master thesis in fluoride

Lithium ion batteries (LIBs) are widely used for portable electronics. However, their application is limited because of energy density, safety issues, and the high cost. This necessitates a search for alternative battery technologies. Many alternative battery systems are currently investigated based on different chemistries, which include sodium, magnesium, chloride, aluminum, and potassium based batteries. Rechargeable batteries based on a fluoride anion shuttle are a promising alternative to Li-ion batteries with theoretical energy densities of more than 5000 WhL-1. However, detailed chemical and structural investigations are necessary to understand the structural changes and the degradation mechanisms to improve the performance of fluoride ion batteries. In the present thesis, TEM has been used to study all-solid-state fluoride ion batteries in situ and ex situ. For in situ TEM studies, two all-solid-state fluoride ion battery systems were used; a half-cell consisting of a Bi composite as electrode and La0.9Ba0.1F2.9 as a solid electrolyte; and a full cell consisting of a Cu composite as cathode, a MgF2 composite as anode, and La0.9Ba0.1F2.9 as a solid electrolyte. Optimization of sample preparation was an essential step to enable reliable in situ TEM studies during electrochemical biasing. Challenges during sample preparation, such as re-deposition/metal contamination, contact resistance, porosity of the battery materials and leakage current were resolved using an optimized FIB based approach. The successful preparation has been demonstrated for two fluoride ion battery systems. The in situ TEM studies of the half-cell revealed the fluorination of Bi and Bi2O3 forming BiF3 and BiO0.1F2.8, and the simultaneous reduction of La0.9Ba0.1F2.9 to La and Ba during charging. During discharging, most of the BiF3 was reduced to Bi metal. Comparing the structural changes with the electrochemical charging curve, the main phase formed was the irreversible phase BiO0.1F2.8, leading to the poor reversibility of the half-cell. On the other hand, the TEM studies of the cathode-electrolyte interface of the full cell revealed fluoride migration into the composite cathode during charging resulting in the formation of CuF2, which was absent in the as-prepared state. Due to the high volumetric changes associated with the CuF2 formation, the cell fractured at the cathode-electrolyte interface during the second charging. However, a detailed electrochemical study during discharging was problematic, as a short circuit between cathode and anode dominated the current. In addition, a fluoride ion battery system consisting of a CuF2 composite as cathode, La0.9Ba0.1F2.9 as a solid electrolyte, and a La sheet as anode was studied ex situ in the as-prepared, discharged, and recharged states. The interfacial studies were performed by lifting-out two lamellae from each pellet at the electrodes-electrolyte interfaces using FIB. The TEM studies of the cathode confirmed the defluorination/fluorination during cycling of CuF2/Cu. However, the TEM studies revealed a high oxygen content in the cathode composite explaining the difference between the theoretical capacity of Cu/CuF2 (528 mAh g-1) and the observed capacity during the first discharge (360 mAh g-1). On the anode side, the presence of La2O3 on the surface led to a side reaction by LaOF formation during recharging, which acts as a significant fluoride trap. Therefore, the capacity faded upon cycling to only 165 mAh g-1 in the second discharge. Moreover, The STEM-EDX maps revealed Cu diffusion from the cathode into the electrolyte due to the high volumetric change in the cathode, partially explain the capacity fading.

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• Published: 11 February 2023

Assessing ternary materials for fluoride-ion batteries

• Don H. McTaggart 1 ,
• Jack D. Sundberg 1 ,
• Lauren M. McRae 1 &
• Scott C. Warren   ORCID: orcid.org/0000-0002-2883-0204 1  

Scientific Data volume  10 , Article number:  90 ( 2023 ) Cite this article

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• Computational methods

Although lithium-ion batteries have transformed energy storage, there is a need to develop battery technologies with improved performance. Fluoride-ion batteries (FIBs) may be promising alternatives in part due to their high theoretical energy density and natural elemental abundance. However, electrode materials for FIBs, particularly cathodes, have not been systematically evaluated, limiting rapid progress. Here, we evaluate ternary fluorides from the Materials Project crystal structure database to identify promising cathode materials for FIBs. Structures are further assessed based on stability and whether fluorination/defluorination occurs without unwanted disproportionation reactions. Properties are presented for pairs of fluorinated/defluorinated materials including theoretical energy densities, cost approximations, and bandgaps. We aim to supply a dataset for extracting property and structural trends of ternary fluoride materials that may aid in the discovery of next-generation battery materials.

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Background & summary.

As our global system transitions to renewable energy, the demand for efficient and affordable energy storage will continue to grow. Currently, lithium-ion batteries (LIBs) bear the major load of electrochemical energy storage requirements due to their high energy density and cyclability 1 . However, it remains unclear whether the production of lithium-ion batteries can scale at a rate and cost that will meet future needs 2 , 3 . In the search for alternatives to lithium, fluoride-ion batteries (FIBs) are promising based on several factors. First, they offer higher theoretical energy densities than current LIBs (~1,000–2,200 Wh/kg vs 220–650 Wh/kg) 2 , 4 . Second, since fluorine is the most electronegative element, fluoride has high redox stability, which enables battery operation within a large electrochemical window. Third, fluoride and many of its prospective electrode materials are more abundant and less expensive than those for lithium 4 .

Significant work has been accomplished in discovering liquid electrolytes 5 , 6 , 7 , 8 and high-performance anodes 9 , 10 for FIBs. Although additional investigation in these components is still critical, there is an especially strong need to identify promising cathode materials. To guide previous cathode discovery, the primary heuristic that has been used is fluoride affinity. During the FIB discharge process, fluoride ions (F − ) spontaneously leave the cathode and migrate through the electrolyte to the anode. For this to be spontaneous, the anode must have higher affinity for fluoride than the cathode. Thus, a general design rule for fluoride electrodes is that more electronegative elements such as Cu or Bi are promising for cathodes, and more electropositive elements such as Mg or Y are promising for anodes 11 , 12 , 13 , 14 , 15 . These simple guidelines have inspired considerable cathode work using the binary metal fluorides like Cu/CuF 2 , Fe/FeF 3 , Sn/SnF 2 and particularly Bi/BiF 3 12 , 16 , 17 , 18 , 19 , 20 . However, the realization of more complex compositions creates an opportunity to alter a material’s physical and electronic properties for cathode use beyond the limited scope of binary compositions. Recent studies have employed three and four elements-containing oxide cathode materials (La 2 NiO 4 , LaSrMnO 4 , La 2 CoO 4 , BaFeO 2.5 ) 14 , 21 , 22 , 23 to begin expanding this design space. Despite these advances, only a small number of more complex compositions have been investigated. In this work, we describe the first systematic exploration of compounds that assesses the cathodic capability of all known ternary fluoride materials.

With thousands of possible ternary metal fluorides, a method for selecting candidates for experimental discovery becomes paramount. The recent development of large crystal structure databases like Materials Project 24 makes computational screening an attractive first step for this purpose. Here, we utilize computational filtering techniques to search for existing ternary metal fluorides in the Materials Project database that may function as cathodes for FIBs. Our search aims to identify fluorinated and defluorinated structure pairs. Identification of fluorinated/defluorinated pairs yields a dataset of possible charged and discharged states for a cathode material. This broader filtering is broken down into two smaller searches: fully defluorinated candidates and partially defluorinated candidates. These are further narrowed down by considering calculated stability and presence of disproportionation reactions along the defluorination pathway. In Fig.  1 , we present a simplified diagram for this filtering algorithm.

The filtering steps used to obtain the final dataset. Several quaternary materials were also identified as promising cathodes and included in this dataset.

A collection of properties was also calculated for each structure pair including redox potentials vs. Li/LiF and vs. F 2 , specific capacity, percent expansion between defluorinated and fluorinated forms, energy densities, and cost approximations. Redox potentials vs. Li/LiF for direct reaction pairs ranged from −0.92 V (Ca 5 (PO 4 ) 3 F/Ca 5 (PO 4 ) 3 ) to 5.77 V (LiAgF 6 / LiAgF 4 ) with an average of 2.9 V. Specific capacity ranged from 6.4 mAh/g (RbSnF 3 /RbSn 2.94 ) to 758 mAh/g (NClOF 4 /NClO) with an average of 150 mAh/g. Figure  2a,b illustrate the relationship between energy density (Wh/kg) and log 10 ($/mol of mobile F) with a colorimetric scale based on percent expansion for each pair. Log 10 ($/mol of mobile F) is used rather than $/mol to visually counteract the Pareto-like distribution of low-cost materials and account for charge transfer capacity. Structures are distributed along the cost axis with a range that spans five orders of magnitude. Most structures have energy densities between 0–900 Wh/kg with moderate expansion between 7–40%. Figure  2b is a zoomed in view of 2a at the desired property overlap of high energy density and low price with points identified by the fluorinated structure and fluoride content of the defluorinated structure.

Cathodes demonstrating a direct reaction between fluorinated/defluorinated pairs. All 168 pairs are shown in ( a ). In ( b ) the graph is zoomed in to highlight the high energy density and low-cost materials. Each pair is identified by the fluorinated structure and “F x ” which indicates the fluoride content of the defluorinated structure. The volumetric expansion of each pair is indicated by the color scale. Values of LiCoO 2 (LIB cathode) are also included for comparison.

Some fluorinated structures appear more than once with different defluorinated structures, such as CaNiF 6 /CaNiF 5 and CaNiF 6 /CaNiF 4 . The presence of these multi-redox capable fluorinated structures highlights differences in chemical potential along a given defluorination pathway. When these materials are present, they are likely to also exhibit a multistep voltage profile. This is observed in the Ca-Ni-F system, where CaNiF 6 /CaNiF 5 is 5.50 V vs. Li/LiF, CaNiF 5 /CaNiF 4 is 4.78 V, and CaNiF 6 /CaNiF 4 is 5.14 V. Although the two-electron transfer of CaNiF 6 /CaNiF 4 pair is likely kinetically complicated compared to the single-electron transfer of the two former pairs, the variations in calculated potentials appear systematic. This type of consideration is expected to play an important role in cathode performance. Our dataset allows for straightforward identification of these and other types of interesting trends.

Structural factors must also be considered in assessing the viability of candidates. Although the NClOF 4 /NClO, S(OF) 2 /SO 2 , and As(BrF 2 ) 3 /AsBr 3 pairs shown in 2b may seem promising, these materials are molecular crystals. These crystals likely lack the conductivity and mechanical stability needed to function as an electrode. Thus, these graphs provide only a snapshot of some properties and should not be taken as the only important criteria. Metrics for the common LIB cathode LiCoO 2 are also displayed on the graph to orient the reader. The theoretical energy density for LiCoO 2 is calculated in the same manner as the energy densities for the fluorination pairs, while the experimental energy density for LiCoO 2 references current literature values 3 . The discrepancy in energy density between the theoretical and experimental values of LiCoO 2 has been attributed to the incomplete deintercalation of Li from LiCoO 2 , which is also accounted for in the cost calculation 25 .

Although our dataset may encourage researchers to focus on materials with energy densities above those of current LIB technology, we also note that other characteristics can be important. These include ionic and electrical conductivity, chemical compatibility with an electrolyte, electrochemical stability, and material recyclability. Some of these additional criteria are also included in our dataset and we encourage researchers to evaluate the dataset holistically. On a broader scale, we hope that this dataset can be used to guide experimental selection of promising new FIB cathodes.

The dataset was produced using the Simulated Materials Ecosystem (Simmate) 26 and Materials Project API 24 . Simmate combines many crystal structure databases in one software package, including Materials Project, the Crystallography Open Database (COD) 27 , the Joint Automated Repository for Various Integrated Simulations (JARVIS) 28 , and the Open Quantum Materials Database (OQMD) 29 . At the time of writing, the Materials Project database contains over 145,000 crystal structures. The Materials Project database (via Simmate) was initially filtered to include all fluoride-containing structures with more than two elements and a hull energy less than or equal to 75 meV (6,525 structures). This cut-off was chosen based on known errors in DFT formation enthalpies and is discussed further in Technical Validation. To ensure that each composition was represented solely by the most stable phase, these structures were sorted by ascending hull energy and entries after the first occurrence of a given reduced formula were excluded. This list comprised the fluorinated half of all possible fluorinated/defluorinated pairs (4,389 structures).

Complete defluorination

A copy of each fluorinated entry was made, and all fluorine atoms were removed from the copied structure. This represented the other half of a possible fluorinated/defluorinated pair. The reduced formula of the defluorinated copy was then compared to the full Materials Project database. If an entry on Materials Project had the same reduced formula and was within 75 meV of hull, the entry was identified as a possible match. Multiple phases of the same composition also appeared during this step and were addressed in a similar manner as above to identify the most stable phase. There were 425 fluorinated/fully defluorinated pairs identified after this step.

Partial defluorination

Identification of partially defluorinated structure pairs was more involved than complete defluorination, as structural compositions along the full defluorination pathway had to be considered. The Materials Project database was searched for each entry in the initial fluorinated list, where structures with the same elements as the fluorinated entry, with the same ratios of non-fluoride elements, and within 75 meV of hull, were identified as possible defluorinated pairs. For structures with identical compositions, we filtered the dataset to select the lowest energy phase. This resulted in 382 fluorinated/partially defluorinated pairs. Thus, a total of 807 fluorinated/defluorinated pairs were taken forward through the remaining analyses.

Disproportionation reactions

The ternary phase diagram of a three-element system is characterized by nodes and tie-lines. Nodes are specific stable (or metastable) structures and tie-lines represent two-phase equilibria between these structures 30 . When a fluorinated/defluorinated pair is identified, it becomes imperative to check the associated phase diagram for a tie-line connecting the two, which shows that there is a direct reaction between the two phases. In the absence of a direct reaction, the fluorinated/defluorinated pair will disproportionate into two or more additional phases at global compositions that are intermediate between the two pairs. To illustrate these direct and indirect reactions, in Fig.  3 we show the phase diagrams and reaction coordinates for two possible fluorinated/defluorinated systems. It is useful to interpret the tie-line ( 3a ) and dotted-line ( 3b ) connecting the two fluorinated/defluorinated structures on the phase diagram as top-down views of reaction coordinates. Each diagram and reaction coordinate shows an example of a direct ( 3a,c , KBrF 4 /KBr) and indirect ( 3b,d , NaBiF 6 /NaBi) reaction. In 3a the KBrF 4 /KBr pair has a tie-line between the two target structures (circled in green), indicating that the structures convert from one to the other as fluorine content changes via a direct reaction. This is reflected in the interface reaction coordinate ( 3c ) with a straight, horizontal line indicating that the pair does not decompose into other phases. However, there is no tie-line connecting the NaBiF 6 /NaBi pair ( 3b , dotted line drawn in to highlight where a tie-line would exist). In fact, there are two other tie-lines that lie between the pair. This means that at global compositions between NaBiF 6 and NaBi, the system will at least partially disproportionate into NaF, BiF 3 , and Bi. The interface reaction coordinate ( 3d ) confirms that these disproportionation reactions are thermodynamically favourable, indicated by the decrease in reaction energy per atom. Once disproportionation occurs, the presence of multiple heterogeneous phases makes it less likely to form the desired product (eg NaBi), even if the global composition exactly matches NaBi. In this event, the amount of active material and the cathode’s cyclability will decrease.

Examples of ( a,c ) direct and ( b,d ) indirect interface reactions for fluorinated/defluorinated structure pairs. In ( a ) there is a single tie-line connecting the fluorinated (KBrF 4 ) and defluorinated (KBr) structures. In ( b ) the drawn-in dotted-line between NaBiF 6 and NaBi crosses over the tie-lines connecting NaF/BiF 3 and NaF/Bi, leading to disproportionation to the phases on either end of the crossed tie-lines as F is removed. The interface reaction coordinates (c/d) reflect these predictions.

To assess each fluorinated/defluorinated pair for the presence of direct or indirect reactions, we used pymatgen’s interface reaction function 31 . This function used the fluorinated and defluorinated structure pair as the two reactants. If there was no thermodynamically favorable reaction between the pair, the function gave the two original structures as “products” of the reaction. This indicated a direct reaction. If an indirect (disproportionation) reaction occurred, the function returned a list of disproportionation products. Of the 807 pairs, 168 had direct reactions. The first 58 of these were complete defluorination pairs, which was 14% of the original 425 complete defluorination pairs. The remaining 110 direct reactions were partial defluorination pairs, or 29% of the original 382 partial defluorination pairs.

Relevant properties were calculated for the 168 direct reaction structure pairs:

It is known that open circuit voltages can be predicted for lithium-ion battery materials using energies calculated from DFT + U methods 32 . It is common to refer to voltages against metallic lithium in these systems, which can be considered the natural limit for the usability of a component in a lithium-ion battery. In fluoride-ion batteries, F 2 can be used analogously to calculate open circuit voltages for materials in these systems 23 . These potentials can be calculated for materials by using a hypothetical F 2 electrode according to the following reaction:

While this reaction is useful theoretically, the realization of a gaseous F 2 electrode is unlikely. Moreover, as written, the potentials obtained are oxidation potentials rather than reduction potentials. To provide a more conventional perspective, we also calculate potentials using the Li/LiF pair as an anode according to:

For this reaction, a good cathode material corresponds to a high voltage. The voltages for these two reactions can be calculated starting from the Nernst equation:

Where ΔG rxn is the change in Gibbs free energy of the reaction (J/mol), x is the number of fluoride ions transferred, and F is Faraday’s constant. Volume (PΔV rxn ) and entropic (TΔS rxn ) effects can be neglected for the calculation of ΔG rxn (=ΔU rxn  + PΔV rxn – TΔS rxn ) because PΔV rxn is on the order of 10 −5  eV and TΔS rxn is on the scale of thermal energy, which are both much smaller than ΔU rxn (~10 1  eV). Thus, ΔG rxn can be reasonably obtained from the change in internal energy (ΔU rxn ) 33 , 34 , 35 . The Materials Project calculates internal energy for every entry in its database using DFT + U, so ΔG rxn can be calculated from these values for (1) and (2) respectively according to:

where U y is the internal energy of each compound. Because Materials Project provides internal energy values in eV rather than J, Faraday’s constant can be dropped from (3). Thus, potentials vs. F 2 and vs. Li/LiF were calculated from -ΔG rxn /x. These oxidation potentials range from −0.35 to 7.07 V vs. F 2 and the reduction potential range from −0.92 to 6.50 V vs. Li/LiF. We use the potentials vs. Li/LiF for energy density calculations. Graphite and LiC 6 were used instead of Li and LiF to calculate the potential for LiCoO 2 /CoO 2 (LIB cathode).

Volume per fluorine (Å 3 )

Volume per fluoride was calculated using the volume per formula unit of the fluorinated structure divided by the difference in fluorine atoms between the fluorinated and defluorinated structures.

Percent expansion

The expansion from the defluorinated to fluorinated structure was calculated by dividing the fluorinated volume per formula unit by the defluorinated volume per formula unit, subtracting 1, and then multiplying by 100%.

Gravimetric capacity (mAh/g)

The gravimetric capacity for each fluorinated structure was calculated according to Faraday’s Law:

Where n is the number of charge carriers (fluoride ions), F is Faraday’s constant (96,485.3 C/mol), C is a conversion factor (3.6 C/mAh), and MW is the molecular weight of the fluorinated structure in g/mol.

Gravimetric energy density (Wh/kg)

The gravimetric energy density was obtained by multiplying the gravimetric capacity by voltage.

Volumetric energy density (Wh/L)

The volumetric energy density was calculated by multiplying the gravimetric energy density by the density of the fluorinated material.

Cost analysis

A cost analysis was done for each material using pymatgen’s cost module. Costs were not calculated for Rb 2 UF 7 due to issues with the module in calculating a phase diagram containing U. For readers interested in replicating these results, column headers must be deleted from the ‘costdb_elements_new.csv’ file before using for the analysis to work properly.

Transport barrier (eV)

When data was available, the activation energy for fluoride transport is presented 36 .

The difference in atoms per formula unit between each structure pair, which is used to calculate the number of fluorides transferred and other properties, assumes that each reduced formula has the same number of each type of non-F atoms. This is not true for all structures, however. Therefore, we counted the number of non-fluoride atoms in each pair and rescaled the reduced formulas so that the number of non-fluoride atoms remained unchanged.

Several 4- and 5-element containing pairs were also identified including Ca 5 (PO 4 ) 3 F, Ca 5 (VO 4 ) 3 F, Pb 5 (PO 4 ) 3 F, Pb 5 (VO 4 ) 3 F, LiVPO 4 F, LiMnPO 4 F, LiFePO 4 F, CeAsO 4 F, BaAlGeF, TmSeO 3 F, LuSeO 3 F, LiCrPO 4 F, Sr 2 FeO 3 F, Ca 6 Al 3 (AlO 4 ) 4 F, Na 3 MoO 4 F, YSeO 3 F, Li 2 CoO 2 F, TiH 8 (NF 3 ) 2 , ReSbOF 10 , MgAs 2 (XeF 9 ) 2 . The filtering criteria worked correctly for these structures and were left in as additional datapoints.

Data Records

The produced datasets are available in Figshare 37 and at the ternary_f_cathodes page on Github. The datasets are provided as two CSV files, one containing all 807 pairs and one containing the 168 direct reaction pairs. The modified cost spreadsheet is also provided. The python script file used to create the dataset is available on the Github page. Table  1 provides the list of column titles in the files and a description of each.

Technical Validation

The data presented is taken from Simmate and Materials Project databases or calculated directly according to the methods described above. Many of the reported properties rely on DFT internal energy calculations, which are known to incorporate systematic and random error. Particularly, the approximate DFT functionals result in errors due to changes of electron self-interaction in localized transition metal states. This originates from changes in oxidation state upon product formation from discrete reactants. Known binding errors of diatomic molecules (F 2 , O 2 , N 2 , Cl 2 , H 2 ) using LDA and GGA functionals further complicate the calculation of accurate internal energies. This is mitigated in transition metal cations by applying a Hubbard U value to d or f orbitals and constant energy corrections based on experimental comparison for anionic species (F − , O 2− , S 2− …). Materials Project employs corrections for both errors with a mix of GGA and GGA + U functionals as well as anion-specific corrections 38 , 39 , 40 , 41 , 42 . Our calculations used these corrections, which reduces the error in GGA or GGA + U formation enthalpies from ≈ 175–450 meV/atom (uncorrected) to ≈ 45–55 meV/atom (corrected). The magnitude of these energies supported the chosen filtering value of 75 meV above hull, slightly above the noted correction error. The calculation of cathode potential relies on internal energies of multiple structures, which somewhat increases the total error. These errors are small compared to the potentials that are spanned across all cathodes, thereby supporting our ability to sort and rank cathode according to the predicted potential. The uncertainties of activation energies for F-ion conduction were described previously 36 .

Adaptations were made to pymatgen’s cost module for more accurate price approximations. Original module reference prices are based on pure elemental forms, which misrepresent the predicted costs because many elements can be obtained as salts for a much lower cost. Therefore, all elemental costs are obtained from the Wikipedia “Prices of chemical elements” page, which more accurately takes this into account. The prices listed on Wikipedia are primarily average market prices for bulk trade, but when this data is not available the price of a compound is used, per mass of the given element.

Code availability

All code used is open source and available at https://github.com/donmctaggart15/ternary_f_cathodes . The datasets are provided on the same repository. We recommend reading the Simmate, Materials Project API, and pymatgen documentation to follow filtering syntax.

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Acknowledgements

We are grateful for constructive feedback from other group members in reviewing the project and manuscript.

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Don H. McTaggart, Jack D. Sundberg, Lauren M. McRae & Scott C. Warren

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Don McTaggart led the writing of the paper and created the filtering scripts and datasets. Jack Sundberg created Simmate and provided suggestions for the interface reaction function, as well as coding advice. Lauren McRae contributed to project conception and direction. Scott Warren provided coding advice and conceptualization for the project.

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McTaggart, D.H., Sundberg, J.D., McRae, L.M. et al. Assessing ternary materials for fluoride-ion batteries. Sci Data 10 , 90 (2023). https://doi.org/10.1038/s41597-023-01954-1

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Journal of Materials Chemistry A

Fluoride ion batteries – past, present, and future.

* Corresponding authors

a Universität Stuttgart, Institut für Materialwissenschaft, Chemische Materialsynthese, Heisenbergstraße 3, Stuttgart, Germany E-mail: [email protected]

b Université Paris-Saclay, CEA, CNRS, NIMBE, LEEL, Gif-sur-Yvette, France

c Institute of Particle Technology, Technical University of Braunschweig, Volkmaroder Str. 5, Braunschweig, Germany

d College of Engineering, Swansea University, Fabian Way, Swansea, UK E-mail: [email protected]

Fluoride-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.

• This article is part of the themed collection: Journal of Materials Chemistry A Recent Review Articles

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M. A. Nowroozi, I. Mohammad, P. Molaiyan, K. Wissel, A. R. Munnangi and O. Clemens, J. Mater. Chem. A , 2021,  9 , 5980 DOI: 10.1039/D0TA11656D

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Approaches to new fluoride ion sources

Emsley, Julian J. (1988) Approaches to new fluoride ion sources. Masters thesis, Durham University.

Fluoride ion sources have been surveyed and perfluoroalkyl anions and hindered amine/HF adducts prepared and investigated as reagents. The perfluoroalkyl anions (I) and (II) have been used in an attempt to fluorinate various organic compounds such as alkyl halides, alkyl tosylates, aryl halides and acetyl chloride. The following new compounds have been synthesised and identified by glc-mass spec and, where possible, (^19)F nmr. These arose from reaction of the substrate with the perfluoroalkyl anion rather than with F(^-). Preliminary work on hindered amine bases, particularly proton sponge and tri-n-octylamine, with HF was undertaken, these being studied as possible soluble fluoride ion sources. Solid adducts were obtained in most cases from ether solutions and they were shown to behave as fluoride ion sources under various conditions.

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Home > Graduate College > Theses > 4397

Masters Theses

Studies involving modification of the megregian method of fluoride determination and application to fluoride balance studies in infants.

Gene R. Wright

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Dr. Robert Nagler

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Lillian H. Meyer

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Introduction

At the request of Dr. Frederick Margolis, M.D., and in association with The Upjohn Company, this research problem was initiated as a participation in the investigation of whether or not fluoride ingested as a constituent of the Upjohn 47-M liquid vitamin preparation is retained in an infant's body to the same extent as is fluoride ingested as the sodium salt by itself--either in solution or in tablet form. The retention patterns may be studied indirectly by measuring the amounts of fluoride excreted in the urine and in the feces during each of a series of equal time intervals after administration of the various fluoride preparations.

Because of experience in these laboratories it was decided to attempt to use the method of fluoride analysis developed by Megregian (44). His procedure basically involves the determination of fluoride spectrophotometrically by reduction of the degree of complex formation between eriochrome cyanine R and zirconium by preferential complexing of the latter with fluoride. To accomplish the objectives of this study it was necessary to exhaustively examine various aspects of the Megregian method.

In order to link this thesis project to the total clinical investigation, there is presented herein a brief history of the samples prior to their receipt for analysis in these laboratories. Also reported is our treatment of the samples prior to application of the Megregian method.

Recommended Citation

Wright, Gene R., "Studies Involving Modification of the Megregian Method of Fluoride Determination and Application to Fluoride Balance Studies in Infants" (1962). Masters Theses . 4397. https://scholarworks.wmich.edu/masters_theses/4397

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Reduction of fluoride in waste water effluent from a semiconductor facility : a case study.

Sarah Bilimoria

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Master of Science in Environmental Management (MSEM)

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Bilimoria, Sarah, "Reduction of fluoride in waste water effluent from a semiconductor facility : a case study" (1992). Master's Theses . 834. https://repository.usfca.edu/thes/834

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Course - master's thesis in general psychology - psy3915, course-details-portlet, psy3915 - master's thesis in general psychology, examination arrangement.

Examination arrangement: Master thesis and oral examination Grade: Letter grades

Course content

The Master's thesis is an academic in-depth work within general psychology, where the student writes a scientific document in line with relevant guidelines in regards to structure and theory. The subject of the master's thesis, which can be either experimental or purely theoretical, should be decided in consultation with a competent supervisor.

Students apply to have their thesis topic approved and a supervisor appointed by filling in a master's thesis agreement. Here the student must include a project description in which the research purpose, theoretical grounding, methodological approach and practical implementation are explained. Check with the department regarding the deadline for submitting this master's thesis agreement. The institute is responsible to assess and approve both topic and supervisor.

Learning outcome

The student:

• has advanced knowledge within general psychology and specialized insight into a limited area

• has in-depth knowledge of theory and method in psychological research and of how a scientific project is carried out

• has in-depth knowledge of what is required of a scientific text in psychology, including advanced knowledge of APA style

• has in-depth knowledge of conducting professional argumentation with the use of theory, research, method and method choice and own data and analysis

• has advanced knowledge of quality requirements for research, including adherence to research ethical guidelines and principles

• can analyze and relate critically to various sources of information and use these to structure and formulate professional reasoning

• can analyze existing theories, methods and interpretations within the subject area and work independently with practical and theoretical problem solving

• can use relevant methods for research and professional development independently

• can design and carry out an independent, limited research project under supervision and in line with applicable research ethics norms

• can analyze professional issues and understand complex research data

• can communicate scientific findings - both in writing and orally.

• can find out and relate critically to various sources of information

• can familiarize themselves with literature that is relevant for carrying out research within a limited area of ​​psychology

• can communicate the research work

• The student can formulate a precise and clear problem with relevance for psychological theory or practice and present a well-considered rationale for the choice and use of method and literature

• The student can think critically and draw scientific conclusions based on research

• The student can use the APA standard for scientific publishing

General competence:

• can analyze relevant professional, professional and research ethical issues

• can apply their knowledge and skills in new areas to carry out advanced tasks and projects

• can convey extensive independent work and masters the subject's forms of expression

• can communicate about professional issues, analyzes and conclusions within psychology

• can apply their knowledge to find answers to relevant issues in psychology

• can convey extensive independent research work within psychology's forms of expression

• can communicate psychological research

Learning methods and activities

Own work with compulsory guidance.

The work on the master's thesis will be a combination of independent activity and work under supervision. The academic guidance must ensure that the student is provided with the necessary knowledge, that all parts of the work have a satisfactory quality (e.g. when collecting and processing data) and that the project as a whole takes place in line with current research ethical guidelines.

The master's thesis seminar in the second semester consists of information on how to find a topic, a presentation of potential supervisors and the design of a project description. The master's thesis seminar in the third semester consists of a lecture that gives tips and advice on the process of writing a master's thesis and a seminar where the student presents his topics and receives constructive feedback from other students and staff. Participation in the master's thesis seminars must be approved before submission of the master's thesis can take place.

Compulsory assignments

• Mandatory participation in the thesis seminar

Further on evaluation

The master's thesis is assessed with letter grades (A-F). The assignment is delivered individually or as a joint work. If the thesis is delivered as joint work, a document describing the individual candidate's contribution must be attached. This will normally involve an individual assessment of the candidates.

The students give a final oral presentation and are examined on the assignment. The oral examination consists of an explanation from the student of approx. 10 minutes and a subsequent questioning. Oral examination is used to adjust the grade. The student can choose an open or closed exam. If it is an open examination, the audience may be present during the examination, if it is a closed examination, only the committee and the student are present.

Check with the institute for the deadline for submitting the project description and master's thesis.

Specific conditions

Admission to a programme of study is required: Psychology (MPSY)

Required previous knowledge

All examinations in the Masters in General Psychology should be passed before the thesis can be submitted.

Version: 1 Credits:  45.0 SP Study level: Second degree level

Term no.: 1 Teaching semester:  AUTUMN 2024

Term no.: 2 Teaching semester:  SPRING 2025

Language of instruction: English, Norwegian

Location: Trondheim

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Department with academic responsibility Department of Psychology

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Examination arrangement: master thesis and oral examination.

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