| 11. |
- Fritze, Stefan, et al.
(author)
-
Magnetron sputtering of carbon supersaturated tungsten films-A chemical approach to increase strength
- 2021
-
In: Materials & design. - : Elsevier. - 0264-1275 .- 1873-4197. ; 208
-
Journal article (peer-reviewed)abstract
- Tungsten (W)-based materials attract significant attention due to their superior mechanical properties. Here, we present a chemical approach based on the addition of carbon (C) for increased strength via the combination of three strengthening mechanisms in W thin films. W:C thin films with C concentrations up to-4 at.% were deposited by magnetron sputtering. All films exhibit a body-centred-cubic structure with strong texture and columnar growth behaviour. X-ray and electron diffraction measurements suggest the formation of supersaturated W:C solid solution phases. The addition of C reduced the average column width from-133 nm for W to-20 nm for the film containing-4 at.% C. The column refinement is explained by a mechanism where C acts as re-nucleation sites. The W film is-13 GPa hard, while the W:C films achieve a peak hardness of-24 GPa. The W:C films are-11 GPa harder than the W film, which is explained by a combination of grain refinement strengthening, solid solution strengthening and increased dislocation density. Additional micropillar compression tests showed that the flow stress increased upon C addition, from-3.8 to-8.3 GPa and no brittle fracture was observed.
|
|
| 12. |
- Menon, Ashok S., et al.
(author)
-
A Crystallographic Reinvestigation of Li1.2Mn0.6Ni0.2O2
-
Other publication (other academic/artistic)abstract
- Despite substantial research interest, the crystallography of the promising Li-ion positive electrode material, Li1.2Mn0.6Ni0.2O2, remains disputed. The dispute is predicated on the description of the cationic arrangement in the structure, and multiple structure models have been proposed. This study attempts to provide a fresh perspective to this debate through a multi-scalar structural characterisation of Li1.2Mn0.6Ni0.2O2. Combining Bragg diffraction, transmission electron microscopy and magnetic measurements with reverse Monte Carlo analysis of total scattering data, a quantitative structural description of Li1.2Mn0.6Ni0.2O2 is developed and the existing single- and multi-phase structural descriptions of this compound have been unified. Furthermore, the merits and drawbacks of each technique is evaluated with respect to the crystallography of Li1.2Mn0.6Ni0.2O2 to explain the factors that have contributed to the lack of clarity pervading the structural description of this material. It is envisioned that a better understanding of the crystallography of Li1.2Mn0.6Ni0.2O2 contributes to harnessing the electrochemical potential of this compound.
|
|
| 13. |
- Menon, Ashok S., et al.
(author)
-
Influence of Synthesis Routes on the Crystallography, Morphology, and Electrochemistry of Li2MnO3
- 2020
-
In: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 12:5, s. 5939-5950
-
Journal article (peer-reviewed)abstract
- With the potential of delivering reversible capacities of up to 300 mAh/g, Li-rich transition-metal oxides hold great promise as cathode materials for future Li-ion batteries. However, a cohesive synthesis-structure-electrochemistry relationship is still lacking for these materials, which impedes progress in the field. This work investigates how and why different synthesis routes, specifically solid-state and modified Pechini sol-gel methods, affect the properties of Li2MnO3, a compositionally simple member of this material system. Through a comprehensive investigation of the synthesis mechanism along with crystallographic, morphological, and electrochemical characterization, the effects of different synthesis routes were found to predominantly influence the degree of stacking faults and particle morphology. That is, the modified Pechini method produced isotropic spherical particles with approximately 57% faulting and the solid-state samples possessed heterogeneous morphology with approximately 43% faulting probability. Inevitably, these differences lead to variations in electrochemical performance. This study accentuates the importance of understanding how synthesis affects the electrochemistry of these materials, which is critical considering the crystallographic and electrochemical complexities of the class of materials more generally. The methodology employed here is extendable to studying synthesis-property relationships of other compositionally complex Li-rich layered oxide systems.
|
|
| 14. |
- Menon, Ashok S., et al.
(author)
-
Synthesis-structure relationships in Li- and Mn-rich layered oxides : phase evolution, superstructure ordering and stacking faults
- 2022
-
In: Dalton Transactions. - : Royal Society of Chemistry. - 1477-9226 .- 1477-9234. ; 51:11, s. 4435-4446
-
Journal article (peer-reviewed)abstract
- Li- and Mn-rich layered oxides are promising positive electrode materials for future Li-ion batteries. The presence of crystallographic features such as cation-mixing and stacking faults in these compounds make them highly susceptible to synthesis-induced structural changes. Consequently, significant variations exist in the reported structure of these compounds that complicate the understanding of how the crystallographic structure influences its properties. This work investigates the synthesis-structure relations for three widely investigated Li- and Mn-rich layered oxides: Li2MnO3, Li1.2Mn0.6Ni0.2O2 and Li1.2Mn0.54Ni0.13Co0.13O2. For each compound, the average structure is compared between two synthetic routes of differing degrees of precursor mixing and four annealing protocols. Furthermore, thermodynamic and synthesis-specific kinetic factors governing the equilibrium crystallography of each composition are considered. It was found that the structures of these compounds are thermodynamically metastable under the synthesis conditions employed. In addition to a driving force to reduce stacking faults in the structure, these compositions also exhibited a tendency to undergo structural transformations to more stable phases under more intense annealing conditions. Increasing the compositional complexity introduced a kinetic barrier to structural ordering, making Li1.2Mn0.6Ni0.2O2 and Li1.2Mn0.54Ni0.13Co0.13O2 generally more faulted relative to Li2MnO3. Additionally, domains with different degrees of faulting were found to co-exist in the compounds. This study offers insight into the highly synthesis-dependent subtle structural complexities present in these compounds and complements the substantial efforts that have been undertaken to understand and optimise its electrochemical properties.
|
|
| 15. |
- Menon, Ashok S.
(author)
-
Synthesis–Structure–Property Relationships in Li- and Mn-rich Layered Oxides
- 2021
-
Doctoral thesis (other academic/artistic)abstract
- The commercialisation of Li-ion batteries over the last decade has provided additional impetus for the improvement of existing energy storage technologies. Towards this, a major portion of the global efforts includes exploratory research aimed at the development of new material chemistries. Aligning with this theme, this Thesis explores the synthesis–structure–property relationships in Li- and Mn-rich layered oxides, a cost-effective high-capacity material system that shows promise as a positive electrode material for future Li-ion batteries. The compositional and crystallographic diversity of Li- and Mn-rich layered oxides make them particularly susceptible to synthesis-dependent variations and exacerbates structural characterisation. Therefore, understanding how synthetic variations influence their structural and electrochemical properties is a crucial step in realising their potential as positive electrode materials.Even for simple compositions like Li2MnO3, dissimilar crystallographic ordering and particle morphologies are produced depending on whether a solid-state or sol-gel synthesis approach was implemented. Subsequently, due to the higher degree of structural disorder and larger surface area, the sol-gel sample exhibited higher initial electrochemical capacities. The structural features present in these compounds such as cation site-mixing and stacking faults, manifest over varying crystallographic regimes. Hence, complementary characterisation techniques that probe different structural length scales are necessary for an accurate structural characterisation of these compounds. This factor, together with their complex crystallography, have led to contradictory single- and multi-phase structure models being reported for complex Li- and Mn-rich layered oxides. By using a combination of diffraction, spectroscopic techniques and magnetic measurements it was discovered that Li1.2Mn0.54Ni0.13Co0.13O2 can exist in both single- and multi-phase structural forms if synthesised through sol-gel and solid-state methods, respectively. Further studies following the same theme revealed that when synthesised under common laboratory conditions these compounds are metastable. Here, the composition and synthesis play a critical role in the thermodynamic and kinetic factors affecting the resultant phase, domain structure and degree of cationic order. Finally, to encompass all the structural features contained in Li- and Mn-rich layered oxides, a supercell-based structure model for Li- and Mn-rich layered oxides, using Li1.2Mn0.6Ni0.2O2 as an example, is presented. Summing all the work together from the thesis, a critical evaluation of commonly used characterisation techniques is also provided as a guideline for future research in this field.
|
|
| 16. |
- Menon, Ashok S., et al.
(author)
-
Synthetic Pathway Determines the Nonequilibrium Crystallography of Li- and Mn-Rich Layered Oxide Cathode Materials
- 2021
-
In: ACS Applied Energy Materials. - : American Chemical Society (ACS). - 2574-0962. ; 4:2, s. 1924-1935
-
Journal article (peer-reviewed)abstract
- Li- and Mn-rich layered oxides show significant promise as electrode materials for future Li-ion batteries. However, an accurate description of its crystallography remains elusive, with both single-phase solid solution and multiphase structures being proposed for high performing materials such as Li1.2Mn0.54Ni0.13Co0.13O2. Herein, we report the synthesis of single- and multiphase variants of this material through sol-gel and solid-state methods, respectively, and demonstrate that its crystallography is a direct consequence of the synthetic route and not necessarily an inherent property of the composition, as previously argued. This was accomplished via complementary techniques that probe the bulk and local structure followed by in situ methods to map the synthetic progression. As the electrochemical performance and anionic redox behavior are often rationalized on the basis of the presumed crystal structure, clarifying the structural ambiguities is an important step toward harnessing its potential as an electrode material.
|
|
| 17. |
- Naylor, Andrew J., et al.
(author)
-
Depth-dependent oxygen redox activity in lithium-rich layered oxide cathodes
- 2019
-
In: Journal of Materials Chemistry A. - : Royal Society of Chemistry. - 2050-7488. ; 7:44, s. 25355-25368
-
Journal article (peer-reviewed)abstract
- Lithium-rich materials, such as Li1.2Ni0.2Mn0.6O2, exhibit capacities not limited by transition metal redox, through the reversible oxidation of oxide anions. Here we offer detailed insight into the degree of oxygen redox as a function of depth within the material as it is charged and cycled. Energy-tuned photoelectron spectroscopy is used as a powerful, yet highly sensitive technique to probe electronic states of oxygen and transition metals from the top few nanometers at the near-surface through to the bulk of the particles. Two discrete oxygen species are identified, On− and O2−, where n < 2, confirming our previous model that oxidation generates localised hole states on O upon charging. This is in contrast to the oxygen redox inactive high voltage spinel LiNi0.5Mn1.5O4, for which no On− species is detected. The depth profile results demonstrate a concentration gradient exists for On− from the surface through to the bulk, indicating a preferential surface oxidation of the layered oxide particles. This is highly consistent with the already well-established core–shell model for such materials. Ab initio calculations reaffirm the electronic structure differences observed experimentally between the surface and bulk, while modelling of delithiated structures shows good agreement between experimental and calculated binding energies for On−.
|
|
| 18. |
- Ojwang, Dickson O., et al.
(author)
-
Moisture-Driven Degradation Pathways in Prussian White Cathode Material for Sodium-Ion Batteries
- 2021
-
In: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 13:8, s. 10054-10063
-
Journal article (peer-reviewed)abstract
- The high-theoretical-capacity (∼170 mAh/g) Prussian white (PW), NaxFe[Fe(CN)6]y·nH2O, is one of the most promising candidates for Na-ion batteries on the cusp of commercialization. However, it has limitations such as high variability of reported stable practical capacity and cycling stability. A key factor that has been identified to affect the performance of PW is water content in the structure. However, the impact of airborne moisture exposure on the electrochemical performance of PW and the chemical mechanisms leading to performance decay have not yet been explored. Herein, we for the first time systematically studied the influence of humidity on the structural and electrochemical properties of monoclinic hydrated (M-PW) and rhombohedral dehydrated (R-PW) Prussian white. It is identified that moisture-driven capacity fading proceeds via two steps, first by sodium from the bulk material reacting with moisture at the surface to form sodium hydroxide and partial oxidation of Fe2+ to Fe3+. The sodium hydroxide creates a basic environment at the surface of the PW particles, leading to decomposition to Na4[Fe(CN)6] and iron oxides. Although the first process leads to loss of capacity, which can be reversed, the second stage of degradation is irreversible. Over time, both processes lead to the formation of a passivating surface layer, which prevents both reversible and irreversible capacity losses. This study thus presents a significant step toward understanding the large performance variations presented in the literature for PW. From this study, strategies aimed at limiting moisture-driven degradation can be designed and their efficacy assessed.
|
|
| 19. |
- S. Menon, Ashok, et al.
(author)
-
Synthesis–Structure Relationships in Li- and Mn-rich Layered Oxides
-
Other publication (other academic/artistic)abstract
- Li- and Mn-rich layered oxides are promising positive electrode materials for future Li-ion batteries. The coexistence of complex crystallographic features like cation-mixing and stacking faults make them highly susceptible to synthesis-induced crystallographic changes. Consequently, this has resulted in significant variations in the reported structure of these materials and exacerbated the difficulty in understanding the crystallography of these materials. Here, the effect of synthesis methods and annealing parameters on the average structure of three Li- and Mn-rich layered oxides—Li2MnO3, Li1.2Mn0.6Ni0.2O2 and Li1.2Mn0.54Ni0.13Co0.13O2—have been systematically investigated. Each compound is synthesized through two methods using four annealing protocols and the resultant structural changes are studied, to improve our understanding of the synthesis–structure relationships in these materials. Furthermore, synthesis-specific thermodynamic and kinetic factors governing the equilibrium crystallography of each composition are also explored. Improving our understanding of how the synthesis affects the pristine structure of these materials is an important step in developing these material systems for use as future positive electrode materials.
|
|
| 20. |
- Tunes, Matheus A., et al.
(author)
-
From high-entropy alloys to high-entropy ceramics : The radiation-resistant highly concentrated refractory carbide (CrNbTaTiW)C
- 2023
-
In: Acta Materialia. - : Elsevier. - 1359-6454 .- 1873-2453. ; 250
-
Journal article (peer-reviewed)abstract
- High-entropy materials represent the state-of-the-art on the alloy design strategy for future applications in extreme environments. Recent data indicates that high-entropy alloys (HEAs) exhibit outstanding radiation resistance in face of existing diluted alloy counterparts due to suppressed damage formation and evolution. An extension of the HEA concept is presented in this paper towards the synthesis and characterization of novel high-entropy ceramics as emergent materials for application in environments where energetic particle irradiation is a major concern. A novel carbide within the quinary refractory system CrNbTaTiW has been synthesized using magnetron-sputtering. The material exhibited nanocrystalline grains, single-phase crystal structure and C content around 50 at.%. Heavy-ion irradiation with in-situ Transmission Electron Microscopy was used to assess the irradiation response of the new high-entropy carbide (HEC) at 573 K and a comparison with the HEA within the system is made. No displacement damage effects appear within the microstructures of both HEA and HEC up to a dose of 10 displacements-per-atom. Surprisingly, the HEC has not amorphized under the investigated conditions. Xe was implanted in both materials and bubbles nucleated, but smaller sizes compared with conventional nuclear materials shedding light they are potential candidates for use in nuclear energy.
|
|
