The transition from laboratory-scale experiments to industrial-scale production frequently exposes fundamental challenges related to process similarity. In the context of silicon porosification, achieving consistent results during scale-up requires maintaining thermal, kinematic, geometric, and electrochemical (current/potential) similarities. On the example of two stages of upscaling, this work aims to elucidate the principal scaling effects that arise during the electrochemical porosification of silicon and to outline strategies for mitigating them. Through a series of representative examples, the paper highlights how process parameters, reactor geometry, and operating modes influence the resulting pore architecture and uniformity. A novel inline etching tool is presented where the wafers pass over tanks of alternating polarity. This approach has the great benefit that it does not need a backside contact; however, the alternating tank coverage leads to current density fluctuations under potentiostatic operation. A simple COMSOL simulation (Finite Element Method) of the series resistance network of the system is able to explain the fluctuations qualitatively as well as quantitatively. On this basis, design rules for the next-generation inline etching tool are suggested that would reduce the current density fluctuations from about 50 % to less than 10 %.
“Upscaling the Electrochemical Porosification of Silicon — A theoretical and experimental process analysis” by Monja GRONENBERG et al. is selected as an Editor’s Choice for the 74th Special Feature, “Advances in Electrochemistry Enabled by Diverse Research Backgrounds and Perspectives” recommended jointly by the guest editors from the Committee Editorial Board of Electrochemistry. This study addresses the fundamental challenges encountered when electrochemical porosification of silicon is transferred from laboratory-scale experiments to industrially relevant production. The authors clarify how thermal, kinematic, geometric, and electrochemical similarities govern pore uniformity during scale-up. In particular, they present a novel inline etching tool in which silicon wafers pass over electrolyte tanks of alternating polarity, enabling porosification without mechanical backside contact. Through COMSOL-based analysis of the series-resistance network, the observed current-density fluctuations are reproduced quantitatively, providing practical design rules for improving next-generation inline etching systems.
Sodium-ion batteries (SIBs) are promising next-generation energy-storage systems, yet their low energy density remains a major challenge. An effective strategy to utilizing low-potential anodes is tuning their electrode potentials with respective to an electrolyte potential window. Herein we propose a molecular framework design of electrolyte solvents to rationally tune sodium electrode potential (ENa). Extending the alkyl chains of phosphate ester solvents upshifted ENa by up to 0.32 V (tripropyl phosphate vs. trimethyl phosphate) despite similar donor numbers, indicating a dominant steric effect to weaken the Na+ solvation. In contrast, cyclic crown ether 15-crown-5 downshifted ENa by 0.16 V compared to its linear counterpart (tetraglyme) via the formation of a more stable chelate coordination. Furthermore, the magnitude of these steric/structural effects depended strongly on the cation species, leading to large variations in the Na-Li electrode potential difference (ΔENa–Li), from 0.53 V in tripropyl phosphate to 0.10 V in 18-crown-6. Machine-learning-based molecular dynamics simulations revealed that the changes in the cation solvation structure, induced by the solvent molecular framework engineering, are responsible for the observed potential shifts. These findings establish solvent molecular framework engineering as a versatile strategy to tune electrode potentials in battery electrolytes.
“Tuning the Sodium Electrode Potential by Solvent Molecular Framework Engineering” by Hiroshi Takida et al. is selected as an Editor’s Choice. This study presents a rational strategy for tuning sodium and lithium electrode potentials through the molecular framework design of electrolyte solvents. By comparing phosphate ester, glyme, and crown ether solvents, the authors demonstrate that steric hindrance and cyclic chelation can significantly alter cation solvation structures and thereby shift electrode potentials. Notably, extending the alkyl chain from trimethyl phosphate to tripropyl phosphate upshifts the sodium electrode potential, whereas crown ether coordination stabilizes the cation and shifts the potential in the opposite direction. Machine-learning-based molecular dynamics simulations further clarify how solvent structure controls cation coordination and anion participation in the solvation shell.
Electrochemical conversion of CO2 into calcium carbide in molten salts has emerged as a promising route for carbon capture and utilization, enabling the production of acetylene, an important industrial chemical. However, continuous operation requires a stable oxygen evolution reaction (OER) at the anode while suppressing competing oxidation of carbonate and carbide species that regenerate CO2. The anodic reaction mechanism in carbide-containing molten salts remains poorly understood. Here, the anodic behavior and durability of the perovskite oxide La0.7Sr0.3FeO3−δ are investigated in molten NaCl–CaCl2 at 873 K under controlled anionic environments containing O2−, CO32−, and C22−. Thermodynamic analysis using potential–pO2− diagrams predicts that carbide oxidation occurs at the most negative potential, followed by carbon, oxide, and carbonate oxidation, which agrees with electrochemical measurements and gas analysis. When O2− and CO32− coexist, selective oxygen evolution is achieved with a Faradaic efficiency of 81.4 % and a low corrosion rate of 1.94 × 10−5 g cm−2 h−1. In contrast, dissolved C22− undergoes anodic oxidation at lower potentials, producing amorphous carbon that accelerates electrode degradation and reduces OER efficiency. These results demonstrate that anodic stability is governed by the local anionic environment, highlighting the importance of maintaining O2− and CO32− coexistence while suppressing carbide transport to the anode.
“Influence of CO32– and C22– on the Oxygen Evolution Performance of Perovskite La0.7Sr0.3FeO3–δ Anode in Molten NaCl–CaCl2” by Ryohei Tasaki et al. is selected as an Editor’s Choice.This study addresses the anodic reactions required for electrochemical conversion of CO2 into calcium carbide in molten salts, a promising carbon capture and utilization route toward acetylene production. Using La0.7Sr0.3FeO3–δ as a perovskite-type oxygen evolution anode, the authors clarify how the local anionic environment controls both oxygen evolution performance and electrode durability. In molten NaCl–CaCl2 containing O2– and CO32–, selective oxygen evolution is achieved with high Faradaic efficiency and low corrosion. In contrast, dissolved C22– is oxidized at lower potentials to form amorphous carbon, which accelerates anode degradation and suppresses oxygen evolution.
Suppressing zincate crossover is necessary for rechargeable alkaline Zn-MnO2 rechargeable batteries using electrolytic manganese dioxide (EMD). We benchmarked six commercial separators for their ability to block zincate ions while maintaining the transport of hydroxide ions. Among the separators, FAAM-75-PK (FP75), a commercial anion-exchange membrane, exhibited moderate conductivity (5.8 mS cm−1) with the lowest diffusion coefficient of zincate ions (DZn = 2.0 × 10−8 cm2 s−1) and a moderate diffusion coefficient of hydroxide ions (DOH = 3.5 × 10−5 cm2 s−1), leading to the highest permselectivity (DOH/DZn = 1.7 × 103). In the galvanostatic discharge–charge tests, FP75 exhibited the best capacity retention of 68 % at the 7th cycle. Characterization of the discharged EMD electrodes revealed that FP75 effectively suppressed ZnMn2O4 formation at the cathode, favoring Mn3O4 formation instead. The low Zn concentration of 6 ppm in the catholyte is consistent with the favored Mn3O4 formation. Beaker-cell tests identify a system-dependent zinc concentration threshold. When the Zn/Mn molar ratio exceeds ∼0.05–0.15, product formation shifts toward ZnMn2O4 from Mn3O4, and thus, the capacity decay accelerates.
“Understanding Separator Properties Governing Zincate Crossover in Rechargeable Alkaline Zn–MnO2 Batteries” by Yimin Lin et al. is selected as an Editor’s Choice for the 73rd Special Feature, “Progress in Aqueous-Based Batteries” recommended jointly by the guest editors from the Committee of Battery Technology and the editorial board. This study clarifies how separator properties govern zincate crossover in rechargeable alkaline Zn–MnO2 batteries. By comparing six commercial separators, the authors showed that the anion-exchange membrane FAAM-75-PK effectively suppresses zincate diffusion while maintaining hydroxide ion transport, leading to improved cycling performance. The cover image schematically represents two alkaline Zn–MnO2 battery systems with different separator functions. The transparent cells visualize ion transport, zincate crossover, and the role of the separator in controlling the chemical environment near the MnO2 electrode, emphasizing the importance of separator design for durable rechargeable alkaline batteries.
It is important to develop a rechargeable battery that is safe and free from resource risk to replace the current lithium–ion battery in various application fields. We have been conducting research and development of aqueous electrolyte batteries with zinc as the negative electrode (anode) through national programs, Research and Development Initiative for Scientific Innovation of New Generation Batteries (RISING, RISING2 and RISING3), commissioned by the New Energy and Industrial Technology Development Organization (NEDO). In RISING2, we demonstrated a full cell that can achieve a target specific energy of 500 Wh kg−1 for a zinc–air system through advancements in elemental technology and full-cell engineering. RISING3 aims to develop a sealed zinc-anode rechargeable battery by developing positive electrode (cathode) materials to replace air electrodes. A notable achievement of this study is proving that the manganese dioxide (MnO2) prepared through electrolysis (EMD) has good rechargeability in alkaline electrolyte systems, in which the amount of structural water in the oxide determines the discharge capacity for the first one-electron reduction. We also found that the newly developed MnO2 from the chemical reduction of permanganate (PMD) enables a reversible two-electron reaction even in the electrolyte containing zinc species, in which hetaerolite (ZnMn2O4) generally forms to inhibit further electrochemical reactions.
“Research and Development of Zinc-based Rechargeable Batteries in RISING3” by Masayuki Morita et al. is selected as an Editor’s Choice for the 73rd Special Feature, “Progress in Aqueous-Based Batteries” recommended jointly by the guest editors from the Committee of Battery Technology and the editorial board. This article summarizes research and development on safe, resource-risk-free zinc-based rechargeable batteries conducted under the RISING, RISING2, and RISING3 national projects. Building on previous achievements in alkaline zinc–air systems, the study focuses on alkaline Zn–MnO2 batteries using manganese dioxide as the positive electrode material. The authors demonstrate that the rechargeability and capacity of electrolytic manganese dioxide are strongly related to its structural water and microstructure. They further show that permanganate-derived manganese dioxide enables a reversible two-electron reaction even in alkaline electrolytes containing zinc species, providing an important approach toward higher-energy sealed zinc-anode rechargeable batteries. The cover image schematically represents the aqueous alkaline Zn–MnO2 battery concept, in which zinc-based negative electrode reactions, MnO2 redox processes, water-mediated proton transfer, and structural changes of manganese oxide are visualized across the cell. The bright ion-transport pathways and contrasting oxide domains emphasize the dynamic interfacial reactions underlying rechargeable zinc battery performance.
Cyclic Voltammetry Part 1: Fundamentals
Released on J-STAGE: October 31, 2022 | Volume 90 Issue 10 Pages 102005
Hirohisa YAMADA, Kazuki YOSHII, Masafumi ASAHI, Masanobu CHIKU, Yuki KITAZUMI
Views: 2,040
Electrochemical Impedance Spectroscopy Part 1: Fundamentals
Released on J-STAGE: October 31, 2022 | Volume 90 Issue 10 Pages 102007
Kingo ARIYOSHI, Zyun SIROMA, Atsushi MINESHIGE, Mitsuhiro TAKENO, Tomokazu FUKUTSUKA, Takeshi ABE, Satoshi UCHIDA
Views: 2,028
Electrochemical Impedance Spectroscopy Part 2: Applications
Released on J-STAGE: October 31, 2022 | Volume 90 Issue 10 Pages 102008
Kingo ARIYOSHI, Atsushi MINESHIGE, Mitsuhiro TAKENO, Tomokazu FUKUTSUKA, Takeshi ABE, Satoshi UCHIDA, Zyun SIROMA
Views: 1,514
Electrical Conductivity Measurement of Electrolyte Solution
Released on J-STAGE: October 31, 2022 | Volume 90 Issue 10 Pages 102011
Minoru MIZUHATA
Views: 1,105
Electrochemical Polarization Part 1: Fundamentals and Corrosion
Released on J-STAGE: October 31, 2022 | Volume 90 Issue 10 Pages 102003
Kentaro KURATANI, Kazuhiro FUKAMI, Hiroaki TSUCHIYA, Hiroyuki USUI, Masanobu CHIKU, Shin-ichi YAMAZAKI
Views: 716