First results from in situ transmission electron microscopy studies of all-solid-state fluoride ion batteries

A focused ion beam (FIB) system is used to fabricate a micron-sized all-solid-state fluoride ion cell from a bulk battery for in situ transmission electron microscopy (TEM) testing. The bulk battery is based on a La0·9Ba0·1F2.9 solid-state electrolyte with a nanocomposite of Cu/C as a cathode and a nanocomposite of MgF2, Mg, La0·9Ba0·1F2.9 and C as an anode. The evolution of the morphology, structure, and composition of the electrodes and their interfaces with the electrolyte is characterized using in-situ TEM during electrochemical cycling. The high-resolution transmission electron microscopy (HRTEM) and scanning transmission electron microscopy-energy dispersive X-ray (STEM-EDX) analysis of the cathode-electrolyte interface reveal the expected formation of CuF2 phase during charging. During cycling, grain growth of Cu in the cathode ingredients and Cu diffusion from the cathode into the electrolyte are observed in addition to void formation

Polysulfides Formation in Different Electrolytes from the Perspective of X-ray Absorption Spectroscopy

Li-S batteries are promising energy storage technology for the future, however there two major problems remained which need to be solved before successful commercialization. Capacity fading due to polysulfide shuttle and corrosion of lithium metal are directly connected with the type and quantity of electrolyte used in the cells. Several recent works show dependence of the electrochemical behavior of Li-S batteries on type of the electrolyte. In this work we compare and discuss a discharge mechanism of sulfur conversion in three different electrolytes based on measurements with sulfur K-edge XAS. The sulfur conversion mechanism in the ether based electrolytes, the most studied type of solvents in the Li-S batteries, which are enabling high solubility of polysulfides are compared with the fluorinated ether based electrolytes with a reduced polysulfide solubility and in carbonate based electrolytes with the sulfur confined into a ultramicroporous carbon. In all three cases the sulfur reduction proceeds through polysulfide intermediate phases with a difference on the type polysulfides detected at different steps of discharge

LaSrMnO4: Reversible Electrochemical Intercalation of Fluoride Ions in the Context of Fluoride Ion Batteries

This article reports on the investigation of LaSrMnO4 with K2NiF4 type structure for use as an intercalation based high voltage cathode material with high capacity for fluoride ion batteries (FIBs). Charging was performed against PbF2 based anodes and shows that fluoride intercalation proceeds stepwise to form LaSrMnO4F and LaSrMnO4F2–x. Ex-situ X-ray diffraction experiments were recorded for different cutoff voltages for a deeper understanding of the charging process, highlighting additional potential of the method to be used to adjust fluorine contents more easily than using conventional fluorination methods. A discharging capacity of approximately 20–25 mAh/g was found, which is ∼4–5 times higher compared to what was reported previously on the discharging of BaFeO2.5/BaFeO2.5F0.5, approaching discharge capacities for conversion based fluoride ion batteries. Density functional theory based calculations confirm the observed potential steps of approximately 1 and 2 V for the first (LaSrMnO4 → LaSrMnO4F) and second (LaSrMnO4F → LaSrMnO4F2–x) intercalation steps against Pb-PbF2, respectively. Additionally, a detailed structure analysis was performed for chemically prepared LaSrMnO4F2–x (x ∼ 0.2), showing strong similarity to the product which is obtained after charging the batteries to voltages above 2 V against Pb-PbF2. It was observed that charging and discharging kinetics as well as coulomb efficiencies are limited for the batteries in the current state, which can be partly assigned to overpotentials arising from the use of conversion based anode composites and the stability of the charged sample toward carbon black and the current collectors. Therefore, the structural stability of LaSrMnO4F2 on the deintercalation of fluoride ions was demonstrated by a galvanostatic discharging to −3 V against Pb-PbF2, which can be used to compensate such overpotentials, resulting in almost complete recovery of fluorine free LaSrMnO4 with a discharge capacity of ∼100 mAh/g. This is the first report showing that selective extraction of fluoride ions from an oxyfluoride matrix is possible, and it highlights that compounds with K2NiF4 type structure can be considered as interesting host lattices for the reversible intercalation/deintercalation of fluoride ions within intercalation based FIBs

Fluoride ion batteries – past, present, and future

International audienceFluoride-Ion Batteries (FIBs) have been recently proposed as a post-lithium-ion battery system. This review article presents recent progress of the synthesis and application aspects of the cathode, electrolyte, and anode materials for fluoride-ion batteries. In this respect, improvements in solid-state electrolytes for FIBs as well as liquid electrolytes will be discussed. Furthermore, the achievements regarding the development of cathode and anode materials will be considered. With the improvements made, the field is currently attracting a steady increase of interest, and we will discuss the potentials of this technology together with necessary future milestones to be achieved in order to develop FIBs for future energy storage

LaSrMnO₄: Reversible Electrochemical Intercalation of Fluoride Ions in the Context of Fluoride Ion Batteries

This article reports on the investigation of LaSrMnO₄ with K₂NiF₄ type structure for use as an intercalation based high voltage cathode material with high capacity for fluoride ion batteries (FIBs). Charging was performed against PbF₂ based anodes and shows that fluoride intercalation proceeds stepwise to form LaSrMnO₄F and LaSrMnO₄F_2–<i>x</i>. Ex-situ X-ray diffraction experiments were recorded for different cutoff voltages for a deeper understanding of the charging process, highlighting additional potential of the method to be used to adjust fluorine contents more easily than using conventional fluorination methods. A discharging capacity of approximately 20–25 mAh/g was found, which is ∼4–5 times higher compared to what was reported previously on the discharging of BaFeO_2.5/BaFeO_2.5F_0.5, approaching discharge capacities for conversion based fluoride ion batteries. Density functional theory based calculations confirm the observed potential steps of approximately 1 and 2 V for the first (LaSrMnO₄ → LaSrMnO₄F) and second (LaSrMnO₄F → LaSrMnO₄F_2–<i>x</i>) intercalation steps against Pb-PbF₂, respectively. Additionally, a detailed structure analysis was performed for chemically prepared LaSrMnO₄F_2–<i>x</i> (<i>x</i> ∼ 0.2), showing strong similarity to the product which is obtained after charging the batteries to voltages above 2 V against Pb-PbF₂. It was observed that charging and discharging kinetics as well as coulomb efficiencies are limited for the batteries in the current state, which can be partly assigned to overpotentials arising from the use of conversion based anode composites and the stability of the charged sample toward carbon black and the current collectors. Therefore, the structural stability of LaSrMnO₄F₂ on the deintercalation of fluoride ions was demonstrated by a galvanostatic discharging to −3 V against Pb-PbF₂, which can be used to compensate such overpotentials, resulting in almost complete recovery of fluorine free LaSrMnO₄ with a discharge capacity of ∼100 mAh/g. This is the first report showing that selective extraction of fluoride ions from an oxyfluoride matrix is possible, and it highlights that compounds with K₂NiF₄ type structure can be considered as interesting host lattices for the reversible intercalation/deintercalation of fluoride ions within intercalation based FIBs

In situ TEM studies of micron-sized all-solid-state fluoride ion batteries: Preparation, prospects, and challenges

Trustworthy preparation and contacting of micron‐sized batteries is an essential task to enable reliable in situ TEM studies during electrochemical biasing. Some of the challenges and solutions for the preparation of all‐solid‐state batteries for in situ TEM electrochemical studies are discussed using an optimized focused ion beam (FIB) approach. In particular redeposition, resistivity, porosity of the electrodes/electrolyte and leakage current are addressed. Overcoming these challenges, an all‐solid‐state fluoride ion battery has been prepared as a model system for in situ TEM electrochemical biasing studies and first results on a Bi/La0.9Ba0.1F2.9 half‐cell are presented

Design of small hobby CNC milling machine with fixed table

The topic of this work is the design of a small model CNC milling machine with a fixed table for machining wood, plastic, or light alloys (Al, Zn, etc.). It also includes a calculation report and drawing documentation of selected nodes. The beginning of this work consists of an introduction to the issue of milling machines, their distribution and subsequent market analysis. Subsequently, the input parameters are designed on the basis of market analysis and in the last part there is a calculation report, the design of the milling machine itself and a short economic evaluation

Sodiation of hard carbon:how separating enthalpy and entropy contributions can find transitions hidden in the voltage profile

Sodium-ion batteries (NIBs) utilise cheaper materials than lithium-ion batteries (LIBs), and can thus be used in larger scale applications. The preferred anode material is hard carbon, because sodium cannot be inserted into graphite. We apply experimental entropy profiling (EP), where the cell temperature is changed under open circuit conditions. EP has been used to characterise LIBs; here, we demonstrate the first application of EP to any NIB material. The voltage versus sodiation fraction curves (voltage profiles) of hard carbon lack clear features, consisting only of a slope and a plateau, making it difficult to clarify the structural features of hard carbon that could optimise cell performance. We find additional features through EP that are masked in the voltage profiles. We fit lattice gas models of hard carbon sodiation to experimental EP and system enthalpy, obtaining: 1. a theoretical maximum capacity, 2. interlayer versus pore filled sodium with state of charge