Kinetic properties of sodium-ion transfer at the interface between graphitic materials and organic electrolyte solutions

Graphitic materials cannot be applied for the negative electrode of sodium-ion battery because the reversible capacities of graphite are anomalously small. To promote electrochemical sodium-ion intercalation into graphitic materials, the interfacial sodium-ion transfer reaction at the interface between graphitized carbon nanosphere (GCNS) electrode and organic electrolyte solutions was investigated. The interfacial lithium-ion transfer reaction was also evaluated for the comparison to the sodium-ion transfer. From the cyclic voltammograms, both lithium-ion and sodium-ion can reversibly intercalate into/from GCNS in all of the electrolytes used here. In the Nyquist plots, the semi-circles at the high frequency region derived from the Solid Electrolyte Interphase (SEI) resistance and the semi-circles at the middle frequency region owing to the charge-transfer resistance appeared. The activation energies of both lithium-ion and sodium-ion transfer resistances were measured. The values of activation energies of the interfacial lithium-ion transfer suggested that the interfacial lithium-ion transfer was influenced by the interaction between lithium-ion and solvents, anions or SEI. The activation energies of the interfacial sodium-ion transfer were larger than the expected values of interfacial sodium-ion transfer based on the week Lewis acidity of sodium-ion. In addition, the activation energies of interfacial sodium-ion transfer in dilute FEC-based electrolytes were smaller than those in concentrated electrolytes. The activation energies of the interfacial lithium/sodium-ion transfer of CNS-1100 in FEC-based electrolyte solutions were almost the same as those of CNS-2900, indicating that the mechanism of interfacial charge-transfer reaction seemed to be the same for highly graphitized materials and low-graphitized materials each other

Sodium/Lithium-Ion Transfer Reaction at the Interface between Low-Crystallized Carbon Nanosphere Electrodes and Organic Electrolytes

Carbon nanosphere (CNS) electrodes are the candidate of sodium-ion battery (SIB) negative electrodes with small internal resistances due to their small particle sizes. Electrochemical properties of low-crystallized CNS electrodes in dilute and concentrated sodium bis(trifluoromethanesulfonyl) amide/ethylene carbonate + dimethyl carbonate (NaTFSA/EC + DMC) were first investigated. From the cyclic voltammograms, both lithium ion and sodium ion can reversibly insert into/from CNSs in all of the electrolytes used here. The cycling stability of CNSs in concentrated electrolytes was better than that in dilute electrolytes for the SIB system. The interfacial charge-transfer resistances at the interface between CNSs and organic electrolytes were evaluated using electrochemical impedance spectroscopy. In the Nyquist plots, the semicircles at the middle-frequency region were assigned to the parallel circuits of charge-transfer resistances and capacitances. The interfacial sodium-ion transfer resistances in concentrated organic electrolytes were much smaller than those in dilute electrolytes, and the rate capability of CNS electrodes in sodium salt-concentrated electrolytes might be better than in dilute electrolytes, suggesting that CNSs with concentrated electrolytes are the candidate of SIB negative electrode materials with high rate capability. The calculated activation energies of interfacial sodium-ion transfer were dependent on electrolyte compositions and similar to those of interfacial lithium-ion transfer

Operando analysis of graphite intercalation compounds with fluoride-containing polyatomic anions in aqueous solutions

The formation of graphite intercalation compounds (GICs) in aqueous solutions has attracted much attention, but reversibility in the formation/deformation of GICs is a challenging issue to construct highly safe rechargeable batteries. In this study, we used an operando analysis (X-ray diffraction and Raman spectroscopy) to discuss the feasibility of using fluoride-containing polyatomic anions in the formation of GICs in aqueous highly concentrated solutions. We found that the intercalation of anions containing a C₂F₅ moiety (such as [N(SO₂CF₃)(SO₂CF₂CF₃)]⁻ or [N(SO₂CF₂CF₃)₂]⁻) does not occur in the bulk of graphite, but only in the surface region. In addition, anions containing a CF₃ moiety show different behaviors: SO₃CF₃⁻ shows greater reversibility and larger stage-number than N(SO₂CF₃)₂⁻ in the formation of GICs. These results provide design guidelines for the reversible intercalation and de-intercalation of anions and their application as a cathode material in aqueous rechargeable batteries

Extracellular and Mixotrophic Symbiosis in the Whale-Fall Mussel Adipicola pacifica: A Trend in Evolution from Extra- to Intracellular Symbiosis

http://www.godac.jamstec.go.jp/darwin/cruise/natsushima/nt05-12/

Distinction of synthetic dl-α-tocopherol from natural vitamin E (d-α-tocopherol) by reversed-phase liquid chromatography. Enhanced selectivity of a polymeric C18 stationary phase at low temperature and/or at high pressure

© 2016 Elsevier B.V. Separation of diastereomers of DL-α-tocopherol was studied by reversed-phase liquid chromatography using three types of stationary phases, polymeric ODS, polymeric C30, and monomeric ODS. Polymeric ODS stationary phase (Inertsil ODS-P, 3 mmID, 20 cm) was effective for the separation of the isomers created by the presence of three chiral centers on the alkyl chain of synthetic DL-α-tocopherol. Considerable improvement of the separation of isomers was observed on ODS-P phase at high pressure and at low temperature. Complete separation of four pairs of diastereomers was achieved at 12.0 °C, 536 bar, while three peaks were observed when the separation was carried out either at 12.0 °C at low pressure or at 20 °C at 488 bar. Higher temperature (30.0 °C) with the ODS-P phase resulted in only partial separation of the diastereomers even at high pressure. Only slight resolution was observed for the mixture of diastereomers with the C30 stationary phase (Inertsil C30) at 12.0 °C and 441 bar, although the stationary phase afforded greater resolution for β- and γ-tocopherol than ODS-P. A monomeric C18 stationary phase did not show any separation at 12.0 °C and 463 bar. The results suggest that the binding site of the polymeric ODS-P phase is selective for flexible alkyl chains that provided the longest retention for the natural form, (R,R,R) form, and the enantiomer, (S,S,S) form, of DL-α-tocopherol