| 1. |
- Menon, Ashok S., et al.
(författare)
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A Crystallographic Reinvestigation of Li1.2Mn0.6Ni0.2O2
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Annan publikation (övrigt vetenskapligt/konstnärligt)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.
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| 2. |
- Menon, Ashok S., et al.
(författare)
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Influence of Synthesis Routes on the Crystallography, Morphology, and Electrochemistry of Li2MnO3
- 2020
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 12:5, s. 5939-5950
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Tidskriftsartikel (refereegranskat)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.
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| 3. |
- Menon, Ashok S., et al.
(författare)
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Synthesis-structure relationships in Li- and Mn-rich layered oxides : phase evolution, superstructure ordering and stacking faults
- 2022
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Ingår i: Dalton Transactions. - : Royal Society of Chemistry. - 1477-9226 .- 1477-9234. ; 51:11, s. 4435-4446
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Tidskriftsartikel (refereegranskat)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.
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| 4. |
- Menon, Ashok S., et al.
(författare)
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Synthetic Pathway Determines the Nonequilibrium Crystallography of Li- and Mn-Rich Layered Oxide Cathode Materials
- 2021
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Ingår i: ACS Applied Energy Materials. - : American Chemical Society (ACS). - 2574-0962. ; 4:2, s. 1924-1935
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Tidskriftsartikel (refereegranskat)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.
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| 5. |
- Naylor, Andrew J., et al.
(författare)
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Depth-dependent oxygen redox activity in lithium-rich layered oxide cathodes
- 2019
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Ingår i: Journal of Materials Chemistry A. - : Royal Society of Chemistry. - 2050-7488. ; 7:44, s. 25355-25368
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Tidskriftsartikel (refereegranskat)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−.
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| 6. |
- S. Menon, Ashok, et al.
(författare)
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Synthesis–Structure Relationships in Li- and Mn-rich Layered Oxides
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Annan publikation (övrigt vetenskapligt/konstnärligt)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.
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