

“…Considering that the magnetic ion V 3+ has a 3d 2 electronic configuration and a ground state 3 F with spin S = 1, we can estimate the effective magnetic moment μ eff as

where μ B is the Bohr magneton, g is the Lande g-factor, Z is the number of magnetic ions in a unit cell and S is the spin. Taking into account that g = 1.95 [ 32 ] for vanadium ions, we obtain a theoretical effective magnetic moment per mole of μ theor = 3.9 μ B . The theoretical and experimental values of the effective magnetic moment for the LVPO composite coincide within a 10% error margin.…”

Section: Resultsmentioning

confidence: 99%

“…Electron spin resonance (ESR) detects the qualitative and quantitative information of unpaired electrons contained in local atoms or molecules of matter and the structural characteristics of its surrounding environment. NMR is commonly used in the study of light elements such as Li, Na, O and F, while ESR is suitable for the evaluation of transition metals (Fe, Co, Mn, V) and oxygen vacancies and for the characterization of redox processes [ 13 , 31 , 32 , 33 ]. Owing to the ultrahigh sensitivity to magnetization, magnetometry can accurately monitor the magnetic changes caused by electron transfer during electrochemical processes, and it is a powerful tool for investigating conversion or alloy-type alkali metal ion batteries (AMIBs), spin-based devices [ 34 , 35 ] or solid electrolyte interphase characterization by operando magnetometry [ 36 ].…”

Section: Introductionmentioning

confidence: 99%

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Li3V2(PO4)3 Cathode Material: Synthesis Method, High Lithium Diffusion Coefficient and Magnetic Inhomogeneity

Gavrilova,

Deeva,

Uporova

et al. 2024

IJMS

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Li3V2(PO4)3 cathodes for Li-ion batteries (LIBs) were synthesized using a hydrothermal method with the subsequent annealing in an argon atmosphere to achieve optimal properties. The X-ray diffraction analysis confirmed the material’s single-phase nature, while the scanning electron microscopy revealed a granular structure, indicating a uniform particle size distribution, beneficial for electrochemical performance. Magnetometry and electron spin resonance studies were conducted to investigate the magnetic properties, confirming the presence of the relatively low concentration and highly uniform distribution of tetravalent vanadium ions (V4+), which indicated low lithium deficiency values in the original structure and a high degree of magnetic homogeneity in the sample, an essential factor for consistent electrochemical behavior. For this pure phase Li3V2(PO4)3 sample, devoid of any impurities such as carbon or salts, extensive electrochemical property testing was performed. These tests resulted in the experimental discovery of a remarkably high lithium diffusion coefficient D = 1.07 × 10−10 cm2/s, indicating excellent ionic conductivity, and demonstrated impressive stability of the material with sustained performance over 1000 charge–discharge cycles. Additionally, relithiated Li3V2(PO4)3 (after multiple electrochemical cycling) samples were investigated using scanning electron microscopy, magnetometry and electron spin resonance methods to determine the extent of degradation. The combination of high lithium diffusion coefficients, a low degradation rate and remarkable cycling stability positions this Li3V2(PO4)3 material as a promising candidate for advanced energy storage applications.

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Section: Resultssupporting

confidence: 87%

“…The LVPO crystal structure visualization is well represented in the literature, for example, as shown in Figure 1 of Ref. [ 32 ].…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…Considering that the magnetic ion V 3+ has a 3d 2 electronic configuration and a ground state 3 F with spin S = 1, we can estimate the effective magnetic moment μ eff as

Section: Resultsmentioning

confidence: 99%