Browsing by Author "Dose, WM"

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    Kinetics of the thermally-induced structural rearrangement of γ-MnO2
    (ACS Publications, 2014-09-17) Dose, WM; Sharma, N; Webster, NAS; Peterson, VK; Donne, SW
    This work presents a temperature-dependent and time-resolved X-ray and neutron diffraction study of the thermally induced structural rearrangement of γ-MnO2. Here, we study electrochemically prepared γ-MnO2, the manganese dioxide phase used in the majority of battery applications, which we find to be ∼64% ramsdellite [a = 4.4351(6) Å, 9.486(2) Å, c = 2.8128(7) Å, and V = 118.33(3) Å3] and ∼36% pyrolusite [a = 4.718(3) Å, c = 2.795(2) Å, and V = 62.22(8) Å3]. Taking a deeper look at the kinetics of the structural rearrangement, we find two steps: a fast transition occurring within 4–8 min with a temperature-dependent ramsdellite to pyrolusite transformation (rate constant 0.11–0.74 min–1) and a slow transition over 4 h that densifies (with changes in unit cell and volume) the ramsdellite and pyrolusite phases to give structures that appear to be temperature-independent. This effectively shows that γ/β-MnO2 prepared in the range of 200–400 °C consists of temperature-independent structures of ramsdellite, unit cell a = 4.391(1) Å, b = 9.16(5) Å, c = 2.847(1) Å, and V = 114.5(6) Å3, and pyrolusite, unit cell a = 4.410(2) Å, c = 2.869(2) Å, and V = 55.79(4) Å3, with a temperature-dependent pyrolusite fraction between 0.45 and 0.77 and increasing with temperature. Therefore, we have linked the temperature and time of heat treatment to the structural evolution of γ-MnO2, which will aid the optimization of γ/β-MnO2 as used in Li-primary batteries. © 2014, American Chemical Society.
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    On disrupting the Na+-ion/vacancy ordering in P2-type sodium–manganese–nickel oxide cathodes for Na+-ion batteries
    (American Chemical Society, 2018-09-06) Gutierrez, A; Dose, WM; Borkiewicz, O; Guo, F; Avdeev, M; Kim, SJ; Fister, TT; Ren, Y; Bareño, J; Johnson, CS
    An investigation of the electrochemical and structural properties of layered P2–Na0.62Mn0.75Ni0.25O2 is presented. The effect of changing the Mn/Ni ratio (3:1) from what is found in Na0.67Mn0.67Ni0.33O2 (2:1) and consequently the introduction of a third metal center (Mn3+) was investigated. X-ray powder diffraction (in situ and ex situ) revealed the lack of Na+-ion/vacancy ordering at the relevant sodium contents (x = 0.33, 0.5, and 0.67). Mn3+ in Na0.62Mn0.75Ni0.25O2 introduces defects into the Ni–Mn interplane charge order that in turn disrupts the ordering within the Na-plane. The material underwent P2–O2 and P2–P2′ phase transitions at high (4.2 V) and low (∼1.85 V) voltages, respectively. The material was tested at several different voltage ranges to understand the effect of the phase transitions on the capacity retention. Interestingly, the inclusion of both phase transitions demonstrated comparable cycling performance to when both phase transitions were excluded. Last, excellent rate performance was demonstrated between 4.3 and 1.5 V with a specific capacity of 120 mA h/g delivered at 500 mA/g current density. © 2018 American Chemical Society
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    Rate and composition dependence on the structural–electrochemical relationships in P2–Na2/3Fe1–yMnyO2 positive electrodes for sodium-ion batteries
    (American Chemical Society, 2018-10-02) Dose, WM; Sharma, N; Pramudita, JC; Avdeev, M; Gonzalo, E; Rojo, T
    Structural–electrochemical compositional evolution of attractive cathode candidates for sodium-ion batteries is illustrated. Varying the Fe/Mn ratio plays a significant role in phase evolution, which ranges from a simple solid solution or two-phase transitions to more complex combinations and sequences of phase transitions dependent on the Na concentration. Further complexity is added by the kinetic limitations placed on the compositions with applied current and associated material utilization. This work provides a standardized set of electrochemical and structural data for members of the Na2/3Fe1–yMnyO2 series, exploring the phase evolution at a selected rate of 15 mA g–1, comparing this with literature data at various current rates, and focusing on the evolution of the y = 0.9 at higher and lower current rates. The y = 0.8 composition shows the highest capacity, while y = 0.9 shows slightly better capacity retention at 15 mA g–1. Structurally, the y = 0.8 features a solid-solution evolution throughout the charge–discharge process, while the y = 0.9 shows a solid solution and two-phase evolution, yet shows better capacity retention. Such studies illustrate how chemical tuning and electrochemical current influences structural evolution with sodium insertion/extraction and how this in turn influences electrochemical performance. © 2018 American Chemical Society
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    Structure–electrochemical evolution of a Mn-rich P2 Na 2/3 Fe 0.2 Mn 0.8 O2 Na-ion battery cathode
    (American Chemical Society, 2017-08-04) Dose, WM; Sharma, N; Pramudita, JC; Brand, HEA; Gonzalo, E; Rojo, T
    The structural evolution of electrode materials directly influences the performance of sodium-ion batteries. In this work, in situ synchrotron X-ray diffraction is used to investigate the evolution of the crystal structure of a Mn-rich P2-phase Na2/3Fe0.2Mn0.8O2 cathode. A single-phase reaction takes place for the majority of the discharge-charge cycle at ∼C/10, with only a short, subtle hexagonal P2 to hexagonal P2 two-phase region early in the first charge. Thus, a higher fraction of Mn compared to previous studies is demonstrated to stabilize the P2 structure at high and low potentials, with neither "Z"/OP4 phases in the charged state nor significant quantities of the P′2 phase in the discharged state between 1.5 and 4.2 V. Notably, sodium ions inserted during discharge are located on both available crystallographic sites, albeit with a preference for the site sharing edges with the MO6 octahedral unit. The composition Na∼0.70Fe0.2Mn0.8O2 prompts a reversible single-phase sodium redistribution between the two sites. Sodium ions vacate the site sharing faces (Naf), favoring the site sharing edges (Nae) to give a Nae/Naf site occupation of 4:1 in the discharged state. This site preference could be an intermediate state prior to the formation of the P′2 phase. Thus, this work shows how the Mn-rich Na2/3Fe0.2Mn0.8O2 composition and its sodium-ion distribution can minimize phase transitions during battery function, especially in the discharged state. © 2017 American Chemical Society.
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    Using in situ synchrotron x-ray diffraction to study lithium- and sodium-ion batteries: a case study with an unconventional battery electrode (Gd2TiO5)
    (Cambridge University Press, 2014-11-04) Pramudita, JC; Aughterson, RD; Dose, WM; Donne, SW; Brand, HEA; Sharma, N
    Designing materials for application as electrodes in sodium-ion batteries may require the use of unconventional materials to realize acceptable reversible sodium insertion/extraction capabilities. To design new materials simple electrochemical methods need to be coupled with other techniques such as in situ x-ray diffraction (XRD) to correlate the influence of electrochemical performance on a parameter that can be modified, e.g., the crystal structure of the material. Here we use in situ synchrotron XRD data on Gd2TiO5-containing cells to show the minor changes in reflection positions during discharge/charge that illustrates minimal volume expansion and contraction due to insertion/extraction reactions. These small changes correlate to the Gd2TiO5 anode material in both lithium- and sodium-ion batteries showing reversible capacities of ∼45 and ∼23 mA h/g after 20 cycles, respectively. Analysis of sodium location in the crystal structure shows a preference for sodium in the smaller channels along the c axis direction during the first discharge before moving to the larger channels at the charged state. Therefore, in this work, in situ studies highlight minimal structural changes with respect to volume expansion during electrochemical cycling and illustrate where sodium ions locate within the Gd2TiO5 structure. © 2014 Materials Research Society