Anna Kallistova

Oxides of Nb with Wadsley-Roth shear structures comprise a family of stable, high-rate anode materials for Li-ion batteries. A particular pair of them offers the unusual opportunity to test how important metallic conduction of the starting electrode is for electrode performance. The selected pair of compounds with similar 4 × 3 Wadsley-Roth block structures are insulating Ti₂Nb₁₀O₂₉ and metallic Nb₁₂O₂₉. A combination of diffraction, electrochemistry, magnetic measurements, and entropic potential measurements is employed to establish key findings for these two anode materials. We find that starting with a metallic oxide is not especially advantageous over a comparable material that readily transitions into a metallic state upon lithiation. Second, the rate performance appears to be dictated by ion mobility, and atomic Ti/Nb disorder in Ti₂Nb₁₀O₂₉ contributes to improved capacity retention at high rates by suppressing Li-ion ordering. However, subtle details in the nature of redox processes make Nb₁₂O₂₉ a slightly better electrode material for long-term cycling at slower rates.

Lithium-ion battery (LIB) recycling aims to recover valuable materials present within end-of-life electrochemical cells. Industrial recycling processes produce “black mass” from recycling feedstock from which desirable materials can be recollected. Spent cells first undergo mechanical shredding and sieving, and organic components are removed by thermal treatment (pyrolysis) before hydrometallurgical processing is employed to recover the constituent elements. Black mass may contain a range of reaction products, formed at high temperature during pyrolysis, due to the compositionally complex and inhomogeneous nature of recycling feedstock. These products, however, may have different elemental compositions, ratios, and structures, making efficient hydrometallurgical recovery difficult. Here, we present three distinct, industrially sourced black mass samples containing Li­(Ni _x Mn _y Co _z )­O₂ (x + y + z = 1) positive electrodes of varying composition. We employ a suite of structural and compositional characterization techniques, including synchrotron X-ray and neutron powder diffraction and element specific analysis (X-ray photoelectron spectroscopy, X-ray fluorescence spectroscopy, energy dispersive X-ray spectroscopy, inductively coupled plasma optical emission spectroscopy), to identify phases formed during commercial treatment of recycling feedstocks and how their relative quantities are affected by process order. Additionally, we also present results of studies on simpler model systems to better identify minor phases present within the complex recycling feedstocks and to direct the efficient recovery of valuable components.

We report on metalorganic chemical vapor deposition (MOCVD) growth of controllably Si-doped 4.5 μm thick β-Ga2O3 films with electron concentrations in the 1015 cm−3 range and record-high room temperature Hall electron mobilities of up to 200 cm2/Vs, reaching the predicted theoretical maximum room temperature phonon scattering-limited mobility value for β-Ga2O3. Growth of the homoepitaxial films was performed on Fe-doped (010) β-Ga2O3 substrates at a growth rate of 1.9 μm/h using TEGa as the Gallium precursor. To probe the background electron concentration, an unintentionally doped film was grown with a Hall concentration of 3.43 × 1015 cm−3 and Hall mobility of 196 cm2/Vs. Growth of intentionally Si-doped films was accomplished by fixing all growth conditions and varying only the silane flow, with controllable Hall electron concentrations ranging from 4.38 × 1015 to 8.30 × 1015 cm−3 and exceptional Hall mobilities ranging from 194 to 200 cm2/Vs demonstrated. C-V measurements showed a flat charge profile with the ND+–NA− values correlating well with the Hall-measured electron concentration in the films. SIMS measurements showed the silicon atomic concentration matched the Hall electron concentration with carbon and hydrogen below detection limit in the films. The Hall, C-V, and SIMS data indicate the growth of high-quality 4.5 μm thick β-Ga2O3 films and controllable doping into the mid 1015 cm−3 range. These results demonstrate MOCVD growth of electronics grade record-high mobility, low carrier density, and thick β-Ga2O3 drift layers for next-generation vertical β-Ga2O3 power devices.

Hybrid halide perovskites AM^IIX₃ (A = ammonium cation, M^II = divalent cation, X = Cl, Br, I) have been extensively studied but have only previously been reported for the divalent carbon group elements Ge, Sn, and Pb. While they have displayed an impressive range of optoelectronic properties, the instability of Ge^II and Sn^II and the toxicity of Pb have stimulated significant interest in finding alternatives to these carbon group-based perovskites. Here, we describe the low-temperature solid-state synthesis of five new hybrid iodide perovskites centered around divalent alkaline earth and lanthanide elements, with the general formula AM^III₃ (A = methylammonium, MA; M^II = Sr, Sm, Eu, and A = formamidinium, FA; M^II = Sr, Eu). Structural, calorimetric, optical, photoluminescence, and magnetic properties of these materials are reported.

Halide double perovskites [A₂M^IM^IIIX₆] are an important class of materials that have garnered substantial interest as non‐toxic alternatives to conventional lead iodide perovskites for optoelectronic applications. While numerous studies have examined chloride and bromide double perovskites, reports of iodide double perovskites are rare, and their definitive structural characterization has not been reported. Predictive models have aided us here in the synthesis and characterization of five iodide double perovskites of general formula Cs₂NaLnI₆ (Ln=Ce, Nd, Gd, Tb, Dy). The complete crystal structures, structural phase transitions, optical, photoluminescent, and magnetic properties of these compounds are reported.

Halide double perovskites [A₂M^IM^IIIX₆] are an important class of materials that have garnered substantial interest as non‐toxic alternatives to conventional lead iodide perovskites for optoelectronic applications. While numerous studies have examined chloride and bromide double perovskites, reports of iodide double perovskites are rare, and their definitive structural characterization has not been reported. Predictive models have aided us here in the synthesis and characterization of five iodide double perovskites of general formula Cs₂NaLnI₆ (Ln=Ce, Nd, Gd, Tb, Dy). The complete crystal structures, structural phase transitions, optical, photoluminescent, and magnetic properties of these compounds are reported.

This work demonstrates the first successful electrochemical cycling of a redox-active boron cluster-based material in the solid state. Specifically, we designed and synthesized an ether-functionalized dodecaborate cluster, B₁₂(OCH₃)₁₂, which is the smallest redox-active building block in the B₁₂(OR)₁₂ family. This species can reversibly access four oxidation states in solution, ranging from a dianion to a radical cation. We show that a chemically isolated and characterized neutral [B₁₂(OCH₃)₁₂]⁰ cluster can be utilized as a cathode active material in a PEO-based rechargeable all-solid-state cell with a lithium metal anode. The cell exhibits an impressive active material utilization close to 95% at C/20 rate, a high Coulombic efficiency of 96%, and reversibility, with only 4% capacity fade after 16 days of cycling. This work represents a conceptual departure in the development of redox-active components for electrochemical storage and serves as an entry point to a broader class of borane-based materials.

This work demonstrates the first successful electrochemical cycling of a redox-active boron cluster-based material in the solid state. Specifically, we designed and synthesized an ether-functionalized dodecaborate cluster, B12(OCH3)12, which is the smallest redox-active building block in the B12(OR)12 family. This species can reversibly access four oxidation states in solution, ranging from a dianion to a radical cation. We show that a chemically isolated and characterized neutral [B12(OCH3)12]0 cluster can be utilized as a cathode active material in a PEO-based rechargeable all-solid-state cell with a lithium metal anode. The cell exhibits an impressive active material utilization close to 95% at C/20 rate, a high Coulombic efficiency of 96%, and excellent reversibility, with only 4% capacity fade after 16 days of cycling. This work represents a conceptual departure in the development of redox-active components for electrochemical storage and serves as an entry point to a broader class of borane-based materials.

Objectives: The hierarchical structure of enamel gives insight on the properties of enamel and can influence its strength and ultimately caries experience. Currently, past caries experience is quantified using the decayed, missing, filled teeth/decayed, missing, filled surface (DMFT/DMFS for permanent teeth; dmft/dmfs for primary teeth), or international caries detection and assessment system (ICDAS) scores. By analyzing the structure of enamel, a new measurement can be utilized clinically to predict susceptibility to future caries experience based on a patient’s individual’s biomarkers. The purpose of this study was to test the hypothesis that number of prisms by square millimeter in enamel and average gap distance between prisms and interprismatic areas, influence caries experience through genetic variation of the genes involved in enamel formation. Materials and Methods: Scanning electron microscopy (SEM) images of enamel from primary teeth were used to measure (i) number of prisms by square millimeter and interprismatic spaces, (ii) prism density, and (iii) gap distances between prisms in the enamel samples. The measurements were tested to explore a genetic association with variants of selected genes and correlations with caries experience based on the individual’s DMFT+ dmft score and enamel microhardness at baseline, after an artificial lesion was created and after the artificial lesion was treated with fluoride. Results: Associations were found between variants of genes including ameloblastin, amelogenin, enamelin, tuftelin, tuftelin interactive protein 11, beta defensin 1, matrix metallopeptidase 20 and enamel structure variables measured (number of prisms by square millimeter in enamel and average gap distance between prisms and interprismatic areas). Significant correlations were found between caries experience and microhardness and enamel structure. Negative correlations were found between number of prisms by square millimeter and high caries experience (r value= −0.71), gap distance between prisms and the enamel microhardness after an artificial lesion was created (r value= −0.70), and gap distance between prisms and the enamel microhardness after an artificial lesion was created and then treated with fluoride (r value= −0.81). There was a positive correlation between number of prisms by square millimeter and prism density of the enamel (r value = 0.82). Conclusions: Our data support that genetic variation may impact enamel formation, and therefore influence susceptibility to dental caries and future caries experience. Clinical Relevance: The evaluation of enamel structure that may impact caries experience allows for hypothesizing that the identification of individuals at higher risk for dental caries and implementation of personalized preventative treatments may one day become a reality.

Objectives: The hierarchical structure of enamel gives insight on the properties of enamel and can influence its strength and ultimately caries experience. Presently, past caries experience is quantified using the decayed, missing, filled teeth/decayed, missing, filled surface (DMFT/DMFS for permanent teeth; dmft/dmfs for primary teeth) or international caries detection and assessment system (ICDAS) scores. By analyzing the structure of enamel, a new measurement can be utilized clinically to predict susceptibility to future caries experience based on a patient’s individual’s biomarkers. The purpose of this study was to test the hypothesis that number of prisms by square millimeter in enamel and average gap distance between prisms and interprismatic areas, influence caries experience through genetic variation of the genes involved in enamel formation. Materials and Methods: Scanning electron microscopy (SEM) images of enamel from primary teeth were used to measure number of prisms by square millimeter and interprismatic spaces, prism density and gap distances between prisms in the enamel samples. The measurements were tested to explore a genetic association with variants of selected genes and correlations with caries experience based on the individual’s DMFT+ dmft score and enamel microhardness at baseline, after an artificial lesion was created and after the artificial lesion was treated with fluoride. Results: Associations were found between variants of genes including ameloblastin, amelogenin, enamelin, tuftelin, tuftelin interactive protein 11, beta defensin 1, matrix metallopeptidase 20 and enamel structure variables measured. Significant correlations were found between caries experience and microhardness and enamel structure. Negative correlations were found between number of prisms by square millimeter and high caries experience (r value= -0.71), gap distance between prisms and the enamel microhardness after an artificial lesion was created (r value= -0.70), and gap distance between prisms and the enamel microhardness after an artificial lesion was created and then treated with fluoride (r value= -0.81). There was a positive correlation between number of prisms by square millimeter and prism density of the enamel (r value= 0.82). Conclusions: our data support that genetic variation may impact enamel formation, and therefore influence susceptibility to dental decay and future caries experience. Clinical Relevance: The evaluation of enamel structure that may impact caries experience allows for hypothesizing that the identification of individuals at higher risk for dental caries and implementation of personalized preventative treatments may one day become a reality.