Concentration profile of dissolved gas during hydrogen gas evolution: an optical approach

We develop an optical image tracking technique for the simultaneous observation of a wide area in proximity to the electrode, and study the growth of bubbles during hydrogen gas evolution in alkaline water electrolysis. Using a diffusion model we can successfully extract the concentration profile of dissolved hydrogen gas as a function of distance from the electrode. The obtained concentrations agree well with the values by the electrochemical method

Probing the Dissolved Gas Concentration on the Electrode through Laser-Assisted Bubbles

We demonstrate that the irradiation of a single laser pulse onto the electrode assists the formation of bubbles, and this phenomenon can be conveniently used to probe the dissolved gas concentration on the electrode. The obtained concentrations agree well with the values inferred through linear extrapolation of gas concentration in proximity to the electrode to the electrode surface

Multiscale and hierarchical reaction mechanism in a lithium-ion battery

The key to improving the performance of lithium-ion batteries is to precisely elucidate the temporal and spatial hierarchical structure of the battery. Lithium-ion batteries consist of cathodes and anodes and a separator containing an electrolyte. The cathodes and anodes of lithium-ion batteries are made of a composite material consisting of an active material, a conductive material, and a binder to form a complex three-dimensional structure. The reaction proceeds as lithium ions are repeatedly inserted into and removed from the active material. Therefore, the lattice of the active material is restructured due to ion diffusion, which results in phase change. At the active material–electrolyte interface, the insertion and de-insertion of lithium ions proceed with the charge transfer reaction. The charge–discharge reaction of a lithium-ion battery is a nonequilibrium state due to the interplay of multiple phenomena. Analysis after disassembling a battery, which is performed in conventional battery research, does not provide an accurate understanding of the dominant factors of the reaction rate and the degradation mechanism, in some cases. This review introduces the results of research on the temporal and spatial hierarchical structure of lithium-ion batteries, focusing on operando measurements taken during charge–discharge reactions. Chapter 1 provides an overview of the hierarchical reaction mechanism of lithium-ion batteries. Chapter 2 introduces the operando measurement technique, which is useful for analysis. Chapter 3 describes the reaction at the electrode–electrolyte interface, which is the reaction field, and Chapter 4 discusses the nonequilibrium structural change caused by the two-phase reaction in the active material. Chapter 5 introduces the study of the unique reaction heterogeneity of a composite electrode, which enables practical energy storage. Understanding the hierarchical reaction mechanism will provide useful information for the design of lithium-ion batteries and next-generation batteries

Disordered Cubic Spinel Structure in the Delithiated Li2MnO3 Revealed by Difference Pair Distribution Function Analysis

An archetypical Li-rich layered oxide, Li2MnO3, shows a large initial charge capacity of ~350 mAh g-1 with little oxidation of the constituent Mn ions, yet, the crystal structure of delithiated Li2MnO3 is still unclarified because the structural disorder induced by the considerable Li extraction makes the analysis challenging. X-ray pair distribution function (PDF) analysis is a powerful tool to experimentally elucidate the structure of the disordered phase. Here, we conducted a comprehensive analysis with a focus on PDF analysis in combination with the X-ray powder diffraction (XRPD), transmission electron microscopy (TEM), and X-ray absorption spectroscopy (XAS) to reveal the disordered crystalline structure of the electrochemically delithiated Li2MnO3. The XRPD and TEM analyses clarified the formation of a low-crystallinity phase in the light of the average structure. The XAS and PDF analyses further revealed that the MnO6–based framework was rearranged with maintaining the MnO6 octahedral coordination after the initial charge. The difference pair distribution function (d-PDF) technique was therefore employed to extract the structural information of the low-crystallinity disordered phase. The delithiated phase was found to have a structure similar to the cubic spinel, LiMn2O4, rather than that of delithiated LiMn2O4 (λ-MnO2). In addition, the middle-range order of the delithiated phase deteriorated after the charge, indicating a decrease of coherent domain size to a single nm order. The composite structure formed after the first charge, therefore, consists of the disordered cubic spinel structure and unreacted Li2MnO3. The formation of the composite structure “activates” the electrode material structurally and eventually induces characteristic large capacity of this material

Adaptive Cation Pillar Effects Achieving High Capacity in Li-Rich Layered Oxide, Li2MnO3-LiMeO2 (Me = Ni, Co, Mn)

Intensive research is underway to further enhance the performance of lithium-ion batteries (LIBs). To increase the capacity of positive electrode materials, Li-rich layered oxides (LLO) are attracting attention but have not yet been put to practical use. The structural mechanisms through which LLO materials exhibit higher capacity than conventional materials remain unclear because their disordered phases make it difficult to obtain structural information by conventional analysis. The X-ray total scattering analysis reveals a disordered structure consisting of metal ions in octahedral and tetrahedral sites of Li layers as a result of cation mixing after the extraction of Li ions. Metal ions in octahedral sites act as rigid pillars. The metal ions move to the tetrahedral site of the Li layer, which functions as a Li-layer pillar during Li extraction, and returns to the metal site during Li insertion, facilitating Li diffusion as an adaptive pillar. Adaptive pillars are the specific structural features that differ from those of the conventional layered materials, and their effects are responsible for the high capacity of LLO materials. An essential understanding of the pillar effects will contribute to design guidelines for intercalation-type positive electrodes for next-generation LIBs

Adaptive Cation Pillar Effects Achieving High Capacity in Li-Rich Layered Oxide, Li₂MnO₃-LiMeO₂ (Me = Ni, Co, Mn)

リチウムイオン電池正極の低結晶層状構造を支える2種類の支柱. 京都大学プレスリリース. 2022-09-05.Intensive research is underway to further enhance the performance of lithium-ion batteries (LIBs). To increase the capacity of positive electrode materials, Li-rich layered oxides (LLO) are attracting attention but have not yet been put to practical use. The structural mechanisms through which LLO materials exhibit higher capacity than conventional materials remain unclear because their disordered phases make it difficult to obtain structural information by conventional analysis. The X-ray total scattering analysis reveals a disordered structure consisting of metal ions in octahedral and tetrahedral sites of Li layers as a result of cation mixing after the extraction of Li ions. Metal ions in octahedral sites act as rigid pillars. The metal ions move to the tetrahedral site of the Li layer, which functions as a Li-layer pillar during Li extraction, and returns to the metal site during Li insertion, facilitating Li diffusion as an adaptive pillar. Adaptive pillars are the specific structural features that differ from those of the conventional layered materials, and their effects are responsible for the high capacity of LLO materials. An essential understanding of the pillar effects will contribute to design guidelines for intercalation-type positive electrodes for next-generation LIBs

Unique Li deposition behavior in Li₃PS₄ solid electrolyte observed via operando X-ray computed tomography

The problem of lithium dendrites must be addressed for practical lithium metal all-solid-state batteries. Herein, three-dimensional morphological changes within Li₃PS₄ electrolyte away from the anode were observed using operando X-ray computed tomography. We revealed that the electronic conduction of decomposition and the electrolyte/void interface cause the lithium deposition within the Li₃PS₄

Mechanistic Insight on the Formation of GaN:ZnO Solid Solution from Zn–Ga Layered Double Hydroxide Using Urea as the Nitriding Agent

A solid solution of GaN and ZnO (GaN:ZnO) is promising as a photocatalyst for visible light-driven overall water splitting to produce H2. However, several obstacles still exist in the conventional preparation procedure of GaN:ZnO. For example, the atomic distributions of Zn and Ga are non-uniform in GaN:ZnO when a mixture of the metal oxides, i.e., Ga2O3 and ZnO, is used as a precursor. In addition, GaN:ZnO is generally prepared under harmful NH3 flow for long durations at high temperatures. Here, a facile synthesis of GaN:ZnO with homogeneous atomic composition via a simple and safe procedure is reported. A layered double hydroxide (LDH) containing Zn2+ and Ga3+ was used to increase the uniformity of the atomic distributions of Zn and Ga in GaN:ZnO. We employed urea as a nitriding agent instead of gaseous NH3 to increase the safety of the reaction. Through the optimization of reaction conditions such as heattreatment temperature and content of urea, single-phase GaN:ZnO was successfully obtained. In addition, the nitridation mechanism using urea was investigated in detail. NH3 released from the thermal decomposition of urea did not directly nitride the LDH precursor. X-ray absorption and infrared spectroscopies revealed that Zn(CN2)-like intermediate species were generated at the middle temperature range and Ga–N bonds formed at high temperature along with dissociation of CO and CO2.This file includes Supporting Information.This work was supported by JSPS KAKENHI Grant Number JP16H06438, JP16H06441, JP17H05483, JP17H03392. This work was partly supported by the Center for Functional Nano Oxide at Hiroshima University. The synchrotron radiation experiments were performed at the BL01B1 beamline of SPring-8 with the approval of the Japan Synchrotron Radiation Research 32 Institute (JASRI) (Proposal No. 2017B1043 and 2018A1749)