Impact of Hydrogen Peroxide on Carbon Corrosion in Aqueous KOH Solution

Impact of hydrogen peroxide on carbon corrosion is investigated by immersion tests of catalyst-deposited highly oriented pyrolytic graphite (HOPG) samples to an aqueous solution of 1.0 mol dm⁻³ KOH + 5 mmol dm⁻³ H₂O₂. The surfaces of the HOPG samples are observed with field-emission scanning electron microscopy and X-ray photoelectron spectroscopy. HOPG without catalyst shows almost no morphological change while the distribution of C-O and C=O functional groups increases. In contrast, Pt-loaded HOPG exhibits the formation of scars and COO functional groups, which shows a relatively severe carbon corrosion reaction resulting in CO₃²⁻ formation. Since the Pt-loaded HOPG after the immersion test to 0.5 mol dm⁻³ H₂SO₄ + 5 mmol dm⁻³ H₂O₂ shows much smaller scars, it can be concluded that hydrogen peroxide corrodes Pt-loaded carbon more severely in the alkaline electrolyte solution than the acid electrolyte solution. Ag-loaded HOPG also shows the scars, while the sizes of scars are much smaller than those on the Pt-loaded HOPG. In contrast, MnOx and CoOx-loaded HOPGs exhibit no scar and minor oxygen-containing functional groups than the HOPG without catalyst, whereas MnOx and CoOx-loaded HOPGs shows larger scars than Pt and Ag-loaded HOPGs after electrochemical carbon corrosion test

Electrochemical Surface Analysis of LiMn₂O₄ Thin-film Electrodes in LiPF6/Propylene Carbonate at Room and Elevated Temperatures

Degradation of LiMn₂O₄ in LiPF₆-based electrolyte solution is complicated due to the influence of PF₆⁻ anion. Decomposition of PF₆⁻ anion accelerates both of dissolution of manganese ion and surface-film formation. In this study, surface states of LiMn₂O₄ thin-film electrodes in LiPF6/propylene carbonate (PC) derived from the surface-film formation were investigated using redox reaction of ferrocene and spectroscopic analyses. The spectroscopic analyses suggested that properties of the surface film depended the operation temperature (30°C and 55°C); a thinner surface film composed of LiF and PC decomposition products formed on LiMn₂O₄ at 30°C and a thicker surface film was formed at 55°C. The redox reaction of ferrocene clearly showed that LiMn₂O₄ was completely passivated at 30°C, while it was partially passivated at 55°C, indicating the surface film formed at 55°C was not compact and LiMn₂O₄ was exposed to the electrolyte solution. It was one of the causes of the rapid degradation of LiMn₂O₄ at elevated temperatures in LiPF6-based electrolyte solution

Relation between Mixing Processes and Properties of Lithium-ion Battery Electrode-slurry

The mixing process of electrode-slurry plays an important role in the electrode performance of lithium-ion batteries (LIBs). The dispersion state of conductive materials, such as acetylene black (AB), in the electrode-slurry directly influences the electronic conductivity in the composite electrodes. In this study, the relation between the mixing process of electrode-slurry and the internal resistance of the composite electrode was investigated in combination with the characterization of the electrode-slurries by the rheological analysis and the alternating current (AC) impedance spectroscopy. Some of the electrode-slurries showed higher value and gentler slope of the dynamic storage modulus in the low-angular-frequency region and higher thixotropic index than the others depending on the way of the mixing process and the AB content, agreeing with the low electronic volume resistivities of the corresponding composite electrodes and the electrode-slurries, which indicates the AB network growth. The results suggested that the low-viscosity state when AB and active electrode material are mixed contributes to the dispersive AB network. (C) The Author(s) 2021. Published by ECSJ

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

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

Kinetics of Interfacial Lithium-ion Transfer between a Graphite Negative Electrode and a Li₂S-P₂S₅ Glassy Solid Electrolyte

All-solid-state lithium-ion batteries that use sulfide solid electrolytes have attracted much attention due to their high safety and wide electrochemical window. In this study, highly oriented pyrolytic graphite (HOPG) and 75Li₂S-25P₂S₅ (mol%) glass were used as a model graphite negative electrode and a sulfide solid electrolyte, respectively. Interfacial lithium-ion transfer between 75Li₂S-25P₂S₅ glass and the HOPG electrode was studied by AC impedance spectroscopy measurements. The activation energy of the interfacial lithium-ion transfer was estimated to be around 37 kJ mol⁻¹, which was much smaller than that at the interface between organic liquid electrolytes and HOPG electrode, indicating that the lithium-ion transfer at the interface between 75Li₂S-25P₂S₅ glass and HOPG electrode proceeded quite rapidly. Furthermore, surface deposition of TiO₂ and surface oxidation on HOPG electrodes were performed using the atomic layer deposition (ALD) method. Interfacial lithium-ion transfer between 75Li₂S-25P₂S₅ glass and ALD-modified-HOPG electrodes was also investigated. The activation energies of the interfacial lithium-ion transfer were slightly higher than that of HOPG, but the resistance of the charge-transfer process was lower, indicating that the affinity of the HOPG electrode for the glass electrolyte was improved by surface modification

タンソ ハクマク ノ サクセイ ト ソノ デンキ カガク トクセイ ニ カンスル ケンキュウ

京都大学0048新制・論文博士博士(工学)乙第11638号論工博第3830号新制||工||1348(附属図書館)UT51-2005-D556(主査)教授 小久見 善八, 教授 垣内 隆, 教授 粟倉 泰弘学位規則第4条第2項該当Doctor of EngineeringKyoto UniversityDFA

Investigations of Electrochemically Active Regions in Bifunctional Air Electrodes Using Partially Immersed Platinum Electrodes

Oxygen reduction reaction (ORR) and oxygen evolution reactions (OER) on glassy-carbon-supported platinum electrodes (Pt/GCs), which are partially immersed in alkaline electrolytes, are investigated as a model of the triple phase boundary (TPB) in air electrodes for metal-air secondary batteries. ORR currents are measured with changing the vertical position of Pt/GCs, and OER currents are measured by linear sweep voltammetry. Based on the electrochemical results, it is found that thin liquid film on Pt/GCs effectively serves to expand TPB regions for ORR, but the liquid film hardly increases OER currents. Therefore, we conclude that the most effective TPB form are determined by the electrode reactions (ORR or OER), which are corresponding to discharge and charge processes for metal-air secondary batteries. In practice, it is strongly necessary to control the wettability of electrode inside, in order to construct high-performance bifunctional air electrodes

Electrochemical intercalation of bis(fluorosulfonyl)amide anions into graphite from aqueous solutions

Graphite intercalation compounds of bis(fluorosulfonyl)amide (FSA-GICs) are electrochemically synthesized in a highly concentrated aqueous solution. While only water decomposition occurs at the graphite electrode in a dilute aqueous solution (1 mol kg−1 NaFSA), redox peaks clearly appear in a highly concentrated aqueous solution (19 mol kg−1 NaFSA). Under the application of a constant current, the electrode potential reaches 1.7 V (vs. Ag/AgCl), which is far beyond the upper limit of the potential window, in 19 mol kg−1 NaFSA aq., and the formation of FSA-GIC is confirmed by X-ray diffraction patterns. Acceptor-type GICs using organic anions are observed for the first time in highly concentrated aqueous solutions of NaFSA