Structural and dynamic behavior of lithium iron polysulfide Li₈FeS₅ during charge–discharge cycling

Lithium sulfide (Li₂S) is one of the promising positive electrode materials for next-generation rechargeable lithium batteries. To improve the electrochemical performance of electronically resistive Li₂S, a Fe-doped Li₂S-based positive electrode material (Li₈FeS₅) has been recently designed and found to exhibit excellent discharge capacity close to 800 mAh g⁻¹. In the present study, we investigate the structural and dynamic behavior of Li₈FeS₅ during charge–discharge cycling. In Li₈FeS₅, Fe ions are incorporated into the Li₂S framework structure. The Li₂S-based structure is found to transform to an amorphous phase during the charge process. The delithiation-induced amorphization is associated with the formation of S-S polysulfide bonds, indicating charge compensation by S ions. The crystalline to non-crystalline structural transformation is reversible, but Li ions are extracted from the material via a two-phase reaction, although they are inserted via a single-phase process. These results indicate that the delithiation/lithiation mechanism is neither a topotactic extraction/insertion nor a conversion-type reaction. Moreover, the activation energies for Li ion diffusion in the pristine, delithiated, and lithiated materials are estimated to be in the 0.30–0.37 eV range, which corresponds to the energy barriers for local hopping of Li ions along the Li sublattice in the Li₂S framework

Microscopic characterization of the C–F bonds in fluorine–graphite intercalation compounds

The structures of fluorine–graphite intercalation compounds (F-GICs, C₂.₈F and C₃.₅F) have been analyzed by high-resolution transmission electron microscopy (TEM). Cross-sectional TEM images of the F-GICs indicate that the interlayer distance increases by insertion of fluorine with randomly buckled carbon layers. Such a structure can form by alternation in the bond angle at a carbon atom covalently bonded with fluorine. Electron energy loss spectroscopy combined with TEM indicates that the π-orbital network over the graphitic carbon layer reduces with fluorination. The C–F bond is essentially covalent

Carbon Nanotube/Nanofibers and Graphite Hybrids for Li-Ion Battery Application

To improve the electrical conductivity of negative electrodes of lithium ion batteries, we applied a direct CVD synthesis of carbon nanomaterials on the surface of graphite particles. To prepare a catalyst, two alternative approaches were utilized: colloidal nanoparticles (NPs) and metal (Ni and Co) nitrate salt precursors deposited on the graphite surface. Both colloidal and precursor systems allowed us to produce carbon nanofibers (CNFs) on the graphite surface with high coverage under the optimum CVD conditions. Electrical measurements revealed that the resistivity of the actual electrodes fabricated from CNFs coated graphite particles was about 40% lower compared to the original pristine graphite electrodes.Peer reviewe

Oxidation behaviour of lattice oxygen in Li-rich manganese-based layered oxide studied by hard X-ray photoelectron spectroscopy

The oxidation/reduction behaviours of lattice oxygen and transition metals in a Li-rich manganese-based layered oxide Li[Li0.25Ni0.20Mn0.55]O1.93 are investigated by using hard X-ray photoelectron spectroscopy (HAX-PES). By making use of its deeper probing depth rather than in-house XPS analyses, we clearly confirm the formation of O- ions as bulk oxygen species in the active material. They are formed on the 1st charging process as a charge compensation mechanism for delithiation and decrease on discharging. In particular, the cation-anion dual charge compensation involving Ni and O ions is suggested during the voltage slope region of the charging process. The Ni ions in the material are considered to increase the capacity delivered by a reversible anion redox reaction with the suppression of O2 gas release. On the other hand, we found structural deterioration in the cycled material. The O- species are still observed but are electrochemically inactive during the 5th charge-discharge cycle. Also, the oxidation state of Ni ions is divalent and inactive, although that of Mn ions changes reversibly. We believe that this is associated with the structural rearrangement occurring after the activation process during the 1st charging, leading to the formation of spinel- or rocksalt-like domains over the sub-surface region of the particles

Direct observation of reversible oxygen anion redox reaction in Li-rich manganese oxide, Li2MnO3, studied by soft X-ray absorption spectroscopy

Li-rich layered oxides have attracted attention as promising positive electrode materials for next-generation lithium-ion secondary batteries because of their high energy storage capacity. The participation of the oxygen anion has been hypothesized to contribute to these oxides' high capacity. In the present study, we used O K-edge and Mn L-edge X-ray absorption spectroscopy (XAS) to study the reversible redox reactions that occur in single-phase Li-rich layered manganese oxide, Li2MnO3. We semiquantitatively analyzed the oxygen and manganese reactions by dividing the charge/discharge voltage region into two parts. The O K-edge XAS indicated that the electrons at the oxygen site reversibly contributed to the charge compensation throughout the charge/discharge processes at operating voltages between 2.0 and 4.8 V vs. Li+/Li0. The Mn L-edge XAS spectra indicated that the Mn redox reaction occurred only in the lower-voltage region. Thus, at higher potentials, the electrons, mainly at the oxygen site, contributed to the charge compensation. Peaks whose energies were similar to peroxide appeared in and then disappeared from the O K-edge spectra obtained during the reversible redox cycles. These results indicate that the reorganization of the oxygen network in the crystal structure affects the redox components. By using two kinds of detection modes with different probing depths in XAS measurements, it was found that these redox reactions are bulk phenomena in the electrode

Microscopic mechanism of biphasic interface relaxation in lithium iron phosphate after delithiation

Charge/discharge of lithium-ion battery cathode material LiFePO4 is mediated by the structure and properties of the interface between delithiated and lithiated phases. Direct observations of the interface in a partially delithiated single crystal as a function of time using scanning transmission electron microscopy and electron energy-loss spectroscopy help clarify these complex phenomena. At the nano-scale, the interface comprises a thin multiphase layer whose composition varies monotonically between those of the two end-member phases. After partial delithiation, the interface does not remain static, but changes gradually in terms of orientation, morphology and position, as Li ions from the crystal bulk diffuse back into the delithiated regions. First-principles calculations of a monoclinic crystal of composition Li₂/₃ FePO₄ suggest that the interface exhibits higher electronic conductivity than either of the end-member phases. These observations highlight the importance of the interface in enabling LiFePO₄ particles to retain structural integrity during high-rate charging and discharging