The thermal stability of the cathode and anode materials for Li-ion and Na-ion batteriesLiNi1/3Mn1/3Co1/3O2, LiFePO4, Li4Ti5O12, graphite, O3-NaNi1/3Fe1/3Mn1/3O2 (NFM), Na3V2(PO4)3 (NVP), β-NaVP2O7 (NVPO), Na3V2(PO4)2F3 (NVPF), and hard carbonwas studied by means of differential scanning calorimetry of the electrodes in the charged state and ex situ powder X-ray diffraction. The obtained results indicate that the thermal stability of the Na-ion cathode materials increases in the order NFM < NVPF < NVP < NVPO. The “heat on energy” term has been proposed and analyzed for all of the studied materials.

The electrical conductivity of La0.5−xSr0.5FeO3−δ, investigated as a function of the nominal cation deficiency in the A-sublattice, x, varying from 0 to 0.02, has demonstrated a nonlinear dependence. An increase in the x value from 0 to 0.01 resulted in a considerable increase in electrical conductivity, which was shown to be attributed mainly to an increase in the mobility of the charge carriers. A combined analysis of the defect equilibrium and the charge transport in La0.5−xSr0.5FeO3−δ revealed the increase in the mobility of oxygen ions, electrons, and holes by factors of ~1.5, 1.3, and 1.7, respectively. The observed effect is assumed to be conditioned by a variation in the oxide structure under the action of the cationic vacancy formation. It was found that the cation deficiency limit in La0.5−xSr0.5FeO3−δ did not exceed 0.01. A small overstep of this limit was shown to result in the formation of (Sr,La)Fe12O19 impurity, which even in undetectable amounts reduced the conductivity of the material. The presence of (Sr,La)Fe12O19 impurity was revealed by X-ray diffraction on the ceramic surface after heat treatment at 1300 °C. It is most likely that the formation of traces of the liquid phase under these conditions is responsible for the impurity migration to the ceramic surface. The introduction of a cation deficiency of 0.01 into the A-sublattice of La0.5−xSr0.5FeO3−δ can be recommended as an effective means to enhance both the oxygen ion and the electron conductivity and improve ceramic sinterability.

Ti2Nb2O9 with a tunnel-type structure is considered as a perspective negative electrode material for Li-ion batteries (LIBs) with theoretical capacity of 252 mAh g–1 corresponding to one-electron reduction/oxidation of Ti and Nb, but only ≈160 mAh g–1 has been observed practically. In this work, highly reversible capacity of 200 mAh g–1 with the average (de)­lithiation potential of 1.5 V vs Li/Li+ is achieved for Ti2Nb2O9 with pseudo-2D layered morphology obtained via thermal decomposition of the NH4TiNbO5 intermediate prepared by K+→ H+→ NH4 + cation exchange from KTiNbO5. Using operando synchrotron powder X-ray diffraction (SXPD), single-phase (de)­lithiation mechanism with 4.8% unit cell volume change is observed. Operando X-ray absorption near-edge structure (XANES) experiment revealed simultaneous Ti4+/Ti3+ and Nb5+/Nb4+ reduction/oxidation within the whole voltage range. Li+ migration barriers for Ti2Nb2O9 along [010] direction derived from density functional theory (DFT) calculations are within the 0.15–0.4 eV range depending on the Li content that is reflected in excellent C-rate capacity retention. Ti2Nb2O9 synthesized via the ion-exchange route appears as a strong contender to widely commercialized Ti-based negative electrode material Li4Ti5O12 in the next generation of high-performance LIBs.

The thermal stability of NASICON-type cathode materials for sodium-ion batteries was studied using differential scanning calorimetry (DSC) and in situ high-temperature powder X-ray diffraction (HTPXRD) applied to the electrodes in a pristine or charged state. Na3V2(PO4)3 and Na4VMn(PO4)3 were analyzed for their peak temperatures and the exothermic effect values of their decomposition processes, as well as the phase transformations that took place upon heating. The obtained results indicate that Mn-substituted cathode material demonstrates much poorer thermal stability in the charged state, although pristine samples of both materials exhibit similar thermal behavior without any DSC peaks or temperature-induced phase transitions in the studied temperature range. The in situ HTPXRD revealed the amorphization of desodiated Na4VMn(PO4)3-based electrodes occurring at 150~250 °C.

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